U.S. patent application number 10/361591 was filed with the patent office on 2003-12-04 for catalysts containing n-pyrrolyl substituted nitrogen donors.
This patent application is currently assigned to Eastman Chemical Company. Invention is credited to Barrett, Anthony Gerard Martin, Coates, Geoffrey William, Killian, Christopher Moore, Lavoie, Gino Georges, MacKenzie, Peter Borden, Moody, Leslie Shane, Pearson, Jason Clay, Ponasik, James Allen JR., Smith, Thomas William.
Application Number | 20030225228 10/361591 |
Document ID | / |
Family ID | 24251989 |
Filed Date | 2003-12-04 |
United States Patent
Application |
20030225228 |
Kind Code |
A1 |
Moody, Leslie Shane ; et
al. |
December 4, 2003 |
Catalysts containing N-pyrrolyl substituted nitrogen donors
Abstract
Catalyst compositions useful for the polymerization or
oligomerization of olefins are disclosed. Certain of the catalyst
compositions comprise N-pyrrolyl substituted nitrogen donors. Also
disclosed are processes for the polymerization or oligomerization
of olefins using the catalyst compositions.
Inventors: |
Moody, Leslie Shane;
(Johnson City, TN) ; MacKenzie, Peter Borden;
(Kingsport, TN) ; Killian, Christopher Moore;
(Gray, TN) ; Lavoie, Gino Georges; (Kingsport,
TN) ; Ponasik, James Allen JR.; (Blountville, TN)
; Smith, Thomas William; (Kingsport, TN) ;
Pearson, Jason Clay; (Kingsport, TN) ; Barrett,
Anthony Gerard Martin; (Chiswick, GB) ; Coates,
Geoffrey William; (Ithaca, NY) |
Correspondence
Address: |
Nhat D. Phan
BURNS, DOANE, SWECKER & MATHIS, L.L.P.
P.O. Box 1404
Alexandria
VA
22313-1404
US
|
Assignee: |
Eastman Chemical Company
|
Family ID: |
24251989 |
Appl. No.: |
10/361591 |
Filed: |
February 11, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10361591 |
Feb 11, 2003 |
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09563812 |
May 3, 2000 |
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6545108 |
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09563812 |
May 3, 2000 |
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09507492 |
Feb 18, 2000 |
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6559091 |
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60121135 |
Feb 22, 1999 |
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60123276 |
Mar 8, 1999 |
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60123385 |
Mar 8, 1999 |
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60130503 |
Apr 23, 1999 |
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60145277 |
Jul 26, 1999 |
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Current U.S.
Class: |
526/172 ;
502/150; 502/152; 502/155; 502/162; 502/167 |
Current CPC
Class: |
C08F 4/659 20130101;
C08F 10/00 20130101; C07C 233/56 20130101; C07D 209/48 20130101;
C08F 110/02 20130101; C07C 251/20 20130101; C07C 211/52 20130101;
C08F 10/00 20130101; C07D 319/12 20130101; C08F 10/00 20130101;
C08F 10/00 20130101; C08F 110/14 20130101; C07D 339/08 20130101;
C08F 10/00 20130101; C07C 2603/20 20170501; C08F 210/16 20130101;
C08F 2500/02 20130101; C08F 2500/02 20130101; C08F 4/64048
20130101; C08F 4/7027 20130101; C08F 2500/02 20130101; C08F 2500/09
20130101; C08F 2500/09 20130101; C08F 4/659 20130101; C08F 4/65916
20130101; C08F 2500/09 20130101; C08F 2500/03 20130101; C08F 4/7004
20130101; C08F 2500/03 20130101; C08F 2500/09 20130101; C08F
2500/03 20130101; C08F 2500/04 20130101; C08F 210/14 20130101; C08F
2500/03 20130101; C08F 4/7022 20130101; C08F 2500/04 20130101; C08F
2500/03 20130101; C08F 2500/09 20130101; C08F 4/80 20130101; C08F
2500/10 20130101; C08F 2500/02 20130101; C08F 4/64072 20130101;
C08F 2500/03 20130101; C08F 4/7042 20130101; C08F 2500/09 20130101;
C08F 210/14 20130101; C08F 4/7021 20130101; C08F 2500/03 20130101;
C08F 2500/02 20130101; C08F 210/16 20130101; C08F 4/7006 20130101;
C07F 17/00 20130101; C07C 2531/22 20130101; C08F 10/00 20130101;
C08F 110/02 20130101; C08F 110/02 20130101; C08F 10/00 20130101;
C07D 207/34 20130101; C08F 10/00 20130101; C07D 265/30 20130101;
C08F 210/16 20130101; C08F 110/14 20130101; C07C 257/14 20130101;
C08F 10/00 20130101; C08F 10/00 20130101; C08F 110/02 20130101;
C07C 251/08 20130101; C08F 4/65912 20130101; C08F 10/00 20130101;
C08F 110/02 20130101; C08F 110/02 20130101; C07D 409/14 20130101;
C07D 207/32 20130101; C07D 295/30 20130101; C07D 207/50 20130101;
C07F 9/58 20130101; C07F 9/572 20130101; C07F 15/045 20130101; C07D
401/14 20130101; C08F 110/02 20130101; C07C 2/32 20130101; C07F
7/0812 20130101; C08F 10/00 20130101; C07F 7/003 20130101; C07C
257/02 20130101; C08F 110/14 20130101 |
Class at
Publication: |
526/172 ;
502/150; 502/152; 502/155; 502/162; 502/167 |
International
Class: |
B01J 031/00; C08F
004/06 |
Claims
We claim:
1. A catalyst composition for the polymerization of olefins,
comprising a Ti, Zr, or Hf complex of a dianionic bidentate ligand,
wherein at least one of the donor atoms of the ligand is a nitrogen
atom substituted by a 1-pyrrolyl or substituted 1-pyrrolyl group;
wherein the remaining donor atoms of the ligand are selected from
the group consisting of C, N, P, As, O, S, and Se.
2. The catalyst composition according to claim 1, wherein the metal
complex is a compound of formula XIV: 135wherein: M is Zr or Ti;
D.sup.1, D.sup.2, and G collectively comprise the dianionic
bidentate ligand; D.sup.1 and D .sup.2 are monodentate donors
linked by a bridging group G, wherein at least one of D.sup.1 and
D.sup.2 is ligated to the metal M by a nitrogen atom substituted by
a 1-pyrrolyl or a substituted 1-pyrrolyl group; T is H,
hydrocarbyl, substituted hydrocarbyl, or other group capable of
inserting an olefin; and X.sup.- is a weakly coordinating
anion.
3. The catalyst composition according to claim 2, wherein the
dianionic bidentate ligand is selected from Set 7, or a tautomer
thereof: 136137wherein: R.sup.3a-h are each independently H,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl,
fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
in addition, any two of R.sup.3a-h may be linked by a bridging
group; and G.sup.4 is a divalent bridging hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl.
4. The catalyst composition according to claim 1, which is attached
to a solid support.
5. A process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of
claim 1, and optionally an aluminum or boron-centered Lewis
acid.
6. A catalyst composition for the polymerization of olefins,
comprising a Ti, Zr, or Hf complex of a monoanionic bidentate
ligand, wherein at least one of the donor atoms of the ligand is a
nitrogen atom substituted by a 1-pyrrolyl or substituted 1-pyrrolyl
group; wherein the remaining donor atoms of the ligand are selected
from the group consisting of C, N, P, As, O, S, and Se.
7. The catalyst composition according to claim 6, optionally
further comprising a second compound Y, wherein the metal complex
is a compound of formula XV: 138wherein: M is Ti, Zr, or Hf; m and
n are integers, defined as follows: when M is Ti and m is 1, n is 2
or 3; when M is Ti and m is 2, n is 1 or 2; when M is Zr and m is
1, n is 3; when M is Zr and m is 2, n is 2; when M is Hf, m is 2
and n is 2; R.sup.3a-i are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, silyl, boryl, fluoro,
chloro, bromo, or nitro, with the proviso that R.sup.3e is other
than halogen or nitro; in addition, any two of R.sup.3a-i on the
same or different N-pyrrol-1-yliminophenoxide ligand may be linked
by a bridging group; Z is H, halogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected
substituted hydrocarbyl, silyl, allyl, benzyl, alkoxy, carboxylate,
amido, nitro, or trifluoromethane sulfonyl; each Z may be the same
or different and plural Z may be taken together to form sulfate,
oxalate, or another divalent group; Y is selected from the group
consisting of a neutral Lewis acid capable of abstracting Z.sup.-
to form a weakly coordinating anion, a cationic Lewis acid whose
counterion is a weakly coordinating anion, and a Bronsted acid
whose conjugate base is a weakly coordinating anion; and when n is
2 or 3, the metal complex may be a salt, comprising a Ti, Zr, or Hf
centered cation with one of the groups Z.sup.- being a weakly
coordinating anion.
8. The catalyst composition according to claims 6 or 7, wherein the
monoanionic bidentate ligand is selected from Set 8, or a tautomer
thereof: 139140wherein: R.sup.2x is H, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl; and R.sup.3a-d,f-i are each
independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo,
cyano, or nitro; in addition, any two of R.sup.3a-d,f-i may be
linked by a bridging group.
9. The catalyst composition according to claim 6, which is attached
to a solid support.
10. A process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of
claim 6, and optionally a second compound Y; wherein Y is selected
from the group consisting of (i) a neutral Lewis acid which is
capable of reacting with said Ti, Zr, or Hf complex to form a salt
comprising a weakly coordinating anion, (ii) a cationic Lewis acid
whose counterion is a weakly coordinating anion, and (iii) a
Bronsted acid whose conjugate base is a weakly coordinating
anion.
11. A catalyst composition for the polymerization of olefins,
comprising a Cr, Mo, or W complex of a monodentate dianionic
ligand, wherein at least one of the donor atoms of the ligand is a
nitrogen atom substituted by a 1-pyrrolyl or substituted 1-pyrrolyl
group; wherein the remaining donor atoms of the ligand are selected
from the group consisting of C, N, P, As, O, S, and Se.
12. The catalyst composition according to claim 11, optionally
further comprising a second compound Y, wherein the metal complex
is a compound of formula XVI: 141wherein: M is Cr, Mo, or W;
D.sup.1 and D.sup.2 are monodentate dianionic ligands that may be
linked by a bridging group to collectively comprise a bidentate
tetraanionic ligand; Z.sup.1a and Z.sup.1b are each, independently
H, halogen, hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, silyl, allyl, benzyl, alkoxy, carboxylate, amido,
nitro, trifluoromethanesulfonyl, or may be taken together to form
sulfate, oxalate, or another divalent group; Y is selected from the
group consisting of a neutral Lewis acid capable of abstracting
(Z.sup.1a).sup.- or (Z.sup.1b).sup.- to form a weakly coordinating
anion, a cationic Lewis acid whose counterion is a weakly
coordinating anion, and a Bronsted acid whose conjugate base is a
weakly coordinating anion; and wherein the metal complex may be a
salt, comprising a Cr, Mo, or W centered cation with one of
(Z.sup.1a).sup.- or (Z.sup.1b).sup.- being a weakly coordinating
anion.
13. The catalyst composition according to claim 12, wherein the
metal is Cr and the monodentate dianionic ligand is selected from
Set 9, or a tautomer thereof: 142143wherein: R.sup.3a-d are each
independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo,
cyano, or nitro; in addition, any two of R.sup.3a-d may be linked
by a bridging group.
14. The catalyst composition according to claim 11, which is
attached to a solid support.
15. A process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of
claims 11, and optionally a second compound Y; wherein Y is
selected from the group consisting of (i) a neutral Lewis acid
which is capable of reacting with said Cr, Mo, or W complex to to
form a salt comprising a weakly coordinating anion, (ii) a cationic
Lewis acid whose counterion is a weakly coordinating anion, and
(iii) a Bronsted acid whose conjugate base is a weakly coordinating
anion.
16. A catalyst composition for the polymerization of olefins,
comprising a V, Nb, or Ta complex of a monodentate dianionic
ligand, wherein at least one of the donor atoms of the ligand is a
nitrogen atom substituted by a 1-pyrrolyl or substituted 1-pyrrolyl
group; wherein the remaining donor atoms of the ligand are selected
from the group consisting of C, N, P, As, O, S, and Se.
17. The catalyst composition according to claim 16, optionally
further comprising a second compound Y wherein the metal complex is
a compound of formula XVII: 144wherein: M is V, Nb, or Ta;
R.sup.3a-d are each independently H, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected
substituted hydrocarbyl, silyl, boryl, fluoro, chloro, bromo, or
nitro; in addition, any two of R.sup.3a-d may be linked by a
bridging group; T.sup.1b is hydrocarbyl, substituted hydrocarbyl,
heteroatom connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, cyclopentadienyl, substituted cyclopentadienyl,
N(hydrocarbyl).sub.2, O(hydrocarbyl), or halide; Z.sup.1a and
Z.sup.1b are each, independently H, halogen, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, silyl, allyl, benzyl,
alkoxy, carboxylate, amido, nitro, trifluoromethane sulfonyl, or
may be taken together to form sulfate, oxalate, or another divalent
group; Y is selected from the group consisting of a neutral Lewis
acid capable of abstracting (Z.sup.1a).sup.- or (Z.sup.1b).sup.- to
form a weakly coordinating anion, a cationic Lewis acid whose
counterion is a weakly coordinating anion, and a Bronsted acid
whose conjugate base is a weakly coordinating anion; and the metal
complex may be a salt, comprising a V, Nb, or Ta centered cation
with one of (Z.sup.1a).sup.- or (Z.sup.1b).sup.- being a weakly
coordinating anion.
18. The catalyst composition according to claim 17, wherein the
monodentate dianionic ligand is selected from Set 10, or a tautomer
thereof, and T.sup.1b is a N(hydrocarbyl).sub.2 group:
145146wherein: R.sup.3a-d are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-d may be linked by a bridging group.
19. The catalyst composition according to claim 16, wherein M is
V.
20. The catalyst composition according to claims 16, which is
attached to a solid support.
21. A process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of
claims 16, and optionally a second compound Y; wherein Y is
selected from the group consisting of (i) a neutral Lewis acid
which is capable of reacting with said V, Nb, or Ta complex to to
form a salt comprising a weakly coordinating anion, (ii) a cationic
Lewis acid whose counterion is a weakly coordinating anion, and
(iii) a Bronsted acid whose conjugate base is a weakly coordinating
anion.
22. A catalyst composition for the polymerization of olefins,
comprising (i) a cationic Ti, Zr or Hf complex of a mono- or
dianionic, nitrogen donor ligand, wherein said nitrogen donor is
substituted by a 1-pyrrolyl or substituted 1-pyrrolyl group and is
linked by a bridging group to a cyclopentadienyl,
phosphacyclopentadienyl, pentadienyl, 6-oxacyclohexadienyl, or
borataaryl group which is also ligated to said metal, and
optionally, (ii) an aluminum or boron-centered Lewis acid.
23. The catalyst composition according to claim 22, wherein the
mono- or dianionic, nitrogen donor ligand is selected from Set 11,
or a tautomer thereof: 147148149wherein: R.sup.2a is H,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl,
boryl, or ferrocenyl; R.sup.3a-h are each independently H,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl,
fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
in addition, any two of R.sup.3a-h may be linked by a bridging
group; R.sup.4a is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl; and G is a divalent bridging hydrocarbyl, substituted
hydrocarbyl, silyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl.
24. The catalyst composition according to claim 22, wherein said
composition is attached to a solid support.
25. A process for the polymerization olefins, which comprises
contacting one or more olefins with the catalyst composition of
claims 22.
26. A process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits improved thermal
stability, and wherein said metal complex comprises a bidentate or
variable denticity ligand comprising one or two nitrogen donor atom
or atoms independently substituted by an aromatic or heteroaromatic
ring, wherein the ortho positions of said ring(s) are substituted
by groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
27. A process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits improved stability in
the presence of an amount of hydrogen effective to achieve chain
transfer, and wherein said metal complex comprises a bidentate or
variable denticity ligand comprising one or two nitrogen donor atom
or atoms independently substituted by an aromatic or heteroaromatic
ring, wherein the ortho positions of said ring(s) are substituted
by groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
28. A process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits either improved thermal
stability, or exhibits improved stability in the presence of an
amount of hydrogen effective to achieve chain transfer, or both,
wherein said metal complex comprises a bidentate or variable
denticity ligand comprising one or two nitrogen donor atom or atoms
independently substituted by an aromatic or heteroaromatic ring,
wherein at least one of the ortho positions of at least one of said
aromatic or heteroaromatic rings is substituted by an aryl or
heteroaryl group which is capable of reversibly forming an agostic
bond to said Group 8-10 transition metal under olefin
polymerization reaction conditions.
29. A process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits either improved thermal
stability, or exhibits improved stability in the presence of an
amount of hydrogen effective to achieve chain transfer, or both,
wherein said composition comprises a bidentate or variable
denticity ligand comprising one or two nitrogen donor atom or atoms
independently substituted by an aromatic or heteroaromatic ring,
wherein the ortho positions of said ring(s) are substituted by
groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
30. The process according to claims 26, 27, 28, or 29, wherein the
ortho positions of said aromatic or heteroaromatic ring are
substituted by aryl or heteroaryl groups.
31. The process according to claims 26, 27, 28, 29, or 30, wherein
the half-life for thermal decomposition is greater than 10 min in
solution at 60.degree. C., 200 psig ethylene, and the average
apparent catalyst activity of said catalyst is greater than 100,000
mol C.sub.2H.sub.4/mol catalyst/h.
32. The process according to claim 31, wherein the half-life for
thermal decomposition is greater than 20 minutes, and the average
apparent catalyst activity of said catalyst is greater than
1,000,000 mol C.sub.2H.sub.4/mol catalyst/h.
33. The process according to claim 31, wherein the half-life for
thermal decomposition of said catalyst is greater than 30 min.
34. The process according to claim 31, 32, or 33 wherein the Group
8-10 transition metal is Ni.
35. The process according to claims 26, 27, 28, 29, or 30, wherein
the process temperature is between about 60 and about 150.degree.
C.
36. The process according to claim 35, wherein the process
temperature is between about 100 and about 150.degree. C.
37. The process according to claims 26, 27, 28, 29, or 30, wherein
the bidentate or variable denticity ligand is selected from Set 12:
150wherein: R.sup.6a and R.sup.6b are each independently an
aromatic or heteroaromatic ring wherein the ortho positions of said
ring(s) are substituted by groups other than H or alkyl; provided
that at least one of the ortho positions of at least one of said
aromatic or heteroaromatic rings is substituted by an aryl or
heteroaryl group; and R.sup.2x and R.sup.2y are each independently
H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, or heteroatom connected substituted hydrocarbyl, and
may be linked by a bridging group.
38. The process according to claim 37, wherein the Group 8-10
transition metal is nickel and the bidentate or variable denticity
ligand is selected from Set 13: 151wherein: R.sup.7a-d are groups
other than H or alkyl; provided that at least one of R.sup.7a-d is
an aryl or heteroaryl group; R.sup.2x and R.sup.2y are each
independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl, and may be linked by a bridging group; and R.sup.3a-f
are each independently H, hydrocarbyl, substituted hydrocarbyl,
heteroatom connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo,
cyano, or nitro; in addition, any two of R.sup.3a-f may be linked
by a bridging group.
39. The process according to claim 38, wherein the composition is
attached to a solid support.
40. The process according to claim 39, wherein the process
temperature is between about 60 and about 100.degree. C.
41. A process for olefin polymerization comprising: contacting one
or more olefin monomers with a single site catalyst attached to a
solid support, wherein said catalyst comprises a cationic Group
4-11 transition metal complex and a weakly coordinating
counteranion, and wherein said catalyst is introduced into a gas
phase olefin polymerization reactor in an inactive form which is
activated by reaction with a second compound Y.sup.1 to form said
catalyst in said reactor; wherein Y.sup.1 is a volatile, Lewis
acidic, metal hydrocarbyl.
42. The process according to claim 41, wherein said transition
metal is selected from the group consisting of Ti, Zr and Hf.
43. The process according to claim 41, wherein said transition
metal is selected from the group consisting of Ni, Co, and Fe.
44. The process according to claims 41, 42, or 43, wherein Y.sup.1
is a trialkylaluminum or dialkylzinc.
45. The process according to claim 44, wherein Y.sup.1 is
trimethylaluminum.
46. The process according to claim 41, wherein (i) said inactive
form of said catalyst is selected from Set 14, (ii) said weakly
coordinating counteranion is either formed by reaction of said
inactive form of said catalyst with Y.sup.1 , or is selected from
the group consisting of
B(C.sub.6F.sub.5).sub.4.sup.-,B(3,5-bis(trifluoromethyl)phenyl).sub.4.sup-
.-,
[(C.sub.6F.sub.5).sub.3B-(imidazole)-B(C.sub.6F.sub.5).sub.3].sup.-,
BF.sub.4.sup.-, and
[(C.sub.6F.sub.5).sub.3B--CN--B(C.sub.6F.sub.5).sub.3- ].sup.-, and
(iii) Y.sup.1 is trimethylaluminum; 152153154155156wherein:
R.sup.2a,b,x,y are each independently H, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected
substituted hydrocarbyl, silyl, boryl, or ferrocenyl; in addition,
any two of R.sup.2a,b,x,y may be linked by a bridging group;
R.sup.3a-m are each independently H, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected
substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro,
bromo, cyano, or nitro; in addition, any two of R.sup.3a-m may be
linked by a bridging group; A.sup.1 is halide or a monoanionic
group which is capable of reacting with Y.sup.1 to generate an
active olefin polymerization catalyst, provided that in the absence
of Y.sup.1 , A.sup.1 is such that said inactive form of said single
site catalyst is at least 10 times less active as a catalyst for
olefin polymerization than said active olefin polymerization
catalyst; A.sup.2 and A.sup.3 are each independently hydrocarbyl,
halide, O(hydrocarbyl) or O(substituted hydrocarbyl), provided that
at least one of A.sup.2 and A.sup.3 is capable of being abstracted
by Y.sup.1 to form a weakly coordinating counteranion, and the
other is either capable of inserting an olefin to initiate polymer
chain growth, or is capable of being exchanged with a group on
Y.sup.1 which can then initiate chain growth; G and G.sup.4 are
divalent bridging hydrocarbyl, substituted hydrocarbyl, silyl,
heteroatom connected hydrocarbyl, or heteroatom connected
substituted hydrocarbyl; Y.sup.1 is a trialkylaluminum or
dialkylzinc; and X.sup.- is a weakly coordinating anion.
47. The process according to claims 26, 27, 28, 29, or 30, wherein
said catalyst is introduced into a gas phase olefin polymerization
reactor in an inactive form attached to a solid support, and
wherein said catalyst is activated by a second compound Y.sup.1 in
said reactor.
48. The process according to claim 47, wherein said bidentate or
variable denticity ligand is selected from Set 15; 157wherein:
R.sup.6a and R.sup.6b are each independently an aromatic or
heteroaromatic ring wherein the ortho positions of said ring(s) are
substituted by groups other than H or alkyl; provided that at least
one of the ortho positions of at least one of said aromatic or
heteroaromatic rings is substituted by an aryl or heteroaryl group;
and R.sup.2x and R.sup.2y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl, and may be linked by
a bridging group.
49. The process according to claim 48, wherein (i) said Group 8-10
transition metal is nickel, (ii) said weakly coordinating
counteranion is either formed by reaction of said inactive form of
said catalyst with a volatile second compound Y.sup.1, or is
selected from the group consisting of
B(C.sub.6F.sub.5).sub.4.sup.-, B(3,5-bis(trifluoromethyl)ph-
enyl).sub.4.sup.-,
[(C.sub.6F.sub.5).sub.3B-(imidazole)-B(C.sub.6F.sub.5).-
sub.3].sup.-, BF.sub.4.sup.-, and
[(C.sub.6F.sub.5).sub.3B--CN--B(C.sub.6F- .sub.5).sub.3].sup.-,
(iii) Y.sup.1 is trimethylaluminum, and (iv) said bidentate or
variable denticity ligand is selected from Set 16; 158wherein:
R.sup.7a-d are groups other than H or alkyl; provided that at least
one of R.sup.7a-d is an aryl or heteroaryl group; R.sup.2x and
R.sup.2y are each independently H, hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl, and may be linked by a bridging
group; and R.sup.3a-f are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-f may be linked by a bridging group.
50. The process according to claims 26, 27, 28, 29, or 30, wherein
said aromatic or heteroaromatic ring is selected from Set 17;
159160wherein: R.sup.7a,b are groups other than H or alkyl;
provided that at least one of R.sup.7a,b is an aryl or heteroaryl
group; R.sup.3a-k are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-k may be linked by a bridging group; and E.sup.5 is O,
S, Se, or NR.sup.3b.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to catalyst
compositions useful for the polymerization or oligomerization of
olefins, and to processes using the catalyst compositions. Certain
of these catalyst compositions comprise N-pyrrolyl substituted
nitrogen donors.
BACKGROUND OF THE INVENTION
[0002] Olefin polymers are used in a wide variety of products, from
sheathing for wire and cable to film. Olefin polymers are used, for
instance, in injection or compression molding applications, in
extruded films or sheeting, as extrusion coatings on paper, for
example photographic paper and digital recording paper, and the
like. Improvements in catalysts have made it possible to better
control polymerization processes and, thus, influence the
properties of the bulk material. Increasingly, efforts are being
made to tune the physical properties of plastics for lightness,
strength, resistance to corrosion, permeability, optical
properties, and the like, for particular uses. Chain length,
polymer branching and functionality have a significant impact on
the physical properties of the polymer. Accordingly, novel
catalysts are constantly being sought in attempts to obtain a
catalytic process for polymerizing olefins which permits more
efficient and better-controlled polymerization of olefins.
[0003] Conventional polyolefins are prepared by a variety of
polymerization techniques, including homogeneous liquid phase, gas
phase, and slurry polymerization. Certain transition metal
catalysts, such as those based on titanium compounds (e.g.
TiCl.sub.3 or TiCl.sub.4) in combination with organoaluminum
cocatalysts, are used to make linear and linear low-density
polyethylenes as well as poly-.alpha.-olefins such as
polypropylene. These so-called "Ziegler-Natta" catalysts are quite
sensitive to oxygen and are ineffective for the copolymerization of
nonpolar and polar monomers. Following the early discovery of
Ziegler-Natta catalysts, there has been intense recent interest in
the development and study of homogeneous early transition metal
(Group 4-6) catalysts for the polymerization of olefins. These
well-defined Ziegler-Natta catalysts, are receiving increasing
commercial attention. Recent advances in Group 4-6 single-site
olefin polymerization catalysis include the following.
[0004] The following documents describe the use of
monocyclopentadienyl amido titanium complexes for the
polymerization of olefins as described by J. M. Canich, EP 420,436
(1991) and Stevens et al., EP 416,815 (1991). Waymouth et al.,
Science, 1995, 267, 217, disclose the use of oscillating catalysts
based on unbridged substituted indenyl complexes of zirconium.
Mitsui Chemicals Inc. disclose the use of nitrogen/oxygen chelate
ligands on Group 4-6 transition metals as catalysts for the
polymerization of olefins, EP 874,005 (1998). McConville et al., J.
Am. Chem. Soc., 1996, 118, 10008-10009, describe the living
polymerization of olefins with chelating diamido complexes of Ti
and Zr. Schrock et al., J. Am. Chem. Soc., 1997, 119, 3830, J. Am.
Chem. Soc., 1999, 121, 5797, also describe catalysts comprising
chelating diamido complexes of Ti and Zr. DSM (WO 94/14854 and EP 0
532 098 A1), BP (EP 0 641 804 A2 and EP 0 816 384 A2), Chevron (WO
94/11410), and Exxon (WO 94/01471) describe the use of Group 4-6
imido catalysts for the polymerization of olefins. Jordan et al.,
WO 98/40421, disclose the use of novel cationic Group 13 complexes
incorporating bidentate ligands as olefin polymerization
catalysts.
[0005] Recent advances in Group 8-10 catalysts for the
polymerization of olefins include the following.
[0006] European Patent Application No. 381,495 describes the
polymerization of olefins using palladium and nickel catalysts,
which contain selected bidentate phosphorous containing
ligands.
[0007] U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606,
and 5,175,326, describes the conversion of ethylene to polyethylene
using anionic phosphorous, oxygen donors ligated to Ni(II). The
polymerization reactions were run between 25 and 100.degree. C.
with modest yields, producing linear polyethylene having a
weight-average molecular weight ranging between 8K and 350 K. In
addition, Klabunde describes the preparation of copolymers of
ethylene and functional group containing monomers.
[0008] M. Peuckert et al., Organomet. 1983, 2(5), 594, disclose the
oligomerization of ethylene using phosphine/carboxylate donors
ligated to Ni(II), which showed modest catalytic activity (0.14 to
1.83 TO/s). The oligomerizations were carried out at 60 to
95.degree. C. and 10 to 80 bar ethylene in toluene, to produce
.alpha.-olefins.
[0009] R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138,
describes the oligomerization of ethylene using phosphine,
sulfonate donors ligated to Ni(II). These complexes show catalyst
activities approximately 15 times greater than those reported with
phosphine, carboxylate analogs.
[0010] W. Keim et al., Angew. Chem. Int. Ed. Eng., 1981, 20, 116,
and V. M. Mohring et al., Angew. Chem. Int. Ed. Eng., 1985, 24,
1001, disclose the polymerization of ethylene and the
oligomerization of .alpha.-olefins with aminobis(imino)phosphorane
nickel catalysts.
[0011] Wilke, Angew. Chem. Int. Ed. Engl., 1988, 27, 185, describes
a nickel allyl phosphine complex for the polymerization of
ethylene.
[0012] K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl.,
1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of
bis(ylide) nickel complexes, used to polymerize ethylene to provide
high molecular weight linear polyethylene.
[0013] L. K. Johnson et al., WO 96/23010; U.S. Pat. Nos. 5,866,663;
5,886,224; 5,891,963; 5,880,323; and 5,880,241; disclose the
polymerization of olefins using cationic nickel, palladium, iron,
and cobalt complexes containing diimine and bisoxazoline ligands.
This document also describes the polymerization of ethylene,
acyclic olefins, and/or selected cyclic olefins and optionally
selected unsaturated acids or esters such as acrylic acid or alkyl
acrylates to provide olefin homopolymers or copolymers. L. K.
Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe the
polymerization of olefins such as ethylene, propylene, and 1-hexene
using cationic .alpha.-diimine-based nickel and palladium
complexes. These catalysts have been described to polymerize
ethylene to high molecular weight branched polyethylene. In
addition to polymerizing ethylene, the Pd complexes act as
catalysts for the polymerization and copolymerization of olefins
and methyl acrylate.
[0014] WO 97/02298 discloses the polymerization of olefins using a
variety of neutral N, O, P, or S donor ligands, in combination with
a nickel(0) compound and an acid.
[0015] Eastman Chemical Company has recently described in a series
of patent applications (WO 98/40374, WO 98/37110, WO 98/47933, and
WO 98/40420) several new classes of Group 8-10 transition metal
catalysts for the polymerization of olefins. Also described are
several new polymer compositions derived from epoxybutene and
derivatives thereof.
[0016] Brown et al., WO 97/17380, WO 97/48777, WO 97/48739, and WO
97/48740, describe the use of Pd .alpha.-diimine catalysts for the
polymerization of olefins including ethylene in the presence of air
and water.
[0017] Fink et al., U.S. Pat. No. 4,724,273, describe the
polymerization of .alpha.-olefins using aminobis(imino)phosphorane
nickel catalysts and the compositions of the resulting
poly(.alpha.-olefins).
[0018] Recently, Vaughan et al., WO 97/48736, Denton et al., WO
97/48742, and Sugimura et al., WO 97/38024, describe the
polymerization of ethylene using silica supported .alpha.-diimine
nickel catalysts.
[0019] Phillips, EP 884,331, discloses the use of nickel
.alpha.-diimine catalysts for the polymerization of ethylene in
their slurry loop process.
[0020] Neutral nickel catalysts for the polymerization of olefins
are described in WO 98/30610; WO 98/30609; WO 98/42665; and WO
98/42664.
[0021] Highly active iron and cobalt catalysts ligated by pyridine
bis(imines) for the polymerization and oligomerization of ethylene
have been independently described by the University of North
Carolina-Chapel Hill (WO 99/02472), DuPont (WO 98/27124), BP
Chemical and Imperial College (WO 99/12981).
[0022] Also recently, Canich et al., WO 97/48735, and Mecking, DE
19707236 A1, describe the use of mixed .alpha.-diimine catalysts
with Group 4 transition metal catalysts for the polymerization of
olefins. Additional recent developments are described by Sugimura
et al. in JP 96-84344 and JP 96-84343, by Yorisue et al. in JP
96-70332, by McLain et al. in WO 98/03559, by Weinberg et al. in WO
98/03521, by Wang et al. in WO 99/09078, by Coughlin in WO
99/10391, and by Matsunaga et al. in WO 97/48737.
[0023] Notwithstanding these advances in non-Ziegler-Natta
catalysis, there remains a need for new transition metal catalysts,
particularly those which are more thermally stable, allow for new
polymer microstructures, or are more functional group tolerant. In
addition, there is a need for novel methods of polymerizing olefins
employing such catalysts, and for the novel polymers which
result.
SUMMARY OF THE INVENTION
[0024] A number of transition metal complexes containing nitrogen
donor ligands have proven valuable as catalysts for olefin
polymerization. A key feature of many of these catalysts is the
introduction of steric hindrance through the use of a substituted
aryl group on the ligated nitrogen. The steric bulk associated with
such fragments tends to suppress premature chain transfer and may,
in some cases, stabilize the catalyst towards decomposition,
increase the catalyst activity, act to modify the polymer
microstructure, or otherwise have beneficial effects.
[0025] We have found that catalysts comprising 1-pyrrolyl or
substituted 1-pyrrolyl substituted N-donor ligands represent a
highly effective and versatile new class of olefin polymerization
catalysts. Indeed, we have discovered that the use of such
fragments represents a new polyolefin catalyst design principle,
wherein aryl substituted nitrogen donors of existing polyolefin
catalysts are replaced by 1-pyrrolyl substituted nitrogen donors,
as shown in Scheme I, where M is Sc, a Group 4-10 transition metal,
Al or Ga, and
[0026] R.sup.3a-i are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro, and where any two of
R.sup.3a-i may be linked by a bridging group. 1
[0027] This strategy is expected to apply to essentially all
previously reported olefin polymerization and oligomerization
catalysts incorporating an aryl-substituted nitrogen donor ligand.
Thus, catalysts reported in U.S. Pat. Nos. 5,866,663; 5,886,224;
5,891,963; 5,880,323; 5,880,241, and in WO 96/23010, WO 99/10391,
WO 99/05189, WO 98/56832, WO 98/03559, WO 98/47934, W097/02298, WO
98/30609, WO 98/42665, WO 98/42664, WO 98/47933, WO 98/40420, WO
98/40374, EP 420,436 (1991), EP 416,815 (1991), Science, 1995, 267,
217, EP 874,005(1998), J. Am. Chem. Soc., 1996, 118, 10008-10009,
WO 94/14854, EP 0 532 098 A1, EP 0 641 804 A2, EP 0 816 384 A2, WO
94/11410, WO 94/01471, WO 98/40421, and Chem. Commun., 1998, 313,
which have their aryl substituted nitrogen donor fragment or
fragments replaced by a N-pyrrol-1-yl or substituted N-pyrrol-1-yl
nitrogen donor fragment or fragments are all contemplated to be
within the scope of our invention. All U.S. Patents referred to
herein are incorporated by reference. Also provided are certain
ligands, as depicted in Sets 1-17 below, which are useful as
intermediates in the preparation of the polyolefin polymerization
and oligomerization catalyst compositions of the present
invention.
[0028] While catalysts containing N-donors substituted by
pyrrol-1-yl or substituted pyrrol-1-yl groups represent a preferred
class, N-donor ligands substituted by other types of
--NR.sup.2aR.sup.2b groups, where R.sup.2a and R.sup.2b are each
independently H, hydrocarbyl, substituted hydrocarbyl, silyl,
boryl, or ferrocenyl, and where R.sup.2a and R.sub.2b may be
connected to form a ring, are also expected to be useful in
constituting olefin polymerization catalysts. Examples of cyclic
--NR.sup.2aR.sup.2b groups are shown in Scheme X, wherein
R.sup.3a-d are as defined above, and include
2,6-dialkyl-4-oxo-4H-pyridin-1-yl, 2,5-dialkyl-1-imidazolyl, and
2,6-dimethyl-3-methoxycarbonyl-4-oxo-4H-pyr- idin-1-yl groups.
2
[0029] It is expected that those cyclic --NR.sup.2aR.sup.2b groups
wherein the electronic characteristics of the nitrogen of the
--NR.sup.2aR.sup.2b group are similar to those of a 1-pyrrolyl
nitrogen will be especially useful. Catalysts containing N-donors
substituted by cyclic --PR.sup.4aR.sup.4b groups (wherein R.sup.4a
and R.sup.4b are each independently hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl, and wherein R.sup.4a and
R.sup.4b may be linked by a bridging group), including especially
1-phospholyl or substituted 1-phospholyl groups, are similarly
expected to be useful in constituting olefin polymerization
catalysts.
DETAILED DESCRIPTION OF THE INVENTION
[0030] Thus, in a first aspect, this invention relates to a
catalyst composition for the polymerization or oligomerization of
olefins, comprising a metal complex ligated by a monodentate,
bidentate, tridentate, or tetradentate ligand, wherein at least one
of the donor atoms of the ligand is a nitrogen atom substituted by
a 1-pyrrolyl or substituted 1-pyrrolyl group; wherein:
[0031] the remaining donor atoms of the ligand are selected from
the group consisting of C, N, P, As, O, S, and Se; and wherein
[0032] said metal of said metal complex is selected from the group
consisting of Sc, Ta, Ti, Zr, Hf, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru,
Os, Co, Rh, Ir, Ni, Cu, Pd, Pt, Al, and Ga.
[0033] Preferred catalyst compositions in this first aspect are
those comprising a bidentate or tridentate ligand. Numerous
examples of such catalyst compositions are contained herein.
[0034] In a second aspect, this invention relates to a process for
the polymerization or oligomerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
first aspect. Polymerization reaction temperatures of between about
20 and about 160.degree. C. are preferred, with temperatures
between about 60 and about 100.degree. C. being especially
preferred. Ethylene, propylene, 1-butene, 1-hexene and 1-octene are
preferred olefin monomers. When ethylene is used as the primary or
predominant olefin monomer, pressures between about 1 and about 100
atm are preferred.
[0035] In a third aspect, this invention relates to a catalyst
composition for the polymerization or oligomerization of olefins,
comprising a catalyst composition of the first aspect, wherein the
metal is selected from the group consisting of Co, Fe, Ni, and Pd,
and the ligand is a neutral bidentate ligand.
[0036] A first preferred embodiment of this third aspect are those
catalyst compositions wherein the metal complex is either (i) a
compound of formula XIa, or (ii) the reaction product of
Ni(1,5-cyclooctadiene).su- b.2, B(C.sub.6F.sub.5).sub.3, one or
more olefins, and said neutral bidentate ligand: 3
[0037] wherein:
[0038] M is Fe, Co, Ni or Pd;
[0039] D.sup.1, D.sup.2, and G collectively comprise the neutral
bidentate ligand;
[0040] D.sup.1 and D.sup.2 are monodentate donors linked by a
bridging group G, wherein at least one of D.sup.1 and D.sup.2 is
ligated to the metal M by a nitrogen atom substituted by a
1-pyrrolyl or a substituted 1-pyrrolyl group;
[0041] T is H, hydrocarbyl, substituted hydrocarbyl, or other group
capable of inserting an olefin;
[0042] L is an olefin or a neutral donor group capable of being
displaced by an olefin; in addition, T and L may be taken together
to form a .pi.-allyl or .pi.-benzyl group; and
[0043] X.sup.- is a weakly coordinating anion.
[0044] A second preferred embodiment in this third aspect are those
catalyst compositions wherein the metal complex is the reaction
product of a compound of formula XIb and a second compound Y: 4
[0045] wherein:
[0046] M is Fe, Co, Ni or Pd;
[0047] D.sup.1, D.sup.2, and G collectively comprise the neutral
bidentate ligand;
[0048] D.sup.1 and D.sup.2 are monodentate donors linked by a
bridging group G, wherein at least one of D.sup.1 and D.sup.2 is
ligated to the metal M by a nitrogen atom substituted by a
1-pyrrolyl or a substituted 1-pyrrolyl group;
[0049] Q and W are each independently fluoro, chloro, bromo or
iodo, hydrocarbyl, substituted hydrocarbyl, heteroatom attached
hydrocarbyl, heteroatom attached substituted hydrocarbyl, or
collectively sulfate, or may be taken together to form a
.pi.-allyl, .pi.-benzyl, or acetylacetonate group, in which case a
weakly coordinating counteranion X.sup.- is also present; and
[0050] Y is a neutral Lewis acid capable of abstracting Q.sup.- or
W.sup.- to form a weakly coordinating anion, a cationic Lewis acid
whose counterion is a weakly coordinating anion, or a Bronsted acid
whose conjugate base is a weakly coordinating anion.
[0051] A third, more preferred, embodiment in this third aspect are
those catalyst compositions of the first or second embodiments in
which the metal M in formulas XIa or XIb is Ni and the neutral
bidentate ligand is selected from Set 1: 56
[0052] wherein:
[0053] R.sup.2x,y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl; silyl, boryl, or
ferrocenyl; in addition, R.sup.2x and R.sup.2y may be linked by a
bridging group; and
[0054] R.sup.3a-h are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-h may be linked by a bridging group.
[0055] In a fourth preferred embodiment, the catalyst compositions
of the third aspect are attached to a solid support, with those
catalyst compositions wherein the metal is nickel and the solid
support is silica representing an especially preferred, fifth
embodiment.
[0056] In a fourth aspect, this invention relates to a process for
the polymerization or oligomerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
third aspect.
[0057] A first preferred embodiment of this fourth aspect is the
process wherein linear .alpha.-olefins are obtained.
[0058] A second preferred embodiment of this fourth aspect is the
process wherein a polyolefin wax is obtained.
[0059] In a fifth aspect, this invention relates to a process for
the polymerization of olefins, which comprises contacting one or
more olefins with a catalyst composition of the fourth or fifth
embodiment of the third aspect. A first preferred embodiment of
this fifth aspect is the process wherein the metal is Ni, the solid
support is silica, and the catalyst is activated by treatment with
an alkylaluminum in a gas phase, fluidized bed, olefin
polymerization reactor, or in an inlet stream thereof. A second,
more preferred, embodiment of this fifth aspect is the process
wherein the alkylaluminum is trimethylaluminum.
[0060] The in situ catalyst activation protocol described as a
first preferred embobiment of the fifth aspect represents a
significant process breakthrough. The in situ catalyst activation
allows for the addition to a gas phase reactor of an inactive or
passivated catalyst that is activated in the reactor, and catalyst
activity increases as additional sites become activated. This
process allows for more convenient catalyst handling as well as
improved control and stability of the gas phase process.
[0061] In a sixth aspect, this invention relates to a compound
selected from Set 2. 789
[0062] wherein:
[0063] R.sup.2x,y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl; silyl, boryl, or
ferrocenyl; in addition, R.sup.2x and R.sup.2y may be linked by a
bridging group;
[0064] R.sup.3a-h are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-h may be linked by a bridging group.
[0065] In a seventh aspect, this invention relates to a catalyst
composition for the polymerization or oligomerization of olefins,
comprising either (i) a cationic Group 8-10 transition metal
complex of a neutral bidentate ligand selected from Set 3, or a
tautomer thereof, and a weakly coordinating anion X.sup.-, or (ii)
the reaction product of Ni(1,5-cyclooctadiene).sub.2,
B(C.sub.6F.sub.5).sub.3, one or more olefin monomers, and a neutral
bidentate ligand selected from Set 3:
10111213141516171819202122
[0066] wherein:
[0067] R.sup.2a-f,x-z are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; R.sup.2a-f may also
be silyl, boryl, or ferrocenyl; in addition, any two of R.sup.2a-d,
or R.sup.2x and R.sup.2y, may be linked by a bridging group;
[0068] R.sup.3a-j are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-j may be linked by a bridging group;
[0069] R.sup.4a and R.sup.4b are each independently hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; in addition, R.sup.4a
and R.sup.4b may be linked by a bridging group;
[0070] G.sup.1 is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl;
[0071] G.sup.1, C, and N collectively comprise a 5- or 6-membered
heterocyclic ring;
[0072] G.sup.2 is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl;
[0073] G.sup.2, V.sup.1, N, and N collectively comprise a 5- or
6-membered heterocyclic ring;
[0074] V.sup.1 is CR.sup.3j, N, or PR.sup.4aR.sup.4b;
[0075] E.sup.1 is O, S, Se, or NR.sup.2e;
[0076] E.sup.2 and E.sup.3 are O, S, or NR.sup.2e; and
[0077] Q.sup.1 is C--R.sup.3j, PR.sup.4aR.sup.6,
S(E.sup.2)(NR.sup.2eR.sup- .2f) or S(E.sup.2)(E.sup.3R.sup.2e);
[0078] provided that the ligand is not of the formula a15, which
has been previously described in the third embodiment of the third
aspect of the present invention.
[0079] In an eighth aspect, this invention relates to a process for
the polymerization or oligomerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
seventh aspect. Polymerization reaction temperatures between about
20 and about 160.degree. C. are preferred, with temperatures
between about 60 and about 100.degree. C. being more preferred.
Ethylene, propylene, 1-butene, 1-hexene and 1-octene are preferred
olefin monomers. When ethylene is used as the primary or
predominant olefin monomer, pressures between about 1 and about 100
atm are preferred.
[0080] In a ninth aspect, this invention relates to a ligand
selected from Set 4: 2324252627282930
[0081] wherein:
[0082] R.sup.2a-f,x-z are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; R.sup.2a-f may also
be silyl, boryl, or ferrocenyl; in addition, any two of R.sup.2a-d,
or R.sup.2x and R.sup.2y, may be linked by a bridging group;
[0083] R.sup.3a-j are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-j may be linked by a bridging group;
[0084] R.sup.4a and R.sup.4b are each independently hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; in addition, R.sup.4a
and R.sup.4b may be linked by a bridging group;
[0085] G.sup.1 is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl;
[0086] G.sup.1, C, and N collectively comprise a 5- or 6-membered
heterocyclic ring;
[0087] G.sup.2 is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl;
[0088] G.sup.2, V.sup.1, N, and N collectively comprise a 5- or
6-membered heterocyclic ring;
[0089] V.sup.1 is CR.sup.3j, N, or PR.sup.4aR.sup.4b;
[0090] E.sup.1 is O, S, Se, or NR.sup.2e;
[0091] E.sup.2 and E.sup.3 are O, S, or NR.sup.2e; and
[0092] Q.sup.1 is C--R.sup.3j, PR.sup.4aR.sup.4b,
S(E.sup.2)(NR.sup.2eR.su- p.2f) or S(E.sup.2)(E.sup.3R.sup.2e);
[0093] provided that (i) the ligand is not of the formula a15,
which has been previously described in the sixth aspect, (ii) when
the ligand is of the formula b7, and E.sup.3 is O, R.sup.3a-d are
H, and R.sup.2x is H, the pyrrol-1-yl group is other than
carbazol-9-yl, 3-phenylinden-1-yl or unsubstituted pyrrol-1-yl, and
(iii) when the ligand is of formula a55, it is other than
carbazol-9-yl-quinolin-2-ylmethylene-amine.
[0094] In a tenth aspect, this invention relates to a catalyst
composition for the polymerization or oligomerization of olefins,
comprising a catalyst composition of the first aspect, wherein the
metal is selected from the group consisting of Co, Ni, and Pd, and
the ligand is a monoanionic bidentate ligand. Preferred catalyst
compositions in this tenth aspect are those wherein the metal is
nickel; more preferred are those catalyst compositions wherein the
metal complex is of formula XII: 31
[0095] wherein:
[0096] M is nickel;
[0097] D.sup.1, D.sup.2, and G collectively comprise the
monoanionic bidentate ligand;
[0098] D.sup.1 and D.sup.2 are monodentate donors linked by a
bridging group G, wherein at least one of D.sup.1 and D.sup.2 is
ligated to the metal M by a nitrogen atom substituted by a
1-pyrrolyl or a substituted 1-pyrrolyl group;
[0099] T is H, hydrocarbyl, substituted hydrocarbyl, or other group
capable of inserting an olefin; and
[0100] L is an olefin or a neutral donor group capable of being
displaced by an olefin; in addition, T and L may be taken together
to form a .pi.-allyl or .pi.-benzyl group.
[0101] Even more preferred catalyst compositions in this tenth
aspect are those wherein the monoanionic bidentate ligand is
selected from Set 5, or a tautomer thereof: 323334
[0102] wherein:
[0103] R.sup.2x-z are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl;
[0104] R.sup.3a-j are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-j may be linked by a bridging group;
[0105] R.sup.4a and R.sup.4b are each independently hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; in addition, R.sup.4a
and R.sup.4b may be linked by a bridging group;
[0106] E.sup.2 and E.sup.3 are O, S, or NR.sup.2x; and
[0107] Q is C--R.sup.3j, PR.sup.4aR.sup.4b,
S(E.sup.2)(NR.sup.2yR.sup.2z), or S(E.sup.2)(E.sup.3R.sup.2x).
[0108] Also preferred in this tenth aspect are those catalyst
compositions wherein the metal complex is attached to a solid
support, with silica being an especially preferred support.
[0109] In an eleventh aspect, this invention relates to a process
for the polymerization or oligomerization of olefins, which
comprises contacting one or more olefins with the catalyst
composition of the tenth aspect. Polymerization reaction
temperatures between about 20 and about 160.degree. C. are
preferred, with temperatures between about 60 and about 100.degree.
C. being more preferred. Ethylene, propylene, 1-butene, 1-hexene,
1-octene, norbornene and substituted norbornenes are preferred
olefin monomers. When ethylene is used as the primary or
predominant olefin monomer, pressures between about 1 and about 100
atm are preferred.
[0110] In a twelfth aspect, this invention relates to a catalyst
composition for the polymerization or oligomerization of olefins,
comprising a catalyst composition of the first aspect, wherein the
metal is selected from the group consisting of Mn, Fe, Ru, and Co,
and the ligand is a neutral tridentate ligand. Preferred catalyst
compositions in this twelfth aspect are those wherein the metals
are Fe and Co; more preferred are those catalyst compositions
comprising a compound of formula XIII: 35
[0111] wherein:
[0112] M is Co or Fe;
[0113] D.sup.1-3 are monodentate donors which are linked by a
bridging group(s) to collectively comprise the neutral tridentate
ligand, wherein at least one of D.sup.1, D.sup.2, and D.sup.3 is
ligated to the metal M by a nitrogen atom substituted by a
1-pyrrolyl or a substituted 1-pyrrolyl group;
[0114] T is H, hydrocarbyl, substituted hydrocarbyl or other group
capable of inserting an olefin;
[0115] L is an olefin or a neutral donor group capable of being
displaced by an olefin; in addition, T and L may be taken together
to form a .pi.-allyl or .pi.-benzyl group; and
[0116] X.sup.- is a weakly coordinating anion.
[0117] Even more preferred catalyst compositions in this twelfth
aspect are those wherein the neutral tridentate ligand is selected
from Set 6, or a tautomer thereof: 36373839404142
[0118] wherein:
[0119] R.sup.2c,x-z are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl; in addition, R.sup.2x
and R.sup.2y may be linked by a bridging group in the ligand of
formula h6;
[0120] R.sup.3a-m are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-m may be linked by a bridging group;
[0121] R.sup.4a-d are each independently hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl; in addition, any two of
R.sup.4a-z may be linked by a bridging group or groups;
[0122] G.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0123] E.sup.2 and E.sup.3 are O, S, or Se; and
[0124] E.sup.4 is O, S, or Se.
[0125] Also preferred in this twelfth aspect are those catalyst
compositions wherein the metal complex is attached to a solid
support, with silica being an especially preferred support.
[0126] In a thirteenth aspect, this invention also relates to a
process for the polymerization or oligomerization of olefins, which
comprises contacting one or more olefins with a catalyst
composition of the twelfth aspect. Polymerization reaction
temperatures between about 20 and about 160.degree. C. are
preferred, with temperatures between about 60 and about 100.degree.
C. being more preferred. Ethylene, propylene, 1-butene, 1-hexene
and 1-octene are preferred olefin monomers. When ethylene is used,
pressures between about 1 and about 100 atm are preferred. Also
preferred are those embodiments wherein non-supported catalysts are
used to produce linear .alpha.-olefins or polyolefin waxes.
[0127] In a fourteenth aspect, this invention relates to a catalyst
composition for the polymerization of olefins, comprising a Ti, Zr,
or Hf complex of a dianionic bidentate ligand, wherein at least one
of the donor atoms of the ligand is a nitrogen atom substituted by
a 1-pyrrolyl or substituted 1-pyrrolyl group; wherein the remaining
donor atoms of the ligand are selected from the group consisting of
C, N, P, As, O, S, and Se. Preferred catalyst compositions in this
fourteenth aspect are those wherein the metal complex is a compound
of formula XIV: 43
[0128] wherein:
[0129] M is Zr or Ti;
[0130] D.sup.1, D.sup.2, and G collectively comprise the dianionic
bidentate ligand;
[0131] D.sup.1 and D.sup.2 are monodentate donors linked by a
bridging group G, wherein at least one of D.sup.1 and D.sup.2 is
ligated to the metal M by a nitrogen atom substituted by a
1-pyrrolyl or a substituted 1-pyrrolyl group;
[0132] T is H, hydrocarbyl, substituted hydrocarbyl, or other group
capable of inserting an olefin; and
[0133] X.sup.- is a weakly coordinating anion.
[0134] More preferred catalyst compositions in this fourteenth
aspect are those wherein the dianionic bidentate ligand is selected
from Set 7, or a tautomer thereof: 4445
[0135] wherein:
[0136] R.sup.3a-h are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-h may be linked by a bridging group; and
[0137] G.sup.4 is a divalent bridging hydrocarbyl, substituted
hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl.
[0138] Also preferred in this fourteenth aspect are those catalyst
compositions which are attached to a solid support.
[0139] In a fifteenth aspect, this invention relates to a process
for the polymerization of olefins, comprising contacting one or
more olefins with the catalyst composition of the fourteenth
aspect, and optionally an aluminum or boron-centered Lewis acid.
Examples of aluminum or boron-centered Lewis acids include MAO,
B(C.sub.6F.sub.5).sub.3, triisobutylaluminum modified MAO, and
B(C.sub.12F.sub.9).sub.3. Polymerization reaction temperatures
between about 20 and about 160.degree. C. are preferred, with
temperatures between about 60 and about 100.degree. C. being more
preferred. Ethylene, propylene, 1-butene, 1-hexene and 1-octene are
preferred olefin monomers. When ethylene is used, pressures between
about 1 and about 100 atm are preferred.
[0140] In a sixteenth aspect, this invention relates to a catalyst
composition for the polymerization of olefins, comprising a Ti, Zr,
or Hf complex of a monoanionic bidentate ligand, wherein at least
one of the donor atoms of the ligand is a nitrogen atom substituted
by a 1-pyrrolyl or substituted 1-pyrrolyl group; wherein the
remaining donor atoms of the ligand are selected from the group
consisting of C, N, P, As, O, S, and Se.
[0141] Preferred catalyst compositions in this sixteenth aspect are
those which optionally further comprise a second compound Y,
wherein the metal complex is a compound of formula XV: 46
[0142] wherein:
[0143] M is Ti, Zr, or Hf;
[0144] m and n are integers, defined as follows: when M is Ti and m
is 1, n is 2 or 3; when M is Ti and m is 2, n is 1 or 2; when M is
Zr and m is 1, n is 3; when M is Zr and m is 2, n is 2; when M is
Hf, m is 2 and n is 2;
[0145] R.sup.3a-i are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, silyl, boryl, fluoro,
chloro, bromo, or nitro, with the proviso that R.sup.3e is other
than halogen or nitro; in addition, any two of R.sup.3a-i on the
same or different N-pyrrol-1-yliminophenoxide ligand may be linked
by a bridging group;
[0146] Z is H, halogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, silyl, allyl, benzyl, alkoxy, carboxylate, amido,
nitro, or trifluoromethane sulfonyl; each Z may be the same or
different and plural Z may be taken together to form sulfate,
oxalate, or another divalent group;
[0147] Y is selected from the group consisting of a neutral Lewis
acid capable of abstracting Z.sup.-to form a weakly coordinating
anion, a cationic Lewis acid whose counterion is a weakly
coordinating anion, and a Bronsted acid whose conjugate base is a
weakly coordinating anion; and
[0148] when n is 2 or 3, the metal complex may be a salt,
comprising a Ti, Zr, or Hf centered cation with one of the groups
Z.sup.- being a weakly coordinating anion.
[0149] Even more preferred catalyst compositions in this sixteenth
aspect are those wherein the monoanionic bidentate ligand is
selected from Set 8, or a tautomer thereof: 4748
[0150] wherein:
[0151] R.sup.2x is H, hydrocarbyl, substituted hydrocarbyl,
heteroatom connected hydrocarbyl, or heteroatom connected
substituted hydrocarbyl; and
[0152] R.sup.3a-d,f-i are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-d,f-i may be linked by a bridging group.
[0153] Also preferred catalyst compositions in this sixteenth
aspect are those catalyst compositions which are attached to a
solid support, with silica being an especially preferred solid
support.
[0154] In a seventeenth aspect, this invention also relates to a
process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
sixteenth aspect, and optionally a second compound Y; wherein Y is
selected from the group consisting of (i) a neutral Lewis acid
which is capable of reacting with said Ti, Zr, or Hf complex to to
form a salt comprising a weakly coordinating anion, (ii) a cationic
Lewis acid whose counterion is a weakly coordinating anion, and
(iii) a Bronsted acid whose conjugate base is a weakly coordinating
anion. Polymerization reaction temperatures between about 20 and
about 160.degree. C. are preferred, with temperatures between about
60 and about 100.degree. C. being more preferred. Ethylene,
propylene, 1-butene, 1-hexene and 1-octene are preferred olefin
monomers. When ethylene is used, pressures between about 1 and
about 100 atm are preferred.
[0155] In an eighteenth aspect, this invention relates to a
catalyst composition for the polymerization of olefins, comprising
a Cr, Mo, or W complex of a monodentate dianionic ligand, wherein
at least one of the donor atoms of the ligand is a nitrogen atom
substituted by a 1-pyrrolyl or substituted 1-pyrrolyl group;
wherein the remaining donor atoms of the ligand are selected from
the group consisting of C, N, P, As, O, S, and Se. Preferred
catalyst compositions in this eighteenth aspect are those which
optionally further comprise a second compound Y, wherein the metal
complex is a compound of formula XVI: 49
[0156] wherein:
[0157] M is Cr, Mo, or W;
[0158] D.sup.1 and D.sup.2 are monodentate dianionic ligands that
may be linked by a bridging group to collectively comprise a
bidentate tetraanionic ligand;
[0159] Z.sup.1a and Z.sup.1b are each, independently H, halogen,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl,
allyl, benzyl, alkoxy, carboxylate, amido, nitro,
trifluoromethanesulfonyl, or may be taken together to form sulfate,
oxalate, or another divalent group;
[0160] Y is selected from the group consisting of a neutral Lewis
acid capable of abstracting (Z.sup.1a).sup.- or (Z.sup.1b).sup.- to
form a weakly coordinating anion, a cationic Lewis acid whose
counterion is a weakly coordinating anion, and a Bronsted acid
whose conjugate base is a weakly coordinating anion; and
wherein
[0161] the metal complex may be a salt, comprising a Cr, Mo, or W
centered cation with one of (Z.sup.1a).sup.- or (Z.sup.1b).sup.-
being a weakly coordinating anion.
[0162] Even more preferred catalyst compositions in this eighteenth
aspect are those wherein the metal is Cr and the monodentate
dianionic ligand is selected from Set 9, or a tautomer thereof:
50
[0163] wherein:
[0164] R.sup.3a-d are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-d may be linked by a bridging group.
[0165] Also preferred in this eighteenth aspect are those catalyst
compositions which are attached to a solid support, with silica
being an especially preferred solid support.
[0166] In a nineteenth aspect, this invention also relates to a
process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
eighteenth aspect, and optionally a second compound Y; wherein Y is
selected from the group consisting of (i) a neutral Lewis acid
which is capable of reacting with said Cr, Mo, or W complex to to
form a salt comprising a weakly coordinating anion, (ii) a cationic
Lewis acid whose counterion is a weakly coordinating anion, and
(iii) a Bronsted acid whose conjugate base is a weakly coordinating
anion. Polymerization reaction temperatures between about 20 and
about 160.degree. C. are preferred, with temperatures between about
60 and about 100.degree. C. being more preferred. Ethylene,
propylene, 1-butene, 1-hexene and 1-octene are preferred olefin
monomers. When ethylene is used, pressures between about 1 and
about 100 atm are preferred.
[0167] In a twentieth aspect, this invention relates to a catalyst
composition for the polymerization of olefins, comprising a V, Nb,
or Ta complex of a monodentate dianionic ligand, wherein at least
one of the donor atoms of the ligand is a nitrogen atom substituted
by a 1-pyrrolyl or substituted 1-pyrrolyl group; wherein the
remaining donor atoms of the ligand are selected from the group
consisting of C, N, P, As, O, S, and Se.
[0168] Preferred catalyst compositions in this twentieth aspect are
those which optionally further comprise a second compound Y,
wherein the metal complex is a compound of formula XVII: 51
[0169] wherein:
[0170] M is V, Nb, or Ta;
[0171] R.sup.3a-d are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, silyl, boryl, fluoro,
chloro, bromo, or nitro; in addition, any two of R.sup.3a-d may be
linked by a bridging group;
[0172] T.sup.1b is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, cyclopentadienyl, substituted cyclopentadienyl,
N(hydrocarbyl).sub.2, O(hydrocarbyl), or halide;
[0173] Z.sup.1a and Z.sup.1b are each, independently H, halogen,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl,
allyl, benzyl, alkoxy, carboxylate, amido, nitro, trifluoromethane
sulfonyl, or may be taken together to form sulfate, oxalate, or
another divalent group;
[0174] Y is selected from the group consisting of a neutral Lewis
acid capable of abstracting (Z.sup.1a).sup.- or (Z.sup.1b).sup.- to
form a weakly coordinating anion, a cationic Lewis acid whose
counterion is a weakly coordinating anion, and a Bronsted acid
whose conjugate base is a weakly coordinating anion; and
wherein
[0175] the metal complex may be a salt, comprising a V, Nb, or Ta
centered cation with one of (Z.sup.1a).sup.- or (Z.sup.1b).sup.-
being a weakly coordinating anion.
[0176] More preferred catalyst compositions in this twentieth
aspect are those wherein the monodentate dianionic ligand is
selected from Set 10, or a tautomer thereof, and T.sup.1b is a
N(hydrocarbyl).sub.2 group: 52
[0177] wherein:
[0178] R.sup.3a-d are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-d may be linked by a bridging group.
[0179] Even more preferred catalyst compositions in this twentieth
aspect are those wherein the metal is V and the metal complex is
attached to a solid support.
[0180] In a twenty-first aspect, this invention relates to a
process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
twentieth aspect, and optionally a second compound Y; wherein Y is
selected from the group consisting of (i) a neutral Lewis acid
which is capable of reacting with said V, Nb, or Ta complex to to
form a salt comprising a weakly coordinating anion, (ii) a cationic
Lewis acid whose counterion is a weakly coordinating anion, and
(iii) a Bronsted acid whose conjugate base is a weakly coordinating
anion.
[0181] In a twenty-second aspect, this invention relates to a
catalyst composition for the polymerization olefins, comprising (i)
a cationic Ti, Zr or Hf complex of a mono- or dianionic, nitrogen
donor ligand, wherein said nitrogen donor is substituted by a
1-pyrrolyl or substituted 1-pyrrolyl group and is linked by a
bridging group to a cyclopentadienyl, phosphacyclopentadienyl,
pentadienyl, 6-oxacyclohexadienyl, or borataaryl group which is
also ligated to said metal, and optionally, (ii) an aluminum or
boron-centered Lewis acid. Preferred catalyst compositions within
this twenty-second aspect are those wherein the mono- or dianionic,
nitrogen donor ligand is selected from Set 11, or a tautomer
thereof: 535455
[0182] wherein:
[0183] R.sup.2a is H, hydrocarbyl, substituted hydrocarbyl,
heteroatom connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, silyl, boryl, or ferrocenyl;
[0184] R.sup.3a-h are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-h may be linked by a bridging group;
[0185] R.sup.4a is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl; and
[0186] G is a divalent bridging hydrocarbyl, substituted
hydrocarbyl, silyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl.
[0187] Also preferred catalyst compositions in this twenty-second
aspect are those wherein the metal complex is attached to a solid
support.
[0188] In a twenty-third aspect, this invention also relates to a
process for the polymerization of olefins, which comprises
contacting one or more olefins with the catalyst composition of the
twenty-second aspect. Polymerization reaction temperatures between
about 20 and about 160.degree. C. are preferred, with temperatures
between about 60 and about 100.degree. C. being more preferred.
Ethylene, propylene, 1-butene, 1-hexene and 1-octene are preferred
olefin monomers. When ethylene is used, pressures between about 1
and about 100 atm are preferred.
[0189] Notwithstanding the above-noted advances in polyolefin
catalysis, set forth in the Background of the Invention section,
there remains a need for new catalysts which can not only produce
novel polyolefin microstructures or incorporate functional
co-monomers, but also possess sufficient thermal stability to be
used in existing production reactors, and exhibit an appropriate
response to hydrogen under such conditions, so as to allow for
control of molecular weight without an unacceptable loss of
catalyst productivity. This is particularly true in the case of
nickel catalysts comprising bidentate N,N-donor ligands, which
typically exhibit very short lifetimes (t.sub.1/2 ca. 2-4 min) at
60.degree. C., and are generally so severely inhibited by hydrogen
that when enough hydrogen is added to bring the molecular weight
down to that of a typical commercial linear low density
polyethylene (LLDPE), the catalyst productivities at elevated
temperature are so low as to be impractical. A common structural
feature of these catalysts is that they contain a nitrogen donor
substituted by an aromatic or heteroaromatic ring, wherein the
substituents ortho to the point of attachment to the ligated
nitrogen are alkyl groups, as exemplified by complex XXI.
[0190] We have discovered that both the thermal stability and the
catalyst productivity in the presence of hydrogen are dramatically
improved if the ortho substituents are aryl groups, as exemplified
by complex XXII. Productivity improvements of about an order of
magnitude, or more, are observed when the ortho-alkyl groups are
replaced by ortho-aryl groups. 56
[0191] Whereas the half-life for catalyst deactivation for complex
XXI is about 2-4 minutes at 60.degree. C., 200 psig ethylene, the
half-life for catalyst deactivation for complex XXII is at least
about 32 minutes at 200 psig ethylene, and even at 1 atm ethylene,
detectable activity is still observed after 16 hours at 60.degree.
C.
[0192] Without wishing to be bound by theory, the inventors
attribute the improved stability to the reversible formation of
agostic aryl intermediates in the catalytic chemistry (c.f.
structure XXIII, wherein R.sub.p represents the growing polymer
chain, X.sup.- is a weakly coordinating anion, and no specific
bonding mode is implied for the interaction of the agostic phenyl
group with the nickel center). 57
[0193] As such, the catalysis no longer involves a strictly
bidentate ligand, but rather a variable denticity ligand, whereby
the ability of the ligand to donate additional electron density
(and possibly also accept .pi.-electron density from the nickel) is
believed to stabilize low coordinate intermediates (e.g.
three-coordinate cationic nickel hydride species), which otherwise
would rapidly decompose to catalytically inactive species. When
ortho-alkyl groups are present, it is believed that rapid
cyclometallation occurs to give species which are either
permanently deactivated, or which are so slowly reactivated as to
render them much less attractive for commercial polyolefin
production. Deactivation reactions of this general type have been
discussed by Brookhart et al. (J. Am. Chem. Soc., 117, 6414,
1995).
[0194] Ligands wherein some, but not all, of the ortho positions
are substituted by bromo groups also give rise to catalysts which
exhibit enhanced thermal stability and stability towards hydrogen.
In contrast, when even one of four ortho substituents in a catalyst
of this invention is alkyl, and the rest are aryl, poor thermal
stabilities are observed (u2, R.sup.7a-c.dbd.Ph; R.sup.7d.dbd.Me or
cyclopropyl; R2.sup.x,y.dbd.Me). Similarly, when all four of the
ortho positions are bromo (u4, R.sup.7a-d.dbd.Br; R.sup.2x,y
collectively OCH.sub.2CH.sub.2O), poor thermal stability is also
observed. Without wishing to be bound by theory, the inventors
believe that catalysts wherein the ortho positions are substituted
by groups other than alkyl will exhibit enhanced thermal stability
and stability towards hydrogen, provided that at least one of the
ortho positions of one of said aromatic or heteroaromatic rings is
an aryl or heteroaryl group.
[0195] Therefore, although the pro-catalyst may comprise, for
example, a bidentate N,N- N,O- or N,P-donor ligand, it is a novel
feature of these ortho-aryl substituted ligands that they can
reversibly form an additional bonding interaction, thereby helping
to stabilize catalytic intermediates under polymerization
conditions.
[0196] Thus, in a twenty-fourth aspect, this invention relates to a
process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits improved thermal
stability, and wherein said metal complex comprises a bidentate or
variable denticity ligand comprising one or two nitrogen donor atom
or atoms independently substituted by an aromatic or heteroaromatic
ring, wherein the ortho positions of said ring(s) are substituted
by groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
[0197] As used herein, examples of groups other than H or alkyl
include aryl, heteroaryl, bromo, fluoroalkyl and cyano.
[0198] In a twenty-fifth aspect, this invention also relates to a
process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits improved stability in
the presence of an amount of hydrogen effective to achieve chain
transfer, and wherein said metal complex comprises a bidentate or
variable denticity ligand comprising one or two nitrogen donor atom
or atoms independently substituted by an aromatic or heteroaromatic
ring, wherein the ortho positions of said ring(s) are substituted
by groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
[0199] In a twenty-sixth aspect, this invention also relates to a
process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits either improved thermal
stability, or exhibits improved stability in the presence of an
amount of hydrogen effective to achieve chain transfer, or both,
wherein said metal complex comprises a bidentate or variable
denticity ligand comprising one or two nitrogen donor atom or atoms
independently substituted by an aromatic or heteroaromatic ring,
wherein at least one of the ortho positions of at least one of said
aromatic or heteroaromatic rings is substituted by an aryl or
heteroaryl group which is capable of reversibly forming an agostic
bond to said Group 8-10 transition metal under olefin
polymerization reaction conditions.
[0200] In a twenty-seventh aspect, this invention also relates to a
process for the polymerization or oligomerization of olefins,
comprising contacting one or more olefins with a catalyst
composition comprising a Group 8-10 transition metal complex,
wherein said catalyst composition exhibits either improved thermal
stability, or exhibits improved stability in the presence of an
amount of hydrogen effective to achieve chain transfer, or both,
wherein said composition comprises a bidentate or variable
denticity ligand comprising one or two nitrogen donor atom or atoms
independently substituted by an aromatic or heteroaromatic ring,
wherein the ortho positions of said ring(s) are substituted by
groups other than H or alkyl; provided that at least one of the
ortho positions of at least one of said aromatic or heteroaromatic
rings is substituted by an aryl or heteroaryl group.
[0201] In a twenty-eighth aspect, the ortho positions of the
aromatic or heteroaromatic ring(s) of the twenty-fourth,
twenty-fifth, twenty-sixth, or twenty-seventh aspect are
substituted by aryl or heteroaryl groups.
[0202] In a first preferred embodiment of the twenty-fourth,
twenty-fifth, twenty-sixth, twenty-seventh or twenty-eighth aspect,
the half-life for thermal decomposition is greater than 10 min in
solution at 60.degree. C., 200 psig ethylene, and the average
apparent catalyst activity of said catalyst is greater than 100,000
mol C.sub.2H.sub.4/mol catalyst/h. In a second, more preferred
embodiment of these aspects, the half-life for thermal
decomposition is greater than 20 minutes, and the average apparent
catalyst activity of said catalyst is greater than 1,000,000 mol
C.sub.2H.sub.4/mol catalyst/h. In a third, also more preferred
embodiment of these aspects, the half-life for thermal
decomposition of said catalyst is greater than 30 min. In a fourth,
especially preferred embodiment of the first, second, and third
embodiments of these aspects, the Group 8-10 metal is Ni. In a
fifth preferred embodiment of these aspects, the process
temperature is between about 60 and about 150.degree. C., more
preferably between about 100 and about 150.degree. C. In a sixth,
more preferred embodiment of these aspects, the bidentate or
variable denticity ligand is selected from Set 12: 58
[0203] wherein:
[0204] R.sub.6a and R.sub.6b are each independently an aromatic or
heteroaromatic ring wherein the ortho positions of said ring(s) are
substituted by groups other than H or alkyl; provided that at least
one of the ortho positions of at least one of said aromatic or
heteroaromatic rings is substituted by an aryl or heteroaryl
group;
[0205] and R.sup.2x and R.sup.2y are each independently H,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, or heteroatom connected substituted hydrocarbyl, and
may be linked by a bridging group.
[0206] In a seventh, especially preferred embodiment of the
twenty-fourth, twenty-fifth, twenty-sixth, twenty-seventh or
twenty-eighth aspect, the Group 8-10 transition metal is nickel and
the bidentate or variable denticity ligand is selected from Set 13:
59
[0207] wherein:
[0208] R.sup.7a-d are groups other than H or alkyl; provided that
at least one of R.sup.7a-d is an aryl or heteroaryl group;
[0209] R.sup.2x and R.sup.2y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl, and may be linked by
a bridging group; and
[0210] R.sup.3a-f are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-f may be linked by a bridging group.
[0211] In an eighth, also especially preferred embodiment of the
twenty-fourth, twenty-fifth, twenty-sixth, twenty-seventh or
twenty-eighth aspect, the composition is attached to a solid
support, with silica being an especially preferred solid support
and reaction temperatures between about 60 and about 100.degree. C.
also being especially preferred in this embodiment.
[0212] In the case of gas phase olefin polymerization reactions, it
can sometimes be advantageous if the catalyst can be introduced
into the olefin polymerization reactor in an inactive form, and
subsequently activated. When the catalyst is introduced in a fully
activated form, there are sometimes problems with overheating of
the supported catalyst particle, which initially has a very high
rate of heat generation per unit volume. Overheating can result in
catalyst deactivation, or excessive agglomeration of the polymer
particles, or both. In addition, unfavorable static charge behavior
may be observed, causing the freshly introduced particles to
migrate to the reactor walls and give rise to deleterious sheeting
phenomena. It is therefore another object of the current invention
to describe methods of activating the catalyst in the gas phase
olefin polymerization reactor itself.
[0213] Thus, in a twenty-ninth aspect, this invention also relates
to a process for olefin polymerization comprising: contacting one
or more olefin monomers with a single site catalyst attached to a
solid support, wherein said catalyst comprises a cationic Group
4-11 transition metal complex and a weakly coordinating
counteranion, and wherein said catalyst is introduced into a gas
phase olefin polymerization reactor in an inactive form which is
subsequently activated by reaction with a second compound Y.sup.1
to form said catalyst in said reactor.
[0214] Preferred Group 4-11 transition metals in this twenty-ninth
aspect include Ti, Zr, Hf, Ni, Co, and Fe. Preferred second
compounds Y.sup.1 in this aspect include trialkylaluminum or
dialkylzinc compounds, with trimethylaluminum being especially
preferred. In a more preferred embodiment, said inactive form of
said catalyst is selected from Set 14, said weakly coordinating
counteranion is either formed by reaction of said inactive form of
said catalyst with Y.sup.1, or is selected from the group
consisting of B(C.sub.6F.sub.5).sub.4.sup.-,
B(3,5-bis(trifluoromethyl)phenyl).sub.4.sup.-,
[(C.sub.6F.sub.5).sub.3B-(-
imidazole)-B(C.sub.6F.sub.5).sub.3].sup.-, BF.sub.4.sup.-, and
[(C.sub.6F.sub.5).sub.3B--CN--B(C.sub.6F.sub.5).sub.3].sup.-, and
Y.sup.1 is trimethylaluminum; 6061626364
[0215] wherein:
[0216] R.sup.2a,b,x,y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, silyl, boryl, or
ferrocenyl; in addition, any two of R.sup.2a,b,x,y may be linked by
a bridging group;
[0217] R.sup.3a-m are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-m may be linked by a bridging group;
[0218] A.sup.1 is halide or a monoanionic group which is capable of
reacting with Y.sup.1 to generate an active olefin polymerization
catalyst, provided that in the absence of Y.sup.1, A.sup.1 is such
that said inactive form of said single site catalyst is at least 10
times less active as a catalyst for olefin polymerization than said
active olefin polymerization catalyst;
[0219] A.sup.2 and A.sup.3 are each independently hydrocarbyl,
halide, O(hydrocarbyl) or O(substituted hydrocarbyl), provided that
at least one of A.sup.2 and A.sup.3 is capable of being abstracted
by Y.sup.1 to form a weakly coordinating counteranion, and the
other is either capable of inserting an olefin to initiate polymer
chain growth, or is capable of being exchanged with a group on
Y.sup.1 which can then initiate chain growth;
[0220] G and G.sup.4 are divalent bridging hydrocarbyl, substituted
hydrocarbyl, silyl, heteroatom connected hydrocarbyl, or heteroatom
connected substituted hydrocarbyl; and
[0221] X.sup.- is a weakly coordinating anion.
[0222] In a thirtieth aspect, this invention also relates to a
process wherein the catalyst of the twenty-fourth, twenty-fifth,
twenty-sixth, twenty-seventh or twenty-eighth aspect is introduced
into a gas phase olefin polymerization reactor in an inactive form
attached to a solid support, and wherein said catalyst is
subsequently activated by a second compound Y.sup.1 in said
reactor. In a first preferred embodiment of this thirtieth aspect,
the bidentate or variable denticity ligand is selected from Set
15:
[0223] Set 15 65
[0224] wherein:
[0225] R.sup.6a and R.sup.6b are each independently an aromatic or
heteroaromatic ring wherein the ortho positions of said ring(s) are
substituted by groups other than H or alkyl; provided that at least
one of the ortho positions of at least one of said aromatic or
heteroaromatic rings is substituted by an aryl or heteroaryl
group;
[0226] and R.sup.2x and R.sup.2y are each independently H,
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, or heteroatom connected substituted hydrocarbyl, and
may be linked by a bridging group.
[0227] In a second, more preferred embodiment of the thirtieth
aspect, (i) the Group 8-10 transition metal is nickel, (ii) the
weakly coordinating counteranion is either formed by reaction of
said inactive form of said catalyst with a volatile second compound
Y.sup.1, or is selected from the group consisting of
B(C.sub.6F.sub.5).sub.4.sup.-,
B(3,5-bis(trifluoromethyl)phenyl).sub.4.sup.-,
[(C.sub.6F.sub.5).sub.3B-(-
imidazole)-B(C.sub.6F.sub.5).sub.3].sup.-, BF.sub.4.sup.-, and
[(C.sub.6F.sub.5).sub.3B--CN--B(C.sub.6F.sub.5).sub.3].sup.-, (iii)
Y.sup.1 is trimethylaluminum, and (iv) the bidentate or variable
denticity ligand is selected from Set 16; 66
[0228] wherein:
[0229] R.sup.7a-d are groups other than H or alkyl; provided that
at least one of R.sup.7a-d is an aryl or heteroaryl group;
[0230] R.sup.2x and R.sup.2y are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl, or
heteroatom connected substituted hydrocarbyl, and may be linked by
a bridging group; and
[0231] R.sup.3a-f are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-f may be linked by a bridging group.
[0232] In a thirty-first aspect, this invention also relates to a
process wherein said aromatic or heteroaromatic rings of the
catalyst of the twenty-fourth, twenty-fifth, twenty-sixth,
twenty-seventh or twenty-eighth aspect is selected from Set 17;
6768
[0233] wherein:
[0234] R.sup.7a,b are groups other than H or alkyl; provided that
at least one of R.sup.7a-b is an aryl or heteroaryl group;
[0235] R.sup.3a-k are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-k may be linked by a bridging group; and
[0236] E.sup.5 is O, S, Se, or NR.sup.3b.
[0237] In this disclosure, symbols ordinarily used to denote
elements in the Periodic Table and commonly abbreviated groups,
take their ordinary meaning, unless otherwise specified. Thus, N,
O, S, P, and Si stand for nitrogen, oxygen, sulfur, phosphorus, and
silicon, respectively, while Me, Et, Pr, .sup.iPr, Bu, .sup.tBu and
Ph stand for methyl, ethyl, propyl, iso-propyl, butyl, tert-butyl
and phenyl, respectively.
[0238] A "1-pyrrolyl or substituted 1-pyrrolyl" group refers to a
group of formula II below: 69
[0239] wherein R.sup.3a-d are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
or more of R.sup.3a-d may be linked by a bridging group or groupsto
form bicyclic or polycyclic ring systems including carbazol-9-yl
and indol-1-yl.
[0240] A "hydrocarbyl" group means a monovalent or divalent,
linear, branched or cyclic group which contains only carbon and
hydrogen atoms. Examples of monovalent hydrocarbyls include the
following: C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl
substituted with one or more groups selected from C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.8 cycloalkyl, and aryl; C.sub.3-C.sub.8
cycloalkyl; C.sub.3-C.sub.8 cycloalkyl substituted with one or more
groups selected from C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.8
cycloalkyl, and aryl; C.sub.6-C.sub.14 aryl; and C.sub.6-C.sub.14
aryl substituted with one or more groups selected from
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.8 cycloalkyl, and aryl.
Examples of divalent (bridging) hydrocarbyls include: --CH.sub.2--,
--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2--- , and
1,2-phenylene.
[0241] The term "aryl" refers to an aromatic carbocyclic
monoradical, which may be substituted or unsubstituted, wherein the
substituents are halo, hydrocarbyl, substituted hydrocarbyl,
heteroatom attached hydrocarbyl, heteroatom attached substituted
hydrocarbyl, nitro, cyano, fluoroalkyl, sulfonyl, and the like.
Examples include: phenyl, naphthyl, anthracenyl, phenanthracenyl,
2,6-diphenylphenyl, 3,5-dimethylphenyl, 4-nitrophenyl,
3-nitrophenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, and the
like.
[0242] A "heterocyclic ring" refers to a carbocyclic ring wherein
one or more of the carbon atoms has been replaced by an atom
selected from the group consisting of O, N, S, P, Se, As, Si, B,
and the like.
[0243] A "heteroaromatic ring" refers to an aromatic heterocycle;
examples include pyrrole, furan, thiophene, indene, imidazole,
oxazole, isoxazole, carbazole, thiazole, pyrimidine, pyridine,
pyridazine, pyrazine, benzothiophene, and the like.
[0244] A "heteroaryl" refers to a heterocyclic monoradical which is
aromatic; examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl,
furyl, thienyl, indenyl, imidazolyl, oxazolyl, isoxazolyl,
carbazolyl, thiazolyl, pyrimidinyl, pyridyl, pyridazinyl,
pyrazinyl, benzothienyl, and the like, and substituted derivatives
thereof.
[0245] A "silyl" group refers to a SiR.sub.3 group wherein Si is
silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl,
as in Si(SiR.sub.3).sub.3.
[0246] A "boryl" group refers to a BR.sub.2 or B(OR).sub.2 group,
wherein R is hydrocarbyl or substituted hydrocarbyl.
[0247] A "heteroatom" refers to an atom other than carbon or
hydrogen. Preferred heteroatoms include oxygen, nitrogen,
phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon,
and fluorine.
[0248] A "substituted hydrocarbyl" refers to a monovalent,
divalent, or trivalent hydrocarbyl substituted with one or more
heteroatoms. Examples of monovalent substituted hydrocarbyls
include: 2,6-dimethyl-4-methoxyphe- nyl,
2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl,
2,6-dimethyl-4-nitrophenyl, 2,6-difluorophenyl, 2,6-dibromophenyl,
2,6-dichlorophenyl, 4-methoxycarbonyl-2,6-dimethylphenyl,
2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl,
2,6-dimethyl-4-trifluoromethylphenyl,
2,6-dimethyl-4-trimethylammoniumphe- nyl (associated with a weakly
coordinated anion), 2,6-dimethyl-4-hydroxyph- enyl,
9-hydroxyanthr-10-yl, 2-chloronapth-1-yl, 4-methoxyphenyl,
4-nitrophenyl, 9-nitroanthr-10-yl, --CH.sub.2OCH.sub.3, cyano,
trifluoromethyl, and fluoroalkyl. Examples of divalent (bridging)
substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,
1-methoxymethyl-1,2-ethanediyl,
1,2-bis(benzyloxymethyl)-1,2-ethanediyl, and
1-(4-methoxyphenyl)-1,2-ethanediyl.
[0249] A "heteroatom connected hydrocarbyl" refers to a group of
the type E.sup.10(hydrocarbyl), E.sup.20H(hydrocarbyl), or
E.sup.20(hydrocarbyl).s- ub.2, where E.sup.10 is an atom selected
from Group 16 and E.sup.20 is an atom selected from Group 15.
[0250] A "heteroatom connected substituted hydrocarbyl" refers to a
group of the type E.sup.10(substituted hydrocarbyl),
E.sup.20H(substituted hydrocarbyl), or E.sup.20(substituted
hydrocarbyl).sub.2, where E.sup.10 is an atom selected from Group
16 and E.sup.20 is an atom selected from Group 15.
[0251] The term "fluoroalkyl" as used herein refers to a
C.sub.1-C.sub.20 alkyl group substituted by one or more fluorine
atoms.
[0252] An "olefin" refers to a compound of the formula
R.sup.1aCH.dbd.CHR.sup.1b, where R.sup.1a and R.sup.1b may
independently be H, hydrocarbyl, substituted hydrocarbyl,
fluoroalkyl, silyl, O(hydrocarbyl), or O(substituted hydrocarbyl),
and where R.sup.1a and R.sup.1b may be connected to form a cyclic
olefin, provided that in all cases, the substituents R.sup.1a and
R.sup.1b are compatible with the catalyst. In the case of most
Group 4-7 catalysts, this will generally mean that the olefin
should not contain good Lewis base donors, since this will tend to
severely inhibit catalysis. Preferred olefins for such catalysts
include ethylene, propylene, butene, hexene, octene, cyclopentene,
norbornene, and styrene.
[0253] In the case of the Group 8-10 catalysts, Lewis basic
substituents on the olefin will tend to reduce the rate of
catalysis in most cases; however, useful rates of
homopolymerization or copolymerization can nonetheless be achieved
with some of those olefins. Preferred olefins for such catalysts
include ethylene, propylene, butene, hexene, octene, and
fluoroalkyl substituted olefins, but may also include, in the case
of palladium and some of the more functional group tolerant nickel
catalysts, norbornene, substituted norbornenes (e.g., norbornenes
substituted at the 5-position with halide, siloxy, silane, halo
carbon, ester, acetyl, alcohol, or amino groups), cyclopentene,
ethyl undecenoate, acrylates, vinyl ethylene carbonate,
4-vinyl-2,2-dimethyl-1,- 3-dioxolane, and vinyl acetate.
[0254] In some cases, the Group 8-10 catalysts can be inhibited by
olefins which contain additional olefinic or acetylenic
functionality. This is especially likely if the catalyst is prone
to "chain-running" wherein the catalyst can migrate up and down the
polymer chain between insertions, since this can lead to the
formation of relatively unreactive .pi.-allylic intermediates when
the olefin monomer contains additional unsaturation. Such effects
are best determined on a case-by-case basis, but may be predicted
to some extent through knowledge of how much branching is observed
with a given catalyst in ethylene homopolymerizations; those
catalysts which tend to give relatively high levels of branching
with ethylene will tend to exhibit lower rates when short chain
diene co-monomers are used under the same conditions. Longer chain
dienes tend to be less inhibitory than shorter chain dienes, when
other factors are kept constant, since the catalyst has farther to
migrate to form the .pi.-allyl, and another insertion may intervene
first.
[0255] Similar considerations apply to unsaturated esters which are
capable of inserting and chain-running to form relatively stable
intramolecular chelate structures wherein the Lewis basic ester
functionality occupies a coordination site on the catalyst. In such
cases, short chain unsaturated esters, such as methyl acrylate,
tend to be more inhibitory than long chain esters, such as ethyl
undecenoate, if all other factors are kept constant.
[0256] The term ".alpha.-olefin" as used herein is a 1-alkene with
from 3 to 40 carbon atoms.
[0257] A ".pi.-allyl" group refers to a monoanionic group with
three sp.sup.2 carbon atoms bound to a metal center in a
.eta..sup.3-fashion. Any of the three sp.sub.2 carbon atoms may be
substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, or O-silyl group. Examples of .pi.-allyl groups
include: 70
[0258] The term .pi.-benzyl group denotes an .pi.-allyl group where
two of the sp.sup.2 carbon atoms are part of an aromatic ring.
Examples of .pi.-benzyl groups include: 71
[0259] A "bridging group" refers to an atom or group which links
two or more groups, which has an appropriate valency to satisfy its
requirements as a bridging group, and which is compatible with the
desired catalysis. Suitable examples include divalent or trivalent
hydrocarbyl, substituted hydrocarbyl, heteroatom connected
hydrocarbyl, heteroatom connected substituted hydrocarbyl,
substituted silicon(IV), boron(III), N(III), P(III), and P(V),
--C(O)--, --SO.sub.2--, --C(S)--, --B(OMe)--, --C(O)C(O)--, O, S,
and Se. In some cases, the groups which are said to be "linked by a
bridging group" are directly bonded to one another, in which case
the term "bridging group" is meant to refer to that bond. By
"compatible with the desired catalysis," we mean the bridging group
either does not interfere with the desired catalysis, or acts to
usefully modify the catalyst activity or selectivity.
[0260] The term "weakly coordinating anion" is well known in the
art per se and generally refers to a large bulky anion capable of
delocalization of the negative charge of the anion. The importance
of such delocalization depends to some extent on the nature of the
transition metal comprising the cationic active species, with the
Group 4-6 transition metals requiring less coordinating anions,
such as B(C.sub.6F.sub.5).sub.4.sup.-, than many Group 8-10
transition metal based catalysts, which can in some cases give
active catalysts with BF.sub.4.sup.- counteranions. Weakly
coordinating anions, not all of which would be considered bulky,
include, but are not limited to: B(C.sub.6F.sub.5).sub.4.sup.-,
PF.sub.6.sup.-, BF.sub.4.sup.-, SbF.sub.6.sup.-, (Ph).sub.4B.sup.-
wherein Ph.dbd.phenyl, and Ar.sub.4B.sup.- wherein
Ar.sub.4B.sup.-=tetrakis[3,5-bis(trifluoromethyl)- phenyl]-borate.
The weakly coordinating nature of such anions is known and
described in the literature (S. Strauss et al., Chem. Rev., 1993,
93, 927).
[0261] The term "agostic" is known to those skilled in the art, and
is generally used to refer to a weak bonding interaction between a
C--H bond and a coordinatively unsaturated transition metal. It is
used herein to denote a weak bonding interaction between any or all
of the atoms of the ortho-aryl or ortho-heteroaryl groups of the
ligands described in the twenty-fourth and higher aspects of the
present invention, and a coordinatively unsaturated Group 8-10
transition metal center to which said ligands are complexed. By
"weak bonding interaction" we mean a bond that is sufficiently weak
that it is formed reversibly under olefin polymerization reaction
conditions, so that it does not, for example, preclude the binding
and insertion of olefin monomer.
[0262] The term "ortho" is used herein in the context of the
ligands of the twenty-fourth and higher aspects to denote the
positions which are adjacent to the point of attachment of said
aromatic or heteroaromatic ring to the ligated nitrogen(s). In the
case of a 1-attached, 6-membered ring, we mean the 2- and
6-positions. In the case of a 1-attached, 5-membered ring, we mean
the 2- and 5-positions. In the case of 1-attached, fused ring
aromatic or heteroaromatic rings, we mean the first positions which
can be substituted; for example, in the case of 1-naphthyl, these
would be the 2- and 8-positions; in the case of 9-anthracenyl,
these would be the 1- and 8-positions.
[0263] The term "variable denticity" is used herein in the context
of otherwise bidentate ligands to refer to the reversible formation
of a third binding interaction between the ligand and the Group
8-10 transition metal center to which it is complexed.
[0264] The abbreviation "acac" refers to acetylacetonate. In
general, substituted acetylacetonates, wherein one or more
hydrogens in the parent structure have been replaced by a
hydrocarbyl, substituted hydrocarbyl, or fluoroalkyl, may be used
in place of the "acac". Hydrocarbyl substituted acetylacetonates
may be preferred in some cases when it is important, for example,
to improve the solubility of a (ligand)Ni(acac)BF.sub.4 salt in
mineral spirits.
[0265] The term "half-life for thermal decomposition" refers to the
time required for the catalyst to lose half of its activity, as
determined under substantially non-mass transport limited
conditions.
[0266] The phrase "substantially non-mass transport limited
conditions" refers to the fact that when an ethylene polymerization
reaction is conducted in solution using gaseous ethylene as the
monomer or co-monomer, the rate of dissolution of ethylene in the
liquid phase can often be the turnover-limiting step of the
catalytic cycle, so that the apparent catalyst activity is less
than would be observed under improved mass transport conditions.
Mass transport limitations may typically be reduced by either
increasing the partial pressure of ethylene, improving the
agitation and mixing of the gaseous phase with the liquid phase, or
decreasing the catalyst loading, to the point where the
polymerization reaction rate exhibits a first order dependence on
the amount of catalyst charged to the reactor, and the reaction can
then be considered to be substantially non-mass transport
limited.
[0267] The phrase "apparent catalyst activity" refers to the moles
of monomer consumed per mole of catalyst per unit time, without
consideration of the impact of mass transport limitations.
[0268] The phrase "wherein said catalyst composition exhibits
improved thermal stability" refers to a catalyst composition which
has a half-life for thermal decomposition which is at least 2
times, preferably 5 times, and most preferably 10 times longer than
that observed under substantially non-mass transport limited
conditions for an otherwise structurally identical catalyst
composition lacking the novel ortho-aryl substitution pattern of
the catalysts of the current invention, described in the
twenty-fourth, twenty-fifth, twenty-sixth, twenty-seventh and
twenty-eighth aspects of the current invention.
[0269] The phrase "an amount of hydrogen effective to achieve chain
transfer" refers to the ability of hydrogen to react with an olefin
polymerization catalyst to cleave off a growing polymer chain and
initiate a new chain. In most cases, this is believed to involve
hydrogenolysis of the metal-carbon bond of the growing polymer
chain, to form a metal hydride catalytic intermediate, which can
then react with the olefin monomer to initiate a new chain. In the
context of the current invention, an effective amount is considered
to be that amount of hydrogen which reduces both the number average
molecular weight and the weight average molecular weight of the
polymer by at least 10%, relative to an otherwise similar reaction
conducted in the absence of hydrogen. In this context, "otherwise
similar" denotes that the catalyst, catalyst loading, solvent,
solvent volume, agitation, ethylene pressure, co-monomer
concentration, reaction time, and other process relevant parameters
are sufficiently similar that a valid comparison can be made.
[0270] In general, previously reported catalysts lacking the novel
ortho-aryl substitution pattern of the current invention are far
less productive in the presence of an amount of hydrogen effective
to achieve chain transfer than they are under otherwise similar
conditions without hydrogen. In order to quantify this effect, the
following terms are defined.
[0271] The productivity P is defined as the grams of polymer
produced per mole of catalyst, over a given period of time. The
productivity P.sub.hydrogen is defined as the grams of polymer
produced per mole of catalyst in the presence of an amount of
hydrogen effective to achieve chain transfer, in an otherwise
similar reaction conducted for the same period of time. Catalysts
lacking the novel ortho-aryl substitution pattern of the catalyst
compositions of the current invention typically exhibit ratios
P.sub.hydrogen/P less than or equal to 0.05 under substantially
non-mass transport limited conditions.
[0272] The phrase "improved stability in the presence of an amount
of hydrogen effective to achieve chain transfer" means that the
ratio P.sub.hydrogen/P is at least 0.1 under substantially non-mass
transport limited conditions. Preferred catalysts of the present
invention exhibit a ratio P.sub.hydrogen/P greater than or equal to
0.2 under substantially non-mass transport limited conditions.
Especially preferred catalysts of the present invention exhibit a
ratio P.sub.hydrogen/P greater than or equal to 0.5 under
substantially non-mass transport limited conditions.
[0273] The phrase "one or more olefins" refers to the use of one or
more chemically different olefin monomer feedstocks, for example,
ethylene and propylene.
[0274] The term "single site catalyst" is used as commonly defined,
and preferably refers to an olefin polymerization catalyst which
can be dissolved and activated to form a single active species,
capable of reacting with one or more olefin monomers to form a
polymer having a narrow molecular weight distribution, typically
characterized by a M.sub.w/M.sub.n<4. Many examples of such
catalysts are illustrated herein; additional specific examples are
given in the following references: EP 420,436 (1991); EP 416,815
(1991); Science, 1995, 267, 217; EP 874,005 (1998); J. Am. Chem.
Soc., 1996, 118, 10008; J. Am. Chem. Soc., 1997, 119, 3830, J. Am.
Chem. Soc., 1999, 121, 5797; WO 94/14854, EP 0 532 098 A1; EP 0 641
804 A2, EP 0 816 384 A2; WO 94/11410; WO 94/01471; WO 96/23010,
U.S. Pat. Nos. 5,866,663, 5,886,224, 5,891,963, 5,880,323,
5,880,241, J. Am. Chem. Soc., 1995, 117, 6414; WO 97/02298; WO
98/40374, WO 98/37110, WO 98/47933, WO 98/40420; WO 97/17380, WO
97/48777, WO 97/48739, WO 97/48740; WO 99/02472; WO 98/27124; WO
99/12981; WO 98/30610, WO 98/30609, WO 98/42665, WO 98/42664; U.S.
Pat. Nos. 4,564,647,; 4,752,597; 5,106,804; 5,132,380; 5,227,440;
5,296,565; 5,324,800; 5,331,071; 5,332,706; 5,350,723; 5,399,635;
5,466,766; 5,468,702; 5,474,962; 5,578,537 and 5,863,853. The
entire contents of these patents are incorporated herein by
reference.
[0275] The term "inactive form" is used to refer to a transition
metal complex which serves as a precursor to the active olefin
polymerization catalyst, and has either no polymerization activity
prior to activation by the second compound Y.sup.1, or is at least
10 times less active than the product of activation.
[0276] Compound Y.sup.1 is a compound which is capable of reacting
with said inactive form of said catalyst to generate an active
olefin polymerization catalyst composition, and which also has a
volatility effective to activate said inactive form of said
catalyst under the conditions of a gas phase olefin polymerization
reactor. Examples include trimethylaluminum, dimethylzinc,
Me.sub.nEt.sub.3-nAl (n=0-3), diethylzinc, and Et.sub.2AlCl.
[0277] The phrase "capable of inserting an olefin" refers to a
group Z bonded to the transition metal M, which can insert an
olefin monomer of the type R.sup.1aCH.dbd.CHR.sup.1b to form a
moiety of the type M--CHR.sup.1a--CHR.sup.1b--Z, which can
subsequently undergo further olefin insertion to form a polymer
chain; wherein R.sup.1a and R.sup.1b may independently be H,
hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, silyl,
O(hydrocarbyl), or O(substituted hydrocarbyl), and wherein R.sup.1a
and R.sup.1b may be connected to form a cyclic olefin, provided
that in all cases, the substituents R.sup.1a and R.sup.1b are
compatible with the desired catalysis; wherein additional groups
will be bound to the transition metal M to comprise the actual
catalyst, as discussed in more detail below.
[0278] The phrase "capable of being exchanged with a group on said
volatile second compound Y.sup.1" refers to the ability of some
activators to transfer a group which will be capable of inserting
an olefin to the transition metal, in exchange for a group which is
not capable of inserting an olefin.
[0279] The term "borataaryl" is used to refer to a monoanionic
heterocyclic group of formula XXX: 72
[0280] wherein:
[0281] R.sup.3a-e are each independently H, hydrocarbyl,
substituted hydrocarbyl, heteroatom connected hydrocarbyl,
heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl,
boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two
of R.sup.3a-e may be linked by a bridging group;
[0282] R.sup.4a is hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, or heteroatom connected substituted
hydrocarbyl; and wherein any one of R.sup.3a-e or R.sup.4a may
function as a divalent bridging group to connect the borataaryl to
the remainder of the ligand.
[0283] In general, the catalysts of the present invention can be
made sufficiently sterically hindered that chain transfer is slow
with respect to chain propagation so that a chain of degree of
polymerization (DP) of 10 or more results. For example, in the case
of a catalyst system comprising a catalyst of the type
[(ligand)Fe(T.sup.1a)(L)].sup.+X.sup.-, where T.sup.1a is a
hydrogen atom, hydrocarbyl, or other group capable of inserting an
olefin, L is an olefin or neutral donor group capable of being
displaced by an olefin, X.sup.- is a weakly coordinating anion, and
ligand is a compound of formula h17, the catalyst system reacts
with ethylene to form low molecular weight polymer. However, it is
to be understood that less hindered forms of these catalysts, for
example those derived from h19, generally comprising ligands which
do not contain bulky substituents, can also be used as dimerization
or oligomerization catalysts.
[0284] The degree of steric hindrance at the active catalyst site
required to give slow chain transfer, and thus form polymer,
depends on a number of factors and is often best determined by
experimentation. These factors include: the exact structure of the
catalyst, the monomer or monomers being polymerized, whether the
catalyst is in solution or attached to a solid support, and the
temperature and pressure. Polymer is defined herein as
corresponding to a degree of polymerization, DP, of about 10 or
more; oligomer is defined as corresponding to a DP of 2 to about
10.
[0285] A variety of protocols may be used to generate active
polymerization catalysts comprising transition metal complexes of
various nitrogen, phosphorous, oxygen and sulfur donor ligands.
Examples include (i) the reaction of a Group 4 metallocene
dichloride with MAO, (ii) the reaction of a Group 4 metallocene
dimethyl complex with N,N-diethylanilinium
tetrakis(pentafluorophenyl)borate, (iii) the reaction of a Group 8
or 9 metal dihalide complex of a tridentate N-donor ligand with an
alkylaluminum reagent, (iv) the reaction of a Group 8 or 9 metal
dialkyl complex of a tridentate N-donor ligand with MAO or
HB(3,5-bis(trifluoromethyl)phenyl).sub.4, (v) the reaction of
(Me.sub.2N).sub.4Zr with 2 equivalents of an
N-pyrrol-1-ylsalicylimine, followed by treatment of the product of
that reaction with Me.sub.3SiCl and then a
triisobutylaluminum-modified methylaluminoxane, and (vi) the
reaction of a nickel or palladium dihalide complex of a bidentate
N-donor ligand with an alkylaluminum reagent. Additional methods
described herein include the reaction of (tridentate N-donor
ligand)M(acac)B(C.sub.6F.sub.- 5).sub.4 salts with an alkylaluminum
reagent, where M is Fe(II) or Co(II), and the reaction of
(bidentate N-donor ligand)Ni(acac)X salts with an alkylaluminum
reagent, where X is a weakly coordinating anion, such as
B(C.sub.6F.sub.5).sub.4.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
SbF.sub.6.sup.- and OS(O).sub.2CF.sub.3.sup.-. Cationic
[(ligand)M(.pi.-allyl)].sup.+ complexes with weakly coordinating
counteranions, where M is a Group 10 transition metal, are often
also suitable catalyst precursors, requiring only exposure to
olefin monomer and in some cases elevated temperatures
(40-100.degree. C.) or added Lewis acid, or both, to form an active
polymerization catalyst.
[0286] More generally, a variety of
(ligand).sub.nM(Z.sup.1a)(Z.sup.1b) complexes, where "ligand"
refers to a compound of the present invention, and comprises at
least one nitrogen donor wherein the nitrogen ligated to the metal
M is substituted by a 1-pyrrolyl or substituted 1-pyrrolyl group, n
is 1 or 2, M is a Group 4-10 transition metal, and Z.sup.1a and
Z.sup.1b are univalent groups, or may be taken together to form a
divalent group, may be reacted with one or more compounds,
collectively referred to as compound Y, which function as
co-catalysts or activators, to generate an active catalyst of the
form [(ligand).sub.nM(T.sup.1a)(L)]- .sup.+X.sup.-, where n is 1 or
2, T.sup.1a is a hydrogen atom or hydrocarbyl, L is an olefin or
neutral donor group capable of being displaced by an olefin, M is a
Group 4-10 transition metal, and X.sup.- is a weakly coordinating
anion. When Z.sup.1a and Z.sup.1b are both halide, examples of
compound Y include: methylaluminoxane (herein MAO) and other
aluminum sesquioxides, R.sub.3Al, R.sub.2AlCl, and RAlCl.sub.2
(wherein R is alkyl, and plural groups R may be the same or
different). When Z.sup.1a and Z.sup.1b are both alkyl, examples of
a compound Y include: MAO and other aluminum sesquioxides,
R.sub.3Al, R.sub.2AlCl, RAlCl.sub.2 (wherein R is alkyl, and plural
groups R may be the same or different), B(C.sub.6F.sub.5).sub.3,
R.sup.0.sub.3Sn[BF.sub.4] (wherein R.sup.0 is hydrocarbyl or
substituted hydrocarbyl and plural groups R.sup.0 may be the same
or different), H.sup.+X.sup.-, wherein X.sup.- is a weakly
coordinating anion, for example, tetrakis[3,5-bis(trifluoromethy-
l)phenyl]borate, and Lewis acidic or Bronsted acidic metal oxides,
for example, montmorillonite clay. In some cases, for example, when
Z.sup.1a and Z.sup.1b are both halide or carboxylate, sequential
treatment with a metal hydrocarbyl, followed by reaction with a
Lewis acid, may be required to generate an active catalyst.
Examples of metal hydrocarbyls include: MAO, other aluminum
sesquioxides, R.sub.3Al, R.sub.2AlCl, RAlCl.sub.2 (wherein R is
alkyl, and plural groups R may be the same or different), Grignard
reagents, organolithium reagents, and diorganozinc reagents.
Examples of Lewis acids include: MAO, other aluminum sesquioxides,
R.sub.3Al, R.sub.2AlCl, RAlCl.sub.2 (wherein R is alkyl, and plural
groups R may be the same or different), B(C.sub.6F.sub.5).sub.3,
R.sup.0.sub.3Sn[BF.sub.4] (wherein R.sup.0 is hydrocarbyl or
substituted hydrocarbyl and plural groups R.sup.0 may be the same
or different), and Lewis acidic metal oxides.
[0287] The term "alkylaluminum" is used to refer to compounds
containing at least one alkyl group bonded to Al(III), which are
capable of reacting with a metal complex of the present invention
to generate an active olefin polymerization catalyst. In general,
this will involve exchanging one or more alkyl groups from the
aluminum with a monoanionic atom or group on the metal complex
pro-catalyst. In some cases, a hydride may be directly transferred
from the .beta.-carbon of the aluminum alkyl to said metal complex.
Subsequent abstraction of a second monoanionic atom or group from
the metal complex may also be required to generate a cationic
active catalyst. When the pro-catalyst is already a cationic metal
complex, the role of the alkylaluminum may simply be to exchange an
alkyl or hydride from the aluminum with a monoanionic group, such
as acetylacetonate, attached to the metal complex. In the case of a
cationic .pi.-allyl or .pi.-benzyl pro-catalyst, the alkylaluminum
reagent may, in some cases, simply act as a Lewis acid, to promote
conversion of the .pi.-allyl or .pi.-benzyl to a .sigma.-allyl or
.sigma.-benzyl bonding mode, thereby facilitating binding and
insertion of the olefin monomer. When a cationic pro-catalyst is
used with an alkylaluminum activator or co-catalyst, it should also
be recognized that the starting counteranion (e.g. BF.sub.4.sup.-)
may react with the alkylaluminum reagent to generate a new
counteranion (or a mixture of several different counteranions)
under olefin polymerization reaction conditions. Examples of
alkylaluminum reagents include: MAO, other aluminum sesquioxides,
Me.sub.3Al, EtAlCl.sub.2, Et.sub.2AlCl, R.sub.3Al, R.sub.2AlCl,
RAlCl.sub.2 (wherein R is alkyl, and plural groups R may be the
same or different), and the like.
[0288] The foregoing discussion is intended to illustrate that
there are frequently many ways to generate an active catalyst, and
that in some cases the structure of the active species has not been
fully elucidated. It is, however, an object of this disclosure to
teach that there are a variety of methods wherein the ligands of
the present invention can be reacted with a suitable metal
precursor, and optionally a co-catalyst, to generate an active
olefin polymerization catalyst. Without wishing to be bound by
theory, the inventors also believe that the active catalyst
typically comprises the catalytically active metal, one or more
ligands of the present invention, the growing polymer chain (or a
hydride capable of initiating a new chain), and a site on the metal
adjacent to the metal-alkyl bond of said chain where ethylene can
coordinate, or at least closely approach, prior to insertion. Where
specific structures for active catalysts have been implied herein,
it should be understood that an object of this invention is to
teach and claim that active catalysts comprising the ligands of the
present invention are formed as the reaction products of the
catalyst activation reactions disclosed herein, regardless of the
detailed structures of those active species.
[0289] Active catalysts may, in some cases, be generated from more
than one oxidation state of a given metal. For example, the present
invention describes the use of both Co(III) and Co(II) catalyst
precursors to effect olefin polymerization using MAO or other
alkylaluminum co-catalysts. In some cases, the oxidation state of
the active catalyst has not been unambiguously established, so that
it is not known if the same metal can give rise to active catalysts
with different oxidation states, or if different oxidation state
precursors all give rise to the same oxidation state catalyst under
polymerization conditions. The latter could arise, for example, by
reduction of a Co(III) catalyst precursor to a Co(II) compound
under reaction conditions. Where only one oxidation state of a
given metal has been specified herein, it is therefore to be
understood that other oxidation states of the same metal, complexed
by the ligands of the present invention, can serve as catalyst
precursors or active catalysts. When different oxidation state
complexes of said ligands are used, appropriate changes in the
ancillary ligands or the counteranion must obviously accompany any
change in oxidation level to balance the charge. Examples where
multiple oxidation state precurors are especially likely to be
encountered include, but are not limited to, Ti(III)/Ti(IV),
Fe(III)/Fe(II), and Co(III)/Co(II).
[0290] The catalysts of the present invention may be used in batch
and continuous processes, in solution or slurry or gas phase
processes.
[0291] In some cases, it is advantageous to attach the catalyst to
a solid support. Examples of useful solid supports include:
inorganic oxides, such as talcs, silicas, titania, silica/chromia,
silica/chromia/titania, silica/alumina, zirconia, aluminum
phosphate gels, silanized silica, silica hydrogels, silica
xerogels, silica aerogels, montmorillonite clay and silica co-gels,
as well as organic support materials such as polystyrene and
functionalized polystyrene. (See, for example, S. B. Roscoe et al.,
"Polyolefin Spheres from Metallocenes Supported on Non-Interacting
Polystyrene," 1998, Science, 280, 270-273 (1998)).
[0292] Thus, in a preferred embodiment, the catalysts of the
present invention are attached to a solid support (by "attached to
a solid support" is meant ion paired with a component on the
surface, adsorbed to the surface or covalently attached to the
surface) that has been pre-treated with a compound Y. More
generally, the compound Y and the solid support can be combined in
any order and any number of compound(s) Y can be utilized. In
addition, the supported catalyst thus formed may be treated with
additional quantities of compound Y. In another preferred
embodiment, the compounds of the present invention are attached to
silica that has been pre-treated with an alkylaluminum compound Y,
for example, MAO, Et.sub.3Al, .sup.iBu.sub.3Al, Et.sub.2AlCl, or
Me.sub.3Al.
[0293] Such supported catalysts are prepared by contacting the
transition metal compound, in a substantially inert solvent (by
which is meant a solvent which is either unreactive under the
conditions of catalyst preparation, or if reactive, acts to
usefully modify the catalyst activity or selectivity) with
MAO-treated silica for a sufficient period of time to generate the
supported catalyst. Examples of substantially inert solvents
include toluene, o-difluorobenzene, mineral spirits, hexane,
CH.sub.2Cl.sub.2, and CHCl.sub.3.
[0294] In another preferred embodiment, the catalysts of the
present invention are activated in solution under an inert
atmosphere, and then adsorbed onto a silica support which has been
pre-treated with a silylating agent to replace surface silanols by
trialkylsilyl groups. Methods to pre-treat silicas in this way are
known to those skilled in the art and may be achieved, for example,
by heating the silica with hexamethyldisilazane and then removing
the volatiles under vacuum. A variety of precurors and procedures
may be used to generate the activated catalyst prior to said
adsorption, including, for example, reaction of a
(ligand)Ni(acac)B(C.sub.6F.sub.5).sub.4 complex with Et.sub.2AlCl
in a toluene/hexane mixture under nitrogen; where "ligand" refers
to a compound of the present invention.
[0295] In several cases, metal complexes are depicted herein with
square planar, trigonal bipyramidal, or other coordination,
however, it is to be understood that no specific geometry is
implied.
[0296] The polymerizations may be conducted as solution
polymerizations, as non-solvent slurry type polymerizations, as
slurry polymerizations using one or more of the olefins or other
solvent as the polymerization medium, or in the gas phase. One of
ordinary skill in the art, with the present disclosure, would
understand that the catalyst could be supported using a suitable
catalyst support and methods known in the art. Substantially inert
solvents, such as toluene, hydrocarbons, methylene chloride and the
like, may be used. Propylene and 1-butene are excellent monomers
for use in slurry-type copolymerizations and unused monomer can be
flashed off and reused.
[0297] Temperature and olefin pressure have significant effects on
polymer structure, composition, and molecular weight. Suitable
polymerization temperatures are preferably from about 20.degree. C.
to about 160.degree. C., more preferably 60.degree. C. to about
100.degree. C.
[0298] The catalysts of the present invention may be used alone, or
in combination with one or more other Group 3-10 olefin
polymerization or oligomerization catalysts, in solution, slurry,
or gas phase processes. Such mixed catalysts systems are sometimes
useful for the production of bimodal or multimodal molecular weight
or compositional distributions, which may facilitate polymer
processing or final product properties.
[0299] After the reaction has proceeded for a time sufficient to
produce the desired polymers, the polymer can be recovered from the
reaction mixture by routine methods of isolation and/or
purification.
[0300] In general, the polymers of the present invention are useful
as components of thermoset materials, as elastomers, as packaging
materials, films, compatibilizing agents for polyesters and
polyolefins, as a component of tackifying compositions, and as a
component of adhesive materials.
[0301] High molecular weight resins are readily processed using
conventional extrusion, injection molding, compression molding, and
vacuum forming techniques well known in the art. Useful articles
made from them include films, fibers, bottles and other containers,
sheeting, molded objects and the like.
[0302] Low molecular weight resins are useful, for example, as
synthetic waxes and they may be used in various wax coatings or in
emulsion form. They are also particularly useful in blends with
ethylene/vinyl acetate or ethylene/methyl acrylate-type copolymers
in paper coating or in adhesive applications.
[0303] Although not required, typical additives used in olefin or
vinyl polymers may be used in the new homopolymers and copolymers
of this invention. Typical additives include pigments, colorants,
titanium dioxide, carbon black, antioxidants, stabilizers, slip
agents, flame retarding agents, and the like. These additives and
their use in polymer systems are known per se in the art.
[0304] The ligands of the present invention may be prepared by
methods known to those skilled in the art, wherein a substituted
1-aminopyrrole is condensed with a di-aldehyde or di-ketone to
afford the desired ligands (Scheme II). The requisite substituted
1-aminopyrroles may be prepared by any of a variety of methods,
including those shown in Scheme III. 737475
[0305] .sup..alpha.Reaction conditions. (a) CH.sub.3COCOCH.sub.3
(2.0 equiv), p-Tolensulfonic Acid (p-TsOH) (3 wt %), 60.degree. C.;
(b) 1-amino-2.5-dimethylpyrrole (1.1 equiv), toluene, p-TsOH (3 wt
%), Dean Stark Trap, 110.degree. C.; (c) Toluene, p-TsOH (3 wt %),
Dean Stark Trap. 110.degree. C. 76
[0306] .sup..alpha.Reaction conditions. (a) NaH (1.2 equiv),
R.sup.1COCH.sub.2Br, Toluene, 75.degree. C.; (b) i.
hydrazinecarboxylic acid 2-trimethylsilanyl-ethyl ester
(TMSECNHNH.sub.2), p-TsOH (3 wt %), Toluene, Dean Stark Trap,
110.degree. C., ii. TBAF (2 equiv), THF, 23.degree. C.; (c) NaOH (5
equiv), i-PrOH, H.sub.2O, 60.degree. C.; (d) NaCl, DMSO, H.sub.2O,
160.degree. C.
[0307] Other features of the invention will become apparent in the
following description of working examples, which have been provided
for illustration of the invention and are not intended to be
limiting thereof.
[0308] The molecular weight data presented in the following
examples is determined at 135.degree. C. in 1,2,4-trichlorobenzene
using refractive index detection, calibrated using narrow molecular
weight distribution poly(styrene) standards.
EXAMPLES
Example 1
[0309] Preparation of a32 77
[0310] A 50 mL round bottom flask was charged with
2,5-dimethyl-pyrrol-1-y- lamine (400 mg), 2,3-butanedione (146 mg),
ethanol (10 mL), and 1 drop of formic acid. The mixture was allowed
to stand for 16 h at 22.degree. C.; upon subsequent agitation the
product crystallized and was isolated by vacuum filtration, washed
with cold ethanol and dried to obtain 100 mg of the desired product
as bright yellow rhombic platelets. The combined filtrate and
washings were concentrated and the residue subjected to flash
chromatography (SiO.sub.2, 2.4 vol % Ethyl Acetate (EtOAc)/hexane)
to obtain an additional 172 mg of product. .sup.1H NMR (CDCl.sub.3,
chemical shifts in ppm relative to tetramethyl silane (TMS)): 2.075
(12p, s); 0.211 (6p, s); 5.912 (4p, s). Field Desorption Mass
Spectrometry: m/z 270.
Example 2
[0311] Preparation of the Nickel Dibromide Complex of a32.
[0312] A 50 mL flame-dried Schlenk flask equipped with a magnetic
stir bar and capped by a septum was charged with 92 mg of a32, and
85 mg of (1,2-dimethoxyethane)nickel(II) dibromide in the drybox,
under nitrogen. On the Schlenk line, 6 mL dry, deoxygenated
dichloromethane was added by syringe, and the mixture was stirred
under nitrogen for 3.25 h at 23.degree. C. to afford a dark brown
mixture. This mixture was diluted with 10 mL of dry, deoxygenated
hexane and stirred for 15 min to precipitate the product, after
which the supernatant was removed via a filter paper-tipped
cannula. The brown powdery residue was dried in vacuo to obtain
73.5 mg (54%) of the nickel dibromide complex of a32.
Example 3
[0313] Polymerization of Ethylene with the Nickel Dibromide Complex
of a32 in the Presence of MMAO (modified methylalumoxane; 23%
iso-butylaluminoxane in heptane; 6.42% Al).
[0314] A 250 mL round bottom Schlenk flask equipped with a magnetic
stir bar and capped with a septum was evacuated and refilled with
ethylene, then charged with 100 mL of dry, deoxygenated toluene and
4.0 mL of a MMAO in toluene (6.42% Al) and stirred under 1 atm
ethylene at 0.degree. C. for 15 min. A 2 mL aliquot of a mixture of
3.5 mg of the nickel dibromide complex of a32 in 3.5 mL dry,
deoxygenated dihloromethane was injected, and the mixture was
stirred under 1 atm ethylene at 0.degree. C. A white polyethylene
precipitate was observed within minutes. After 10 minutes, the
mixture was quenched by the addition of acetone (50 mL), methanol
(50 mL) and 6 N aqueous HCl (100 mL). The swollen polyethylene
which separated was isolated by vacuum filtration and washed with
water, methanol and acetone, then dried under reduced pressure (200
mm Hg) at 80.degree. C. for 16 h to obtain 3.95 g of a white
polyethylene. .sup.1H NMR: 3.7 branches/1000 carbon atoms;
M.sub.n=8563. GPC: M.sub.n=9,190; M.sub.w/M.sub.n=3.48.
Example 4
[0315] Ethylene Polymerization with a37,
bis(1,5-cyclooctadiene)nickel(0) and B(C.sub.6F.sub.5).sub.3.
78
[0316] A 200 mL septum-capped Schlenk flask was charged with 12 mg
of N,N'-bis(2,5-dimethylpyrrol-1-yl)oxalamide (a37), 109 mg of
tris(pentafluorophenyl)boron, and 7 mg of
bis(1,5-cyclooctadiene)nickel(0- ) under an Ar atmosphere. On the
Schlenk line, the flask was evacuated and refilled with ethylene.
100 mL of dry, deoxygenated toluene were added with rapid magnetic
stirring at room temperature. Polyethylene precipitated from the
golden-yellow solution. After 11 minutes, the reaction was quenched
by the addition of methanol. The polymer was collected by vacuum
filtration, washed with methanol, and dried in vacuo (200 mm Hg) at
80.degree. C. overnight to yield 0.14 g. .sup.1H NMR: 8.6
branchpoints/1000 carbon atoms; M.sub.n=17,106 g/mol.
Example 5
[0317] Ethylene Polymerization with a37,
bis(1,5-cyclooctadiene)Nickel(0) and B(C.sub.6F.sub.5).sub.3.
[0318] 10 mg of N,N'-bis(2,5-dimethylpyrrol-1-yl)oxalamide, 132 mg
of tris(pentafluorophenyl)boron, and 4.7 mg of
bis(1,5-cyclooctadiene)nickel- (0) were weighed to 500 mL
septum-capped Schlenk flask under an Ar atmosphere. On the Schlenk
line, the flask was evacuated, then provided an ethylene
atmosphere. 200 mL of dry, deoxygenated toluene were added with
rapid magnetic stirring at room temperature. Polyethylene
precipitated from the golden-yellow solution. After 70 minutes, the
reaction was quenched by the addition of methanol. The polymer was
collected by vacuum filtration, washed with methanol, and dried in
vacuo (200 mm Hg) at 80.degree. C. overnight to yield 1.1 g.
.sup.1H NMR: 5.8 branchpoints/1000 carbon atoms. GPC:
M.sub.n=24,400 g/mol; M.sub.w/M.sub.n=8.3.
Example 6
[0319] Ethylene Polymerization with a34,
bis(1,5-cyclooctadiene)Nickel(0) and B(C.sub.6F.sub.5).sub.3.
79
[0320] 10 mg of compound a34, 65 mg of
tris(pentafluorophenyl)boron, and 5 mg of
bis(1,5-cyclooctadiene)nickel(0) were weighed to 20 mL
septum-capped vial under an Ar atmosphere. On the Schlenk line, the
vial was provided an ethylene atmosphere. 10 mL of dry,
deoxygenated toluene were added with rapid magnetic stirring at
room temperature to give a brown mixture. After 20 minutes, the
reaction was quenched by the addition of methanol. The polymer was
collected by vacuum filtration, washed with methanol, and dried in
vacuo (200 mm Hg) at 80.degree. C. overnight to yield 30 mg.
.sup.1H NMR: 27.5 branchpoints/1000 carbon atoms; M.sub.n=2319
g/mol. GPC: M.sub.n=1760 g/mol; M.sub.w/M.sub.n=5.03.
Example 7
[0321] Ethylene Polymerization with a32,
bis(1,5-cyclooctadiene)nickel(0) and B(C.sub.6F.sub.5).sub.3.
[0322] 10 mg of compound a32, 65 mg of
tris(pentafluorophenyl)boron, and 4.2 mg of
bis(1,5-cyclooctadiene)nickel(0) were weighed to 20 mL
septum-capped vial under an Ar atmosphere. On the Schlenk line, the
vial was provided an ethylene atmosphere. 10 mL of dry,
deoxygenated toluene was added with rapid magnetic stirring at room
temperature to give a brown mixture. After 20 minutes, the reaction
was quenched by the addition of methanol. The polymer was collected
by vacuum filtration, washed with methanol, and dried in vacuo (200
mm Hg) at 80.degree. C. overnight to yield 847 mg. .sup.1H NMR:
46.8 branchpoints/1000 carbon atoms; M.sub.n=2347 g/mol. GPC:
M.sub.n=1220 g/mol; M.sub.w/M.sub.n=4.84.
Example 8
[0323] 1-Hexene Polymerization with a32,
bis(1,5-cyclooctadiene)nickel(0) and B(C.sub.6F.sub.5).sub.3.
[0324] 6 mg of compound a32, 24 mg of tris(pentafluorophenyl)boron,
and 3.6 mg of bis(1,5-cyclooctadiene)nickel(0) were weighed to 20
mL septum-capped vial under an Ar atmosphere. On the Schlenk line,
the vial was provided a nitrogen atmosphere. 10 mL of dry 1-hexene
were added with rapid magnetic stirring at room temperature to give
a brown mixture. After 120 minutes, the reaction was quenched by
the addition of methanol. The oily polymer was stirred with
methanol, and then the methanol was decanted away. The polymer was
dried in vacuo (200 mm Hg) at 80.degree. C. overnight to yield 350
mg. .sup.1H NMR: 157.5 branchpoints/1000 carbon atoms; M.sub.n=2220
g/mol. GPC: M.sub.n=1480 g/mol; M.sub.w/M.sub.n=2.22.
Example 9
[0325] 1-Hexene Polymerization with a32,
bis(1,5-cyclooctadiene)nickel(0) and B(C.sub.6F.sub.5).sub.3.
[0326] 4.2 mg of compound a32, 28 mg of
tris(pentafluorophenyl)boron, and 2.2 mg of
bis(1,5-cyclooctadiene)nickel(0) were weighed to 20 mL
septum-capped vial under an Ar atmosphere. On the Schlenk line, the
vial was provided an ethylene atmosphere. 10 mL of dry toluene was
added with rapid magnetic stirring at room temperature to give a
brown mixture. 5 mL of 1-hexene were immediately added, and the
ethylene supply replaced with nitrogen. After 120 minutes, the
reaction was quenched by the addition of methanol. The oily polymer
was stirred with methanol, and then the methanol was decanted away.
The polymer was dried in vacuo (200 mm Hg) overnight to yield 2 g.
.sup.1H NMR: 142.9 branchpoints/1000 carbon atoms; M.sub.n=1952
g/mol. GPC: M.sub.n=1200 g/mol; M.sub.w/M.sub.n=3.79.
Example 10
[0327] Polymerization of Ethylene with the Nickel Dibromide Complex
of a32 in the Presence of MMAO (Methylaluminoxane Modified with 23%
iso-butylaluminoxane in Heptane; 6.42% Al).
[0328] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene. The
reactor was pressurized to 200 psig with ethylene and then relieved
to ambient pressure (2.times.). 3 mL of MMAO solution were added.
With stirring and with the ethylene pressure rising to 200 psig,
2.0 mL of a stock solution (4.30 mg in 17.2 mL CH.sub.2Cl.sub.2) of
the nickel dibromide complex of a32 were injected. The pressure was
maintained at 200 psig. The autoclave temperature was controlled at
30.degree. C. After 10 minutes, the reaction was quenched by the
addition of methanol and the pressure relieved. The swollen
polyethylene which separated was stirred with a mixture of acetone
and aqueous HCl. The polymer was isolated by filtration, washed
with acetone and dried in vacuo (200 mm Hg) overnight to yield 8.3
g. GPC: M.sub.n=1370; M.sub.w/M.sub.n=18.88.
Example 11
[0329] Preparation of a34. 80
[0330] A 100 mL round bottom flask was charged with
2,6-diisopopylaniline (10 g) and 2,3-butanedione (4.87 g). After 6
days, the volatiles were removed in vacuo to give an amber oil (13
g). This oil (5.13 g) was treated with methanol (25 mL), 4-amino
morpholine (1 mL), and 8 drops of formic acid. The mixture was
allowed to stand for 16 h at 22.degree. C. The mixture was
concentrated, and the residue was subjected to flash chromatography
(SiO.sub.2, 8 vol % of EtOAc/hexane) to obtain a34 as a pale yellow
oil (2.5 g) which crystallized upon exposure to methanol. Field
Desorption Mass Spectrometry: m/z 329.
Example 12
[0331] Preparation of a35 81
[0332] A 100 mL round bottom flask was charged with methanol (20
mL), 4-amino morpholine (5 mL), 2,3-butanedione (1.95 mL), and
formic acid (0.2 mL). A precipitate separated almost immediately.
After 3 days, the product was collected by vacuum filtration as
pale green-yellow crystals.
Example 13
[0333] Preparation of a36 82
[0334] A 50 mL round bottom flask was charged with methanol (10
mL), 1-amino-2,6-dimethylpiperidine (2.0 mL), 2,3-butanedione (0.54
mL), and formic acid (0.2 mL). The mixture was stirred at
22.degree. C. for 3 days, and the yellow crystals that separated
were isolated by filtration. Field Desorption Mass Spectrometry:
m/z 306.
Example 14
[0335] Preparation of a30 83
[0336] A 100 mL round bottom flask was provided a nitrogen
atmosphere, a magnetic stirrer, and a reflux condenser, and was
charged with toluene (16 mL), N-aminophthalimide (4.5 g),
2,3-butanedione (1 mL), and formic acid (0.25 mL). The mixture was
heated to and maintained at reflux for 1 hour, then allowed to cool
to room temperature overnight. The white crystals that separated
were isolated by filtration and washed with methanol. Field
Desorption Mass Spectrometry: m/z 374.
Example 15
[0337] Preparation of the Nickel Dibromide Complex of a36
[0338] A 50 mL flame-dried Schlenk flask equipped with a magnetic
stir bar and capped by a septum was charged with 100 mg of a36, and
92 mg of (1,2-dimethoxyethane)nickel(II) dibromide in the drybox,
under nitrogen. On the Schlenk line, 6 mL of dry, deoxygenated
dichloromethane were added by syringe to quickly give a dark brown
mixture. The mixture was stirred under nitrogen for overnight at
23.degree. C. The mixture was then diluted with 10 mL of dry,
deoxygenated hexane, then 28 mg more of a36 were added, and the
mixture was stirred for 1 h more. Some CH.sub.2Cl.sub.2 was
evaporated under a stream of nitrogen to completely precipitate the
product, after which the supernatant was removed via a filter
paper-tipped cannula. The brown powdery residue was dried in
vacuo.
Example 16
[0339] Preparation of the Cobalt Dichloride Complex of a36
[0340] A 50 mL flame-dried Schlenk flask equipped with a magnetic
stir bar and capped by a septum was charged with 100 mg of a36, and
44 mg of cobalt dichoride in the drybox, under nitrogen. On the
Schlenk line, 9 mL of dry, deoxygenated dichloromethane were added
by syringe to slowly give a green supernatant. The mixture was
stirred under nitrogen for overnight at 23.degree. C. The mixture
was then diluted with 10 mL of dry, deoxygenated hexane, then some
CH.sub.2Cl.sub.2 was evaporated under a stream of nitrogen to
completely precipitate the product as green crystals. The
supernatant was removed via a filter paper-tipped cannula, and the
crystals were dried in vacuo to afford the desired complex.
Example 17
[0341] Oligomerization of Ethylene with the Cobalt Dichloride
Complex of a36 in the Presence of MAO (Methylaluminoxane; 10%
Solution in Toluene)
[0342] A 200 mL round bottom Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 9.8 mg of the
cobalt dichloride complex of a36, then evacuated and refilled with
ethylene. The flask was then charged with 50 mL of dry,
deoxygenated toluene and stirred under 1 atm of ethylene at
0.degree. C. for 24 min. 4 mL of MAO (methylaluminoxane; 10%
solution in toluene) were added, and the ethylene was rapidly
consumed to form ethylene oligomers. After 62 minutes, the mixture
was quenched by the addition of acetone (50 mL), methanol (50 mL),
and 6 N aqueous HCl (100 mL).
Example 18
[0343] Preparation of the Nickel Dibromide Complex of a35
[0344] A 200 mL flame-dried Schlenk flask equipped with a magnetic
stir bar and capped by a septum was charged with 103 mg of a35, and
109 mg of (1,2-dimethoxyethane)nickel(II) dibromide in the drybox,
under nitrogen. On the Schienk line, 5 mL of dry, deoxygenated
dichloromethane were added by syringe to quickly give a dark brown
mixture. The mixture was stirred under nitrogen for overnight at
23.degree. C. This mixture was diluted with 10 mL of dry,
deoxygenated hexane to completely precipitate the product, after
which the supernatant was removed via a filter paper-tipped
cannula. The brown powdery residue was dried in vacuo.
Example 19
[0345] Oligomerization of Ethylene with the Nickel Dibromide
Complex of a35 in the Presence of MAO (Methylaluminoxane; 10%
Solution in Toluene)
[0346] A 500 mL round bottom Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 19.5 mg of the
nickel dibromide complex of a35, then evacuated and refilled with
ethylene. The flask was then charged with 50 mL of dry,
deoxygenated toluene and stirred under 1 atm of ethylene at
0.degree. C. for 3 min. 4 mL of MAO (methylaluminoxane; 10%
solution in toluene) were added, and the ethylene was rapidly
consumed. After 130 minutes, the mixture was quenched by the
addition of acetone (50 mL), methanol (50 mL), and 6 N aqueous HCl
(100 mL). A small amount of polyethylene precipitated and, as
evidenced by gas chromatography, a distribution of higher olefins
was produced.
Example 20
[0347] Preparation of a38
[0348] In a 500 mL round bottom flask, 2,4,6-tri-tert-butylaniline
(2.0 g) and 2.6 mL triethylamine were dissolved in dichloromethane
(50 mL) and cooled to 0.degree. C. A mixture of ethyl
chloroglyoxylate (0.85 mL) and dichloromethane (33 mL) was slowly
added via dropping funnel, after which the mixture was stirred at
0.degree. C. for 1 h, and then at 25.degree. C. for 3 h. The
resultant mixture was quenched with 100 mL of water. The aqueous
layer was extracted with 100 mL of dichloromethane. The combined
organic layers were dried over sodium sulfate, filtered, and
concentrated under reduced pressure (20 mm Hg). The residue was
purified by flash chromatography (silica; hexane/EtOAc; linear
gradient). The N-(2,4,6-tri-tert-butylphenyl)oxalamic acid ethyl
ester so obtained (201.5 mg) was reacted with excess hydrazine
hydrate (81 .mu.L) in 5 mL of EtOH at 50.degree. C. for 14 h. The
resultant solid was isolated by filtration and washed with EtOH to
obtain compound a38.
Example 21
[0349] Ethylene Polymerization with a38,
bis(1,5-cyclooctadiene)nickel(0), and B(C.sub.6F.sub.5).sub.3.
[0350] 8.9 mg of compound a38, 85 mg of
tris(pentafluorophenyl)boron, and 4.2 mg of
bis(1,5-cyclooctadiene)nickel(0) were weighed to 20 mL
septum-capped vial under an Ar atmosphere. On the Schlenk line, the
vial was provided an ethylene atmosphere. 10 mL of dry,
deoxygenated toluene were added with rapid magnetic stirring at
room temperature to give a brown mixture. After 61 minutes, the
reaction was quenched by the addition of methanol. The polymer was
collected by vacuum filtration, washed with methanol, and dried in
vacuo (200 mm Hg) at 80.degree. C. overnight to yield 147 mg.
.sup.1H NMR: 74.8 branchpoints/1000 carbon atoms; M.sub.n=8423
g/mol. GPC: M.sub.n=35700 g/mol; M.sub.w/M.sub.n=1.21.
Example 22
[0351] Ethylene Polymerization with a17,
bis(1,5-cyclooctadiene)nickel(0), and B(C.sub.6F.sub.5).sub.3.
[0352] 6.2 mg of compound a17, 30 mg of
tris(pentafluorophenyl)boron, and 1.9 mg of
bis(1,5-cyclooctadiene)nickel(0) were weighed to 20 mL
septum-capped vial under an Ar atmosphere. On the Schlenk line, the
vial was provided an ethylene atmosphere. 10 mL of dry,
deoxygenated toluene were added with rapid magnetic stirring at
room temperature to give a brown mixture. After 15 minutes, the
reaction was quenched by the addition of methanol. The polymer was
collected by vacuum filtration, washed with methanol, and dried in
vacuo (200 mm Hg) at 80.degree. C. overnight to yield 370 mg.
Example 23
[0353] Synthesis of a50 84
[0354] Phenylhydrazine (0.551 mL, 5.6 mmol) was added to a solution
of N-(2,6-dimethyl-phenyl)-2,2,2-trifluoro-acetimidoyl chloride
(263.4 mg, 1.12 mmol) (prepared from TFA, 2,6-dimethyl aniline,
Ph.sub.3P, CCl.sub.4, and Et.sub.3N according to the procedure of
Tamura, K., et al., J. Org. Chem. 1993, 58, 32-35) in toluene (8.0
mL). The resulting solution was heated at reflux for 2 days, cooled
to room temperature and concentrated in vacuo. The residue was
partitioned between H.sub.2O (3 mL) and CH.sub.2Cl.sub.2 (3 mL).
The aqueous layer was further extracted with CH.sub.2Cl.sub.2
(3.times.2 mL).
[0355] The combined organic layers were dried over
Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue
was purified by flash chromatography (SiO.sub.2, 4% EtOAc/Hex) to
afford amidrazone a50 (182 mg, 53%); R.sub.f 0.27 (5% EtOAc/Hex);
.sup.1H NMR (300 MHz, CD.sub.3OD) .delta.7.09-7.14 (m, 5H),
6.79-6.82 (m, 3H), 2.26 (s, 6H); IR (CDCl.sub.3 Film) cm.sup.-1
3383, 3360, 1661, 1604, 1496, 1226, 1164, 1119; FDMS m/z 307
(M.sup.+, 100%).
Example 24
[0356] Polymerization of Ethylene
Ni(COD).sub.2/a50/HB(3,5-CF.sub.3C.sub.6- H.sub.3).sub.4
(Et.sub.2O).sub.2.
[0357] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 20 mg (0.073 mmol) of bis(1,5-cyclooctadiene)
nickel(0) and 22 mg of the ligand of formula CI. The flask was
removed from the box and backfilled with ethylene. Toluene (50 ml)
was added resulting in a yellow solution. After 15 minutes, H.sup.+
B(3,5-CF.sub.3C.sub.6H.sub.3).sub.4 (Et.sub.2O).sub.2 was added as
a solid resulting in an orange solution with modest ethylene uptake
rates. After 1 hour methanol was added to quench the
polymerization. The solvent was removed in vacuo resulting in a
free flowing oil. The .sup.1H NMR is consistent with branched
polyethylene.
Example 25
[0358] Synthesis of the Nickel(II) Dibromide Complex of a50 and
Test for Ethylene Polymerization.
[0359] To a flame dried Schlenk flask equipped with a rubber septum
and a stir bar was added 10 mg (0.0325 mmol) of a50 and 9 mg (0.03
mmol) of (DME)NiBr.sub.2. To the solid mixture, 10 ml of
CH.sub.2Cl.sub.2 was added and the reaction left to stir under an
argon atmosphere for 16 hours. The solvent was removed in vacuo
resulting in a powder. The powder was then taken up in 50 ml of
toluene and the flask backfilled with ethylene. MAO (1.5 ml, 10-wt
% solution in toluene) was added resulting in a purple solution.
After 30 minutes of vigorous stirring at 23.degree. C. and 1
atmosphere ethylene, methanol, acetone and 6M HCl were added to
quench the reaction. The organic layer was isolated and the solvent
removed in vacuo giving an oily solid. .sup.1H NMR confirms the
preparation of a highly branched ethylene homopolymer
(M.sub.n=870).
Example 26
[0360] Polymerization of Ethylene with
Ni(COD).sub.2/b1/B(C.sub.6F.sub.5).- sub.3. 85
[0361] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 10 mg (0.036 mmol) of
bis(1,5-cyclooctadiene)nickel(0), 18.4 mg (0.036 mmol) of
tris(pentafluorophenyl)borane, and 12 mg (0.036 mmol) of b1. The
flask was removed from the box and evacuated and refilled with
ethylene. Toluene (50 ml) was added, resulting in a orange
solution. The polymerization mixture was allowed to stir at room
temperature for 15 hours. After 15 hours, methanol and acetone were
added to quench the reaction and a white flocculent polyethylene
precipitated from solution. The polymer was collected by suction
filtration and dried in the vacuum oven overnight at -100.degree.
C. resulting in 1.1 grams of polyethylene. DSC T.sub.m=41.degree.
C.; GPC M.sub.n=3,500, M.sub.w/M.sub.n=1.76; .sup.1H NMR 65
branches/1000 carbon atoms.
Example 27
[0362] Synthesis of b2 86
[0363] 1-Amino-2,5-diisopropylpyrrole (100 mg) and
3,5-di-tert-butyl-2-hyd- roxybenzaldehyde (126 mg) were weighed to
a septum capped scintillation vial. The vial was well purged with
dry nitrogen gas, then methanol (1 ml) was added. All solids
dissolved after a few minutes, then 4 drops of a solution of formic
acid in methanol (2 drops formic acid in 1-ml methanol) was added.
The reaction was allowed to stand at room temperature for 16 h. The
light yellow crystalline product that separated was collected by
vacuum filtration. The crystals were washed with methanol on the
filter and then dried several hours in vacuo to yield 160 mg.
Example 28
[0364] Representative Ligand Synthesis
[0365] 1-Amino-2-phenyl-5-methylpyrrole (174 mg) and
3,5-di-tert-butyl-2-hydroxybenzaldehyde (236 mg) were weighed to a
scintillation vial then dissolved methanol (2 ml). Formic acid (1
drop) was added. The reaction was allowed to stand at room
temperature for 16 h. The light yellow crystalline product that
separated was collected by vacuum filtration. The crystals were
washed with methanol on the filter and then dried several hours in
vacuo to yield 254 mg.
Example 29
[0366] Polymerization of Ethylene
Ni(COD).sub.2/b2/B(C.sub.6F.sub.5).sub.3
[0367] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 10 mg (0.036 mmol) of
bis(1,5-cyclooctadiene)nickel(0), 18.4 mg (0.036 mmol) of
tris(pentafluorophenyl)borane, and 13.75 mg (0.036 mmol) of the
ligand of formula b2. The flask was removed from the box and
evacuated and refilled with ethylene. Toluene (50 ml) was added,
resulting in a orange solution. The polymerization mixture was
allowed to stir at room temperature for 15 hours. After 15 hours,
methanol and acetone were added to quench the reaction and a white
flocculent polyethylene precipitated from solution. The polymer was
collected by suction filtration and dried in the vacuum oven
overnight at -100.degree. C. resulting in 3.8 grams of
polyethylene. DSC T.sub.m=41.degree. C.; GPC M.sub.n=12,400,
M.sub.w/M.sub.n=1.96; .sup.1H NMR 67 branches/1000 carbon
atoms.
Example 30
[0368] Polymerization of Ethylene
Ni(COD).sub.2/b2/B(C.sub.6F.sub.5).sub.3
[0369] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene. In
an inert atmosphere glove box, a flame dried Schlenk flask equipped
with a magnetic stir bar and a rubber septum was charged with 10 mg
(0.036 mmol) of bis(1,5-cyclooctadiene)nickel(0), 18.4 mg (0.036
mmol) of tris(pentafluorophenyl)borane, and 13.75 mg (0.036 mmol)
of the ligand of formula b2. The flask was removed from the box and
evacuated and refilled with ethylene. Toluene (50 ml) was added
resulting in a orange solution. After 15 minutes, the contents of
the reaction flask were transferred via SS cannula to the
autoclave. The reactor was sealed and pressurized up to 400-psig
ethylene and left to stir at room temperature for 5 hours. After 5
hours, the reactor was vented and the contents poured into a beaker
containing a methanol acetone/mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
-100.degree. C. resulting in 9 grams of polyethylene. DSC
T.sub.m=111.degree. C.; GPC M.sub.n=39,000, M.sub.w/M.sub.n=2.23;
.sup.1H NMR 25 branches/1000 carbon atoms.
Example 31
[0370] Ethylene Polymerization with d1 87
[0371] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 200 ml of dry toluene and a
5-ml solution of tris(pentafluorophenyl)borane (20 mg) in toluene.
The reactor was pressurized to 200-psig ethylene and vented. The
catalyst solution (7.5 mg of d1 in 2 ml of toluene) was added to
the reactor and the autoclave was sealed and pressurized to
200-psig ethylene. After 30 minutes, the reactor was vented and the
contents poured into a beaker containing a methanol/acetone
mixture. The polymer was collected by suction filtration and dried
in the vacuum oven overnight at -100.degree. C. resulting in 0.1
grams of polyethylene. .sup.1H NMR branched polyethylene with a
M.sub.n=3600.
Example 32
[0372] Ethylene Polymerization with d2 88
[0373] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 200 ml of dry toluene and a
5 ml solution of tris(pentafluorophenyl)borane (6.5 mg, 0.027 mmol)
in toluene. The reactor was pressurized to 200-psig ethylene and
vented. The catalyst solution (5.25 mg of d2 in 3 ml of toluene)
was added to the reactor and the autoclave was sealed and
pressurized to 200-psig ethylene. After 60 minutes at 35.degree.
C., the reactor was vented and the contents poured into a beaker
containing a methanol acetone/mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
-100.degree. C. resulting in 0.13 grams of polyethylene. .sup.1H
NMR is consistent with branched polyethylene.
Example 33 to Example 36
[0374] Polymerization of Ethylene with
Ni(COD).sub.2/ligand/B(C.sub.6F .sub.5).sub.3 89
[0375] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene. In
an inert atmosphere glove box, a flame dried Schlenk flask equipped
with a magnetic stir bar and a rubber septum was charged with
between 0.018 mmol and 0.036 mmol of
bis(1,5-cyclooctadiene)nickel(0), between 0.018 mmol and 0.036 mmol
of tris(pentafluorophenyl)borane, and between 0.018 mmol and 0.036
mmol of the ligand in a 1:1:1 ratio. The flask was removed from the
box and evacuated and refilled with ethylene. Toluene (50 ml) was
added. After 10-15 minutes, the contents of the reaction flask were
transferred via SS cannula to the autoclave. The reactor was sealed
and pressurized up to 400-psig ethylene and left to stir at room
temperature for 2-3 hours at 30.degree. C. After the desired
reaction time, the reactor was vented and the contents poured into
a beaker containing a methanol acetone/mixture. The polymer was
collected by suction filtration and dried in the vacuum oven
overnight at -100.degree. C.
1 Branching/ mmol Rxn time PE yield M.sub.w 1000 C T.sub.m Example
Ligand cat (minutes) (g) (.times. 10.sup.-3) (.sup.1H NMR)
(.degree. C.) 33 b3 0.036 180 2.4 1,254 20 128 34 b4 0.036 120 8.2
4.5 64 76 35 b2 0.018 120 2.2 71 33 108 36 b5 0.036 120 0.22 610 10
128
Example 37
[0376] Polymerization of Norbornene with
Ni(COD).sub.2/b1/B(C.sub.6F.sub.5- ).sub.3. 90
[0377] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 10 mg (0.036 mmol) of
bis(1,5-cyclooctadiene)nickel(0), 18.4 mg (0.036 mmol) of
tris(pentafluorophenyl)borane, and 12 mg (0.036 mmol) of the ligand
of formula b1. The flask was removed from the box and evacuated and
refilled with argon. Toluene (50 ml) was added, resulting in a
orange solution. To the polymerization mixture was added a toluene
solution containing 3 g of norbornene. After 1 hour, methanol and
acetone were added to quench the reaction and a white flocculent
polynorbornene precipitated from solution. The polymer was
collected by suction filtration and dried in the vacuum oven
overnight at -100.degree. C. resulting in 2.3 grams of
polynorbornene.
Example 38
[0378] Synthesis of d3 91
[0379] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged in the inert atmosphere glove box with 50
mg (0.10 mmol) [(H.sub.2CC(CO.sub.2Me)CH.sub.2)Ni(.mu.-Br)] and 100
mg of the sodium salt of ligand b3. The flask was removed from the
glove box attached to the Schlenk line and evacuated and refilled
with argon. Diethyl ether (10-ml) was then added and the mixture
was stirred for 2-3 hours. The reaction mixture was transferred via
cannula through a pad of celite to remove the NaBr. The pad of
celite and SS cannula was rinsed with an additional 10-ml of ether.
The solvent was removed in vacuo giving 65 mg of the desired
product d3. [(H.sub.2CC(CO.sub.2Me)CH.sub.2)N- i(.mu.-Br)] was
prepared by the procedure described in Angew. Chem., Int. Ed. Eng.
1966, 5, 151.
Example 39
[0380] Ethylene Polymerization with d3 92
[0381] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and a
5-ml catalyst solution (5 mg of d3 in 5 ml of toluene). The reactor
was pressurized to 200 psig ethylene and tri(phenyl)borane (4 mg,
0.017 mmol) in toluene was added to the reactor via the
high-pressure sample loop while the reactor was being pressurized
to 400 psig. After 120 minutes at 30.degree. C., the reactor was
vented and the contents poured into a beaker containing a methanol
acetone/mixture. The polymer was collected by suction filtration
and dried in the vacuum oven overnight at -100.degree. C. resulting
in 0.350 grams of polyethylene. .sup.1H NMR is consistent with
branched polyethylene (7 branches/1000 carbon atoms and
M.sub.n=97,000).
Example 40 to Example 42
[0382] Polymerization of Ethylene Zr(Me.sub.2).sub.4/b6/Cocatalyst
93
[0383] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 5 mg (1.9.times.10.sup.-5 mol) of
tetrakis(dimethylamino) zirconium and 11 mg (3.7.times.10.sup.-5
mol) of the ligand of formula b6. The flask was removed from the
box and evacuated and refilled with ethylene. Toluene (50 ml) was
added followed by the addition of the desired amount of
cocatalyst(s) (see table for details). The polymerization mixture
was allowed to stir at room temperature and 1 atmosphere ethylene
for 30 minutes. After 30 minutes, methanol, 6 M HCl and acetone
were added to quench the reaction and a white flocculent
polyethylene precipitated from solution. The polymer was collected
by suction filtration and dried in the vacuum oven overnight at
-100.degree. C.
2 mmol Rxn time PE yield Ex. Cocatalysts Zr(Me.sub.2).sub.4
(minutes) (g) M.sub.w T.sub.m (.degree. C.) 40 TMA (0.18 mmol)/
0.019 30 0.13 2300 122 MAO (5.2 mmol) 41 mMAO.sup.a (3.2 mmol)
0.019 30 0.25 1400 118 42 TMA (0.18 mmol)/ 0.019 30 0.24 1700 123
mMAO.sup.a (3.2 mmol) .sup.amMAO-3A from Akzo Nobel.
Example 43
[0384] Polymerization of Ethylene Zr(Me.sub.2).sub.4/b6/mMAO
[0385] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and
3-ml of mMAO-3A (Akzo Nobel). In an inert atmosphere glove box, 5
mg (0.019 mmol) of Zr(Me.sub.2).sub.4 and 11 mg (0.037 mmol) of the
ligand of formula b6 were weighed into a septum-capped vial. To the
vial was added 4-ml of toluene. The resulting solution (2-ml of it)
was added to the autoclave at pressure using a sample loop. The
reactor was pressurized up to 400 psig ethylene and left to stir at
room temperature for 15 minutes. After 15 minutes, the reaction was
quenched by addition of methanol via the sample loop and the
reactor was vented and the contents poured into a beaker containing
a methanol/acetone/6M HCl mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
-100.degree. C. resulting in 8.9 grams of polyethylene. DSC
T.sub.m=125.degree. C.; GPC M.sub.w=36,000.
Example 44
[0386] Synthesis of i1 94
[0387] A flame dried reaction flask equipped with a rubber septum
and a stir bar was charged in the glove box with the ligand b6.
Diethyl ether (10-ml) was added to the flask and the solution was
cooled to -78.degree. C. using a dry ice/acetone bath. To the
solution was added 0.58-ml of n-BuLi resulting in a bright yellow
solution. The mixture was stirred as the flask was warmed to room
temperature over the period of 1 hour. The solution containing the
lithium salt of the ligand was transferred via a SS cannula to
another Schlenk flask that contained a suspension of ZrCl.sub.4.
The mixture was stirred for 3 hours and the solvent was removed in
vacuo. Methylene Chloride (5-ml) was added to solubilize the
resulting Zr-complex and leave the LiCl undissolved. The mixture
was transferred via SS cannula through a pad celite to a new
Schlenk flask. The solvent was again removed in vacuo leaving a
glassy yellow solid that was then recrystallized from hexane. The
.sup.1H NMR is consistent with the desired procatalyst i1.
Example 45 to Example 50
[0388] Polymerization of Ethylene Using Ligand i1 and mMAO-3A (Akzo
Nobel)
[0389] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and
mMAO-3A (Akzo Nobel). In an inert atmosphere glove box, a
septum-capped vial was charged with ligand i1. To the vial was
added 4-ml of toluene. The resulting solution (2-ml of it) was
added to the autoclave at pressure using a sample loop (initial
pressure 200 psig ramped up to 400 psig). The reactor was left to
stir for 15 minutes at the appropriate temperature. After 15
minutes, the reaction was quenched by addition of methanol via the
sample loop. The reactor was vented and the contents poured into a
beaker containing a methanol/acetone/6M HCl mixture. The polymer
was collected by suction filtration and dried in the vacuum oven
overnight.
3 Eq PE yield kg PE Ex. (mMAO) mmol i1 T (.degree. C.) (g) per mmol
i1 M.sub.w T.sub.m(.degree. C.) 45 9400 0.00033 70 5.2 15 98,000
132 46 3100 0.00033 70 4 12 195,000 132 47 1000 0.00033 70 4 12
190,000 135 48 667 0.00033 70 4.2 13 65,000 136 49 300 0.00033 70
4.9 15 -- 135 50 1000 0.00017 50 6.5 38 934,000 131
Example 51
[0390] Preparation of h17. Reaction of 2,6-diacetylpyridine and
1-amino-2,5-diisopropylpyrrole to afford the corresponding
bis(hvdrazone).
[0391] A 65 mL round bottom flask equipped with a magnetic stir bar
was sequentially charged with 2,6-diacetylpyridine (50 mg),
1-amino-2,5-diisopropylpyrrole (115 mg) and ethanol (1 mL). Upon
addition of formic acid (1 drop), the product began to crystallize,
however, TLC analysis indicated both these crystals, and a second
crop isolated from the filtrate, to contain a second compound,
presumed to be the mono(hydrazone). The crystals and filtrate were
therefore recombined and heated at reflux under nitrogen for 2 h,
then let stand at 23 C for 6 days, after which time no
mono(hydrazone) was detected by TLC analysis. The volatiles were
removed in vacuo, and the residue was passed through silica using 4
vol % ethyl acetate in hexane as eluent to afford the
bis(hydrazone) as a yellow powder (67 mg). Field desorption mass
spectrometry: 459 m/z.
Example 52
[0392] Preparation of h16. Reaction of 2,6-diacetylpyridine and
1-amino-2,5-dimethylpyrrole to afford the corresponding
bis(hydrazone).
[0393] A 250 mL round bottom flask was sequentially charged with
2,6-diacetylpyridine (427 mg), 1-amino-2,5-dimethylpyrrole (668
mg), ethanol (10 mL), and formic acid (2 drops), then concentrated
to a volume of ca. 3 mL under a stream of dry nitrogen and stand at
23 C for 16 h. The yellow crystals that separated were collected by
vacuum filtration, washed with cold ethanol (3.times.5 mL), and
dried in vacuo to yield 740 mg (81%). Field desorption mass
spectrometry: 347 m/z.
Example 53
[0394] Preparation of g18. Reaction of 2,6-diacetylpyridine and
4-aminomorpholine to Afford the Corresponding Bis(hydrazone).
[0395] A 2 dram vial was sequentially charged with
2,6-diacetylpyridine (0.810 g), 4-aminomorpholine (1.22 g), ethanol
(1 mL), and formic acid (1 drop) and agitated to afford a crusty
yellow mass. The mixture was triturated with an additional 5 mL
ethanol and then allowed to stand at 23 C for 16 h. The yellow
crystals that separated were collected by vacuum filtration, washed
with ethanol and dried on the filter for several hours to give 1.6
g product.
Example 54
[0396] Preparation of g19. Reaction of 2,6-diacetylpyridine and
1-amino-4-methylpiperazine to Afford the Corresponding
Bis(hydrazone)
[0397] A 2 dram vial was sequentially charged with
2,6-diacetylpyridine (0.830 g), 1-amino-4-methylpiperazine (1.28
g), ethanol (4 mL), and formic acid (1 drop). After 1 h, the
mixture was briefly concentrated under a flow of nitrogen gas until
the product began to crystallize, then let stand at 23 C for 16 h.
The yellow crystals that separated were collected by vacuum
filtration, washed with ethanol, and dried in vacuo for several
hours to obtain 1.2 g of the bis(hydrazone).
Example 55
[0398] Preparation of g17. Reaction of 2,6-diacetylpyridine and
1-amino-2,6-dimethylpiperidine to Afford the Corresponding
Bis(hydrazone)
[0399] A 2 dram vial was sequentially charged with
2,6-diacetylpyridine (0.248 g), 1-amino-2,6-dimethylpiperidine
(0.525 g), ethanol (4 drops), and formic acid (1 drop) to afford a
viscous mixture. After 2 h, 0.6 g ethanol was added to obtain a
homogeneous mixture, which was allowed to stand at 23 C for 16 h.
The yellow crystals that separated were collected by vacuum
filtration, washed with ethanol (2.times.2 mL) and dried to obtain
0.366 g of the bis(hydrazone).
Example 56
[0400] Preparation of the Iron Dichloride Complex of g17
[0401] Under an inert nitrogen atmosphere, a solution of g17 (95.4
mg; 0.249 mmol) in 4 mL THF (tetrahydrofuran) was added dropwise to
a suspension of FeCl.sub.2 in 2 mL THF. Upon addition the yellow
drops immediately turned dark green. The mixture was agitated at
room temperature for 24 h. Hexanes (12 mL) was then added. The
precipitate was allowed to settle and the supernatant removed. The
residue was washed with hexane (2.times.20 mL) and dried in vacuo
to give 87.6 mg of a dark green solid.
Example 57
[0402] Ethylene Polymerization Using the Iron Dichloride Complex of
g17
[0403] Under nitrogen, a 1000-mL Parr.RTM. reactor was charged with
300 mL toluene and heated to 35.degree. C. MMAO in toluene (Akzo
Nobel, 7.12 wt % Al; 2 mL) was added, followed by the title complex
(3.0 mL; 1.18 mM in toluene/CH.sub.2Cl.sub.2 1:1). The vessel was
pressurized to 200 psig and agitated for 54 min. The reaction was
then quenched at elevated pressure with methanol. The reaction
mixture was agitated in the presence of 6M HCl and then filtered.
The collected solid was dried in vacuo to give 21.8 mg polymer.
(T.sub.m=124.degree. C., M.sub.n=330,000, M.sub.w=675,000, 11
branches/1000 C by .sup.1H NMR).
Example 58
[0404] Preparation of the Iron Dichloride Complex of h16
[0405] Under an inert nitrogen atmosphere, a solution of h16 (93.8
mg; 0.270 mmol) in 8 mL THF was added dropwise to a suspension of
FeCl.sub.2 (33.2 mg; 0.262 mmol) in 2 mL THF. Addition of the
ligand caused an immediate color change to dark green. The
suspension was stirred at room temperature for 5 days. Hexane (15
mL) was then added and the solid allowed to settle. The supernatant
was then removed and the solid residue washed twice with 15 mL
hexane. The green solid was dried in vacuo to yield 122 mg.
Example 59
[0406] Polymerization of Ethylene with the iron Dichloride Complex
of h16
[0407] A 300-mL pear-shaped flask was charged with the title
complex (5.0 mg; 10.5 .mu.mol) under nitrogen. The flask was placed
in a room-temperature water bath and the atmosphere replaced with
ethylene. MMAO in toluene (Akzo Nobel, 7.12 wt % Al; 2 mL) was
added under vigorous stirring. No significant color change was
observed. The reaction was quenched after 3.5 min by addition of
methanol and 6M HCl. The slurry was filtered and the cake dried in
a vacuum oven to give 1.37 g (M.sub.n(NMR)=1154, T.sub.m=93.degree.
C., 11 branches/1000 C by .sup.1H NMR). The filtrate was recovered
and extraction with toluene. The combined organic fractions were
dried and the volatiles removed under reduced pressure to give 1.73
g. Combined yield of both fractions: 3.10 g (180,000 TO
h.sup.-1).
Example 60
[0408] Polymerization of Ethylene with the Iron Dichloride Complex
of h16 at Elevated Pressure (200 psig)
[0409] Under nitrogen, a 1000-mL Parr.RTM. reactor was charged with
300 mL toluene and heated to 45.degree. C. A solution of the title
complex (2.0 mL; 0.749 mM in toluene) was added, followed by MMAO
in toluene (Akzo Nobel, 7.12 wt % Al; 2 mL). The vessel was
pressurized to 200 psig and agitated for 15 min. The reaction was
then quenched at elevated pressure with methanol. The reaction
mixture was agitated in the presence of 6M HCl and then filtered.
The collected solid was dried in a vacuum oven to give 28.62 g of
polymer. The filtrate was recovered and extracted with toluene. The
combined organic fractions were dried over sodium sulfate and the
volatiles removed in vacuo, yielding 14.90 g additional material.
The combined yield of the reaction was 43.52 g
(4.14.times.10.sup.-6 TO h.sup.-1).
Example 61
[0410] Preparation of the Supported Iron Dichloride Complex of
h16
[0411] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with 1.70 g MAO-treated silica (purchased from
Witco TA 02794/HL/04) and the iron dichloride complex of h16 (8.0
mg; 17 .mu.mol) under a nitrogen inert atmosphere. The flask was
equipped with a magnetic stirring bar and a septum cap. The solid
was cooled to 0.degree. C. and dichloromethane (15 mL) was added
under vigorous stirring. After 1 hour, the volatiles were removed
in vacuo. The resulting solid was stored at -30.degree. C. Yield:
1.57 g. Loading of Fe complex/g support: 15.2 .mu.mol/g (based on
Fe-content analysis).
Example 62
[0412] Polymerization of Ethylene with the Supported Iron
Dichloride Complex of h16
[0413] A 300-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with 227 mg of the title catalyst under
nitrogen. Toluene (100 mL) was then added and the atmosphere
immediately replaced with ethylene. The suspension was agitated for
90 min, at room temperature, under 1 atm ethylene. The reaction was
then quenched with methanol and 6M HCl. The mixture was filtered,
the solid collected and dried in a vacuum oven (133 mg; GPC
M.sub.n=810, M.sub.w/M.sub.n=6.4; NMR M.sub.n=1379 (77% terminal
olefin); Tm=119.degree. C.). The filtrate was also recovered and
extracted with toluene. The organic layers were combined and the
volatiles removed under reduced pressure. The residue was dried in
a vacuum oven (0.07 g; GPC M.sub.n=380, M.sub.w/M.sub.n=20; NMR
M.sub.n=531 (98% terminal olefin); Tm=63.degree. C.).
Example 63
[0414] Preparation of the Cobalt Dichloride Complex of h16
[0415] Under an inert nitrogen atmosphere, h16 (107.7 mg; 0.310
mmol) in 10 mL THF was added dropwise to a suspension of CoCl.sub.2
(39.1 mg; 0.301 mmol) in 2 mL THF. No color change was observed.
The suspension was agitated for 5 days. Hexane (15 mL) was added
and the solid allowed to settle. The supernatant was removed and
the solid subsequently washed with 2.times.15 mL hexane. The solid
residue was dried in vacuo and a mustard yellow solid was
collected.
Example 64
[0416] Polymerization of Ethylene with the Cobalt Dichloride
Complex of h16
[0417] Under nitrogen, a 300-mL pear-shaped flask was charged with
the title complex (8.9 mg; 19 .mu.mol) and 100 mL toluene. The
flask was placed in a room-temperature water bath and the
atmosphere replaced with ethylene. MMAO in toluene (Akzo Nobel,
7.12 wt % Al; 2 mL) was added under vigorous stirring, leading to
an immediate color change to purple. The reaction was quenched
after 3.5 min by addition of methanol and 6M HCl. The slurry was
filtered and the cake dried in a vacuum oven to give 823 mg
(M.sub.n (NMR)=948, T.sub.m=97.degree. C.). The filtrate was
recovered and extraction with toluene. The combined organic
fractions were dried and the volatiles removed under reduced
pressure to give 0.91 g. Combined yield of both fractions: 1.73 g
(56,900 TO h.sup.-1).
Example 65
[0418] Preparation of the Iron Dichloride Complex of g18
[0419] Under an inert nitrogen atmosphere, g18 (96.6 mg; 0.291
mmol) in 5 mL THF was added to a suspension of FeCl.sub.2 (35.2 mg;
0.278 mmol) in 2 mL THF. The suspension was agitated for 4 days.
Hexane (15 mL) was added and the solid allowed to settle. The
supernatant was removed and the solid subsequently washed with
2.times.20 mL hexane. The solid residue was dried in vacuo and a
dark green solid was collected (101 mg).
Example 66
[0420] Polymerization of Ethylene with the Iron Dichloride Complex
of g18
[0421] A 300-mL pear-shaped flask was charged with the title
complex (2.7 mg; 5.9 .mu.mol) under nitrogen. The atmosphere was
replaced with ethylene. MMAO in toluene (Akzo Nobel, 7.12 wt % Al;
2 mL) was subsequently added under vigorous stirring. No ethylene
uptake was apparent. The reaction was quenched after 20 min by
addition of methanol and 6M HCl.
Example 67
[0422] Preparation of the Cobalt Dichloride Complex of g18
[0423] Under an inert nitrogen atmosphere, g18 (91.8 mg; 0.277
mmol) in 5 mL THF was added to a suspension of CoCl.sub.2 (34.9 mg;
0.277 mmol) in 2 mL THF. The suspension was agitated for 4 days.
Hexane (15 mL) was added and the solid allowed to settle. The
supernatant was removed and the solid subsequently washed with
2.times.20 mL hexane. The solid residue was dried in vacuo and an
orange solid was collected (119 mg).
Example 68
[0424] Polymerization of Ethylene with the Cobalt Dichloride
Complex of g18
[0425] A 300-mL pear-shaped flask was charged with the title
complex (4.5 mg; 9.8 .mu.mol) under nitrogen. The atmosphere was
replaced with ethylene. MMAO in toluene (Akzo Nobel, 7.12 wt % Al;
2 mL) was subsequently added under vigorous stirring. The solution
immediately turned purple. The reaction was quenched after 60 min
by addition of methanol and 6M HCl. An organic extraction with
toluene was performed on the reaction mixture. The organic
fractions were combined and the volatiles removed in vacuo. The
residue was heated and dried in vacuo to give 0.09 g polymer (327
TO h.sup.-1).
Example 69
[0426] Preparation of the Iron Dichloride Complex of g19
[0427] Under an inert nitrogen atmosphere, g19 (83.8 mg; 0.234
mmol) in 5 mL THF was added to a suspension of FeCl.sub.2(28.2 mg;
0.222 mmol) in 2 mL THF. An immediate color change to green was
observed. The suspension was agitated for 24 hours. Hexane (15 mL)
was added and the solid allowed to settle. The supernatant was
removed and the solid subsequently washed with 2.times.20 mL
hexane. The solid residue was dried in vacuo and a dark green solid
was collected (96.5 mg).
Example 70
[0428] Polymerization of Ethylene with the Iron Dichloride Complex
of g19
[0429] A 300-mL pear-shaped flask was charged with the title
complex (5.9 mg; 12 .mu.mol) under nitrogen. The atmosphere was
replaced with ethylene. MMAO in toluene (Akzo Nobel, 7.12 wt % Al;
2 mL) was subsequently added under vigorous stirring. No ethylene
uptake was apparent. The reaction was quenched by addition of
methanol and 6M HCl.
Example 71
[0430] Preparation of the Cobalt Dichloride Complex of g19
[0431] Under an inert nitrogen atmosphere, g19 (42.3 mg; 0.118
mmol) in 5 mL THF was added to a suspension of CoCl.sub.2(14.9 mg;
0.115 mmol) in 2 mL THF. The suspension was agitated for 24 hours.
Hexane (15 mL) was added and the solid allowed to settle. The
supernatant was removed and the solid subsequently washed with
2.times.20 mL hexane. The solid residue was dried in vacuo and an
orange-brown solid was collected (48.6 mg).
Example 72
[0432] Polymerization of Ethylene with the Cobalt Dichloride
Complex of g19
[0433] A 300-mL pear-shaped flask was charged with the title
complex (7.2 mg; 15 .mu.mol) under nitrogen. The atmosphere was
replaced with ethylene. MMAO in toluene (Akzo Nobel, 7.12 wt % Al;
2 mL) was subsequently added under vigorous stirring. The solution
immediately turned purple. The reaction was quenched after 20 min
by addition of methanol and 6M HCl. An organic extraction with
toluene was performed on the reaction mixture. The organic
fractions were combined and the volatiles removed in vacuo. The
residue was heated and dried in vacuo to give 0.06 g polymer (433
TO h.sup.-1).
Example 73
[0434] Preparation of the Iron Dichloride Complex of h17
[0435] Under an inert nitrogen atmosphere, a solution of h17 (26.6
mg; 57.9 .mu.mol) in 5 mL THF was added dropwise to a suspension of
FeCl.sub.2 (7.2 mg; 57 .mu.mol) in 2 mL THF. The solution gradually
turned green over 12 hours. Addition of hexane (15 mL) presumably
led to decomposition of the complex, as evidenced by the resulting
white solid suspended in a yellow solution. THF (10 mL) was then
added to the mixture that was subsequently pumped to dryness under
a reduced atmosphere. The solid was then suspended in THF (10 mL)
and the suspension allowed to stir at room temperature for 18
hours. The volatiles were then removed in vacuo to give a green
solid.
Example 74
[0436] Polymerization of Ethylene with the Iron Dichloride Complex
of h17
[0437] Under nitrogen, a 1000-mL Parr.RTM. reactor was charged with
300 mL toluene and 0.45 mL of MMAO (Akzo Nobel, 7.12 wt % Al) and
heated to 50.degree. C. A solution of the title complex (2.0 mL;
0.17 mM in toluene:dichloromethane 1:1) was introduced via an
injection loop as the vessel was being pressurized. The solution
was vigorously agitated for 30 min. The reaction was then quenched
at elevated pressure with methanol. The solution was then
transferred to a beaker and stirred with 6M HCl. The solution was
extracted with toluene. The organic layers were combined and the
volatiles removed on a rotary evaporator to give, after drying in
an oven, 0.83 g of product (174,000 TO/h).
Example 75
[0438] Preparation of the Cobalt Dichloride Complex of h17
[0439] Under an inert nitrogen atmosphere, a solution of h17 (19.3
mg; 42.0 .mu.mol) in 7 mL THF was added to a suspension of
CoCl.sub.2 (5.3 mg; 41 .mu.mol) in 2 mL THF. The solution gradually
turned amber and within 45 min, had evolved to an olive-green
color. The mixture was stirred at room temperature for about 18 h
after which, the volatiles were removed in vacuo.
Example 76
[0440] Polymerization of Ethylene with the Cobalt dichloride
Complex of h17
[0441] Under nitrogen, a 300-mL pear-shaped flask was charged with
the title complex (3.5 mg; 5.9 .mu.mol) and 100 mL toluene. The
atmosphere was then replaced with ethylene. The flask was placed in
a room temperature water bath and MMAO in toluene (Akzo Nobel, 7.12
wt % Al; 2 mL) was added under vigorous stirring, leading to an
immediate color change to purple. The reaction medium rapidly
turned cloudy. The reaction was quenched after 4 min by addition of
methanol and 6M HCl. The slurry was filtered and the cake dried in
a vacuum oven to give 628 mg polymer. The filtrate was recovered
and extracted with toluene. The combined organic fractions were
dried and the volatiles removed under reduced pressure to give 335
mg. Combined yield of both fractions: 963 mg (87,300 TO
h.sup.-1).
Example 77
[0442] Synthesis of b4 95
[0443] A solution of
1-Amino-2-methyl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester
(208 mg, 0.89 mmol) in toluene (17.6 mL) was treated with
pyridinium p-toluenesulfonate (2.4 mg) and
3,5-di-tert-butyl-2-hydro- xy-benzaldehyde (238 mg, 0.975 mmol) at
room temperature. The resulting solution was immersed in a
130.degree. C. oil bath, and stirred vigorously under Ar for 1.5 h.
The solution was cooled to room temperature, and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
30%-60% CH.sub.2Cl.sub.2/Hex) to afford b4 (190 mg, 46%).
Example 78
[0444] Synthesis of b5 96
[0445] A solution of
1-Amino-5-tert-butyl-2-phenyl-1H-pyrrole-3-carboxylic acid ethyl
ester (240 mg, 0.79 mmol) in toluene (14.2 mL) was treated with
pyridinium p-toluenesulfonate (1.7 mg) and
3,5-di-tert-butyl-2-hydro- xy-benzaldehyde (160 mg, 0.69 mmol) at
room temperature. The resulting solution was immersed in a
130.degree. C. oil bath, and stirred vigorously under Ar for 6 h.
The reaction was cooled to room temperature and allowed to stand
under Ar overnight. A second portion of
3,5-di-tert-butyl-2-hydroxy-benzaldehyde (65 mg, 0.28 mmol) was
added and the reaction heated at reflux for 3 h, cooled to room
temperature and concentrated in vacuo. The residue was purified by
flash chromatography (SiO.sub.2, 2%-15% EtOAc/Hex, where EtOAc and
Hex refer to ethyl acetate and hexane, respectively) to afford b5
(230 mg, 58%).
Example 79
[0446] Synthesis of b3
[0447] A solution of
1-Amino-5-tert-butyl-2-methyl-1H-pyrrole-3-carboxylic acid ethyl
ester (258 mg, 1.15 mmol) in toluene (20.8 mL) was treated with
pyridinium p-toluenesulfonate (2.5 mg) and
3,5-di-tert-butyl-2-hydro- xy-benzaldehyde (234 mg, 1.0 mmol) at
room temperature. The flask was fitted with a Dean Stark trap, and
immersed in a 150.degree. C. oil bath for 6 h, after which the
temperature was raised to 170.degree. C. for one hour. The reaction
was cooled to room temperature and allowed to stand under Ar
overnight, then treated with a second portion of
3,5-di-tert-butyl-2-hydroxy-benzaldehyde (70 mg, 0.30 mmol) and
heated to 150.degree. C. in an oil bath for 2.5 h. The solution was
cooled to room temperature, and concentrated in vacuo. The residue
was purified by flash chromatography (SiO.sub.2, 2%-15% EtOAc/Hex)
to afford b3 (325.5 mg, 74%).
Example 80
[0448] Preparation of the Iron Dichloride Complex of h19
[0449] A solution of h19 (129.7 mg; 0.275 mmol) in 6 mL THF was
added to a suspension of FeCl.sub.2 (33.4 mg; 0.264 mmol) at room
temperature. The color of the supernatant immediately turned
emerald-green. The suspension was agitated for 5 days. The
volatiles were removed in vacuo to give a dark green solid.
Example 81
[0450] Preparation of the Cobalt Dichloride Complex of h19
[0451] A solution of h19 (96.2 mg; 0.204 mmol) in 6 mL THF was
added to a suspension of CoCl.sub.2 (25.5 mg; 0.196 mmol) at room
temperature. The color of the supernatant turned amber/orange
within 30 min. The suspension was agitated for 6 days. The solid
was then allowed to settle and the supernatant removed. The
residual solid was dried in vacuo to give a brownish solid.
Example 82
[0452] Preparation of the Iron Dichloride Complex of h20
[0453] A solution of h20 (86.2 mg; 0.270 mmol) in 8 mL THF was
added to a suspension of FeCl.sub.2 (33.0 mg; 0.260 mmol) at room
temperature. The suspension was agitated for 8 days. The volatiles
were removed in vacuo to give a brownish solid.
Example 83
[0454] Preparation of the Cobalt Dichloride Complex of h20
[0455] A solution of h20 (40.6 mg; 0.127 mmol) in 6 mL THF was
added to a suspension of CoCl.sub.2 (15.8 mg; 0.122 mmol) at room
temperature. The suspension was agitated for 8 days. The volatiles
were removed in vacuo and the residual solid dried in vacuo.
Example 84
[0456] Preparation of the Iron Dichloride Complex of h21
[0457] A solution of h21 (77.4 mg; 0.130 mmol) in 8 mL THF was
added to a suspension of FeCl.sub.2 (15.8 mg; 0.125 mmol) at room
temperature. The suspension was agitated for 8 days. The volatiles
were removed in vacuo to give a brownish solid.
Example 85
[0458] Preparation of a Stock Solution of the Iron Dichloride
Complex of h21
[0459] A solution of h21 (4.8 mg; 20 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to a suspension of FeCl.sub.2.x THF
(12.2 mg; 20.4 .mu.mol) at room temperature. The suspension was
agitated for 8 days. Dichloromethane was added to give a total
volume of 10 mL (2.04 mM).
Example 86
[0460] Preparation of a Stock Solution of the Iron Complex of
h21
[0461] A solution of h21 (8.7 mg; 15 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to a suspension of
bis(acetylacetonato)iron (3.7 mg; 15 .mu.mol) at room temperature.
The suspension was agitated for 8 days. Dichloromethane was added
to give a total volume of 20 mL (0.75 mM).
Example 87
[0462] Preparation of the Cobalt Dichloride Complex of h21
[0463] A solution of h21 (89.4 mg; 0.150 mmol) in 6 mL THF was
added to a suspension of CoCl.sub.2 (18.7 mg; 0.144 mmol) at room
temperature. The suspension was agitated for 8 days. The volatiles
were removed in vacuo and the residual solid dried in vacuo.
Example 88
[0464] Preparation of a Stock Solution of the Cobalt Complex of
h21
[0465] A solution of h21 (4.1 mg; 6.9 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to
bis(1,1,1,5,5,5,-hexafluoroacetylacetonato)cobalt.2.5 H.sub.2O (3.6
mg; 6.9 .mu.mol) in 3 mL CH.sub.2Cl.sub.2 at room temperature. The
purple solution readily turned orange. Dichloromethane was added to
give a total volume of 20 mL (0.35 mM).
Example 89
[0466] Preparation of a Cobalt Complex of h22
[0467] A solution of h22 (8.1 mg; 16 .mu.mol) in 5 mL n-butanol was
added to bis(acetylacetonato)cobalt (4.1 mg; 16 .mu.mol) in 3 mL
n-butanol at room temperature. The suspension gradually turned
homogeneous. The volatiles were removed in vacuo.
Example 90
[0468] Preparation of an Iron Complex of h23
[0469] A solution of h23 (21.4 mg; 33.3 .mu.mol) in 2 mL THF was
added to FeCl.sub.2 (4.2 mg; 33 .mu.mol) in 4 mL THF at room
temperature. After 1 day, n-butanol (10 mL) was added and the
resulting mixture heated with a constant flow of nitrogen to strip
off any volatiles. The residue was redispersed in n-butanol and a
suspension TIPF.sub.6 (11.6 mg; 33.3 .mu.mol) in 5 mL n-butanol was
added. The suspension was stirred for 1 day and the volatiles then
removed under reduced pressure.
Example 91
[0470] Preparation of a Stock Solution of the Iron Complex of
h23
[0471] A solution of h23 (11.7 mg; 20.2 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to bis(acetylacetonato)iron (4.9 mg; 19
.mu.mol) in 3 mL CH.sub.2Cl.sub.2 at room temperature. The purple
solution readily turned orange. Dichloromethane was added to give a
total volume of 15 mL (1.29 mM).
Example 92
[0472] Preparation of a Stock Solution of the Cobalt Complex of
h23
[0473] A solution of h23 (9.6 mg; 17 .mu.mol) in 3 mL
CH.sub.2Cl.sub.2 was added to
bis(1,1,1,5,5,5,-hexafluoroacetylacetonato)cobalt (8.5 mg; 16
.mu.mol) in 2 mL CH.sub.2Cl.sub.2 at room temperature. The purple
solution readily turned orange. Dichloromethane was added to give a
total volume of 10 mL (1.7 mM).
Example 93
[0474] Preparation of a Stock Solution of the Iron Dichloride
Complex of h24
[0475] A solution of h24 (10.0 mg; 20.9 .mu.mol) in 4 mL
CH.sub.2Cl.sub.2 was added to FeCl.sub.2.x THF (4.9 mg; 21 .mu.mol)
in 2 mL CH.sub.2Cl.sub.2 at room temperature. The suspension slowly
turned orange. Dichloromethane was added to give a total volume of
20 mL (1.0 mM).
Example 94
[0476] Preparation of a Stock Solution of the Iron Complex of
h24
[0477] A solution of h24 (44.8 mg; 93.0 .mu.mol) in 10 mL
CH.sub.2Cl.sub.2 was added to bis(acetylacetonato)iron (23.3 mg;
91.7 .mu.mol) in 10 mL CH.sub.2Cl.sub.2 at room temperature. The
purple solution readily turned orange and was used as a stock
solution for polymerization (4.59 mM).
Example 95
[0478] Preparation of a Stock Solution of the Iron Complex of
h24
[0479] A solution of h24 (4.0 mg; 8.3 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to
bis(1,1,1,5,5,5,-hexafluoroacetylacetonato)iron (3.4 mg; 7.2
.mu.mol) (prepared as described in J. Chem. Soc. (A) 1970, 3153 by
F. G. A. Stone et al.) in 3 mL CH.sub.2Cl.sub.2 at room
temperature. The purple solution readily turned orange.
Dichloromethane was added to give a total volume of 10 mL (0.72
mM).
Example 96
[0480] Preparation of a Stock Solution of the Cobalt Complex of
h24
[0481] A solution of h24 (4.0 mg; 8.3 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to
bis(1,1,1,5,5,5,-hexafluoroacetylacetonato)cobalt.2.5 H.sub.2O (4.4
mg; 8.5 .mu.mol) in 4 mL CH.sub.2Cl.sub.2 at room temperature.
Dichloromethane was added to give a total volume of 20 mL (0.42
mM).
Example 97
[0482] Preparation of a Stock Solution of the Iron Complex of
h25
[0483] A solution of h25 (4.3 mg; 18 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to a suspension of FeCl.sub.2.x THF
(11.1 mg; 20.3 .mu.mol) at room temperature. The suspension was
agitated for 8 days. Dichloromethane was added to give a total
volume of 10 mL (1.83 mM).
Example 98
[0484] Preparation of a Stock Solution of the Cobalt Complex of
h25
[0485] A solution of h25 (6.5 mg; 12 .mu.mol) in 5 mL
CH.sub.2Cl.sub.2 was added to
bis(1,1,1,5,5,5,-hexafluoroacetylacetonato)cobalt.2.5 H.sub.2O (5.5
mg; 11 .mu.mol) in 3 mL CH.sub.2Cl.sub.2 at room temperature. The
purple solution readily turned orange. Dichloromethane was added to
give a total volume of 15 mL (0.71 mM).
Example 99
[0486] High-pressure Polymerization of Ethylene Using a Catalyst
Prepared as in Example 91
[0487] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 44.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of an iron complex prepared as in
Example 91 (0.68 .mu.mol total Fe) was added under pressure through
an injection loop by slightly depressurizing the reactor. Upon
injection, the internal temperature rose to 47.degree. C. The
reaction mixture was agitated under 200 psi ethylene for 5 min and
then quenched with MeOH under elevated pressure. The reactor was
vented and the mixture further treated with 6M HCl. A liquid-liquid
extraction was performed on the slurry. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 4.26 g
polyethylene. GPC: M.sub.n=29,500; M.sub.w/M.sub.n=2.4.
Example 100 to Example 125
[0488] High Pressure Polymerization of Ethylene Using Pro-catalysts
Prepared as in Examples 80-98
[0489] The examples summarized in Table I were generated following
the procedure of Example 99.
4 TABLE 1 Catalyst Toluene-insoluble Prepared Fraction Toluene
soluble as in Qty of metal Pressure (psi); NMR Mn Fraction: NMR Mn;
Example # Example # used (.mu.mol) Temperature (.degree. C.) Time
(min) Total yield (g) GPC Mn % terminal olefin Tm % terminal olefin
100 56.sup..function. 3.5 200; 35 54 0.022 330K -- 124 -- 101
58.sup..English Pound. 0.016 200; 60 60 12.22 590 655; >99% 89
362; >99% 102 63.sup..English Pound. 0.21 200; 62 60 44.85 660
585; >99% 89 355; 98% 103 67.sup..function. 9.8 15; RT 60 0.09
-- -- -- 400.sup.GPC Mn 104 71.sup..function. 15 15; RT 20 0.06 460
-- -- 666 105 73.sup..function. 0.68 200; 50 15 14.78 600 1694; 99%
127 -- 106 75.sup..function. 42 15; RT 4 0.96 2960 3374; 83% 132
869; >99% 107 80.sup..function. 3.8 15; RT 3 0.57 -- -- -- 830;
97% 108 81.sup..function. 3.5 15; RT 3 10.63 -- -- -- 209; 93% 109
82.sup..function. 7.2 15; RT 10 3.26.sup..dagger. -- -- -- 175; 93%
110 83.sup..function. 7.6 15; RT 10 2.08.sup..dagger-dbl. -- -- --
183; 93% 111 84.sup..function. 7.9 15; RT 10 0.21 3220 1362;
>99% -- 112 85.sup..English Pound. 1.4 200; 59 5 1.23 1270 2848;
>99% 131 -- 113 86.sup..English Pound. 1.5 200; 59 60 3.77 3890
3281; 90% 132 360; >99% 114 87.sup..function. 3.7 15; RT 10 0.01
-- 472; 93% -- -- 115 88.sup..English Pound. 0.70 200; 60 60 0.14
110 292; >99% -- -- 116 89.sup..English Pound. 16 15; RT 15 0.23
74.3K 28.0K; 93% 138 1968; 83% 117 90.sup..English Pound. 33 15; RT
15 0.59 23.4K -- 137 -- 118 91.sup..English Pound. 0.68 200; 47 5
4.26 61.8K >75K 136 -- 119 92.sup..English Pound. 5.8 15; RT 15
0.097 15.4K -- 138 -- 120 93.sup..English Pound. 0.85 200; 57 5
2.65 6320 15.8K; 90% 134 5105; >99% 121 94.sup..English Pound.
0.46 600; 58 60 2.99 800 2873; >99% 132 414; 17% 122
95.sup..English Pound. 1.44 200; 58 58 1.21 4240 10.2K; 67% 132
500; 99% 123 96.sup..English Pound. 0.21 200; 47 60 7.10 5160 4838;
99% 133 1229; 99% 124 97.sup..English Pound. 3.6 200; 43 60 0.25
36.4K >75K 139 -- 125 98.sup..English Pound. 2.1 15; RT 6 0.22
300 4624; 10% 133 -- .sup..English Pound.MAO (10 wt % Al in
toluene)was used as cocatalyst. .sup..function.MMAO (modified
methylalumoxane; 23% iso-butylaluminoxane in heptane; 6.4% Al) was
used as cocatalyst. .sup..sctn. Total calculated yield from the
isolated yield using GC analysis. Schultz-Flory constant = 0.52.
.sup..dagger. Total calculated yield from the isolated yield using
GC analysis. Schultz-Flory constant = 0.61. .sup..dagger-dbl. Total
calculated yield from the isolated yield using GC analysis.
Schultz-Flory constant = 0.61.
Example 126
[0490] Preparation of the Supported Cobalt Dichloride Complex of
h17
[0491] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with 2.05 g MAO-treated silica (purchased from
Witco TA 02794/HL/04) and the iron dichloride complex of h 17 (17.1
mg; 29.0 .mu.mol) under a nitrogen inert atmosphere. The flask was
equipped with a magnetic stirring bar and a septum cap. The solid
was cooled to 0.degree. C. and dichloromethane (20 mL) was added
under vigorous stirring. After 1 hour, the volatiles were removed
in vacuo. The resulting solid was stored at -30.degree. C. Yield:
2.05 g.
Example 127
[0492] Polymerization of Ethylene with the Supported Cobalt
Dichloride Complex of h17
[0493] A 300-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with 184 mg of the title catalyst under
nitrogen. Toluene (100 mL) was then added and the atmosphere
immediately replaced with ethylene. The suspension was agitated for
4 hours, at room temperature, under 1 atm ethylene. The reaction
was then quenched with methanol and 6M HCl. The mixture was
filtered, the solid collected and dried in a vacuum oven (86 mg).
NMR M.sub.n=5510 (100% terminal olefin); T.sub.m=127.degree. C.
Example 128
[0494] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0495] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron dichloride complex of h16
(11 nmol Fe) was added under pressure through an injection loop.
The reaction mixture was agitated under 200 psi ethylene for 60 min
and then quenched with MeOH under elevated pressure. The reactor
was vented and the mixture further treated with 6M HCl. Solid
material was isolated by filtration (3.44 g; .sup.1H NMR:
M.sub.n=5090,21 BP/1000 C, where BP/1000 C refers to branch points
per 1000 carbons, >99% terminal olefin; GPC: M.sub.n=580,
M.sub.w/M.sub.n=1.5; T.sub.m=89.degree. C.). Additional material
was isolated by performing a liquid-liquid extraction on the
filtrate using toluene. The organic layers were combined and the
volatiles removed on a rotary evaporator. The solid residue was
further dried in a vacuum oven to give 14.46 g polyethylene
(.sup.1H NMR: M.sub.n=4118, 64 BP/1000 C, 99% terminal olefin; GPC:
M.sub.n=130, M.sub.w/M.sub.n=1.8; T.sup.m=55.degree. C.), for a
total combined yield of 13.50 g (1.4M TO, where TO refers to mol
olefin monomer/mol metal). The combined fractions was further
analyzed by NMR to give an M.sup.n value of 477 (99% terminal
olefin) with 4 BP/1000 C.
Example 129
[0496] Copolymerization of Ethylene and 1-hexene Using the Iron
Dichloride Complex of h16
[0497] A 1000-mL Parr.RTM. reactor was charged with 270 mL toluene,
30 mL 1-hexene and 2.0 mL MAO (10 wt % in toluene). The resulting
solution was heated to 60.degree. C. and then pressurized to 200
psi with vigorous stirring. A solution of the iron dichloride
complex of h16 (6.0 nmol Fe) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (7.62 g;
.sup.1H NMR: M.sub.n=1590, 2 BP/1000 C, 98% terminal olefin; GPC:
M.sub.n=540, M.sub.w/M.sub.n=1.8; T.sub.m=91.degree. C.).
Additional material was isolated by performing a liquid-liquid
extraction on the filtrate using toluene. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 6.92 g
polyethylene (.sup.1H NMR: M.sub.n=364, 20 BP/1000 C, >99%
terminal olefin; GPC: M.sub.n=210, M.sub.w/M.sub.n=1.2;
T.sub.m=55.degree. C.), for a total combined yield of 14.54 g (86M
TO). .sup.13C NMR showed poor incorporation of 1-hexene.
Example 130
[0498] Preparation of the Iron Dichloride Complex of h21
[0499] A solution of h21 (3.7 mg; 6.2 .mu.mol) in 5 mL
dichloromethane was added to a suspension of FeCl.sub.2.THF (1.4
mg; 6.0 .mu.mol) in 1 mL CH.sub.2Cl.sub.2. The solution gradually
turned green and then back to yellow after 7 hours. Additional
dichloromethane was added to reach an iron concentration of 0.31
.mu.mol/mL. This solution was used as is for Example 131.
Example 131
[0500] Polymerization of Ethylene Using the Dichloride Complex
Prepared in Example 130
[0501] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 45.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron complex as prepared in
Example 130 (0.62 .mu.mol Fe) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. The product was isolated by performing a liquid-liquid
extraction on the reaction mixture. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 0.22 g
(12,600 TO) polyethylene (.sup.1H NMR: M.sub.n=597, <1 BP/1000
C, 74% terminal olefin; GPC: M.sub.n=300, M.sub.w/M.sub.n=6.7;
T.sub.m=119.degree. C.).
Example 132
[0502] Preparation of the Iron Dichloride Complex of Ligand h28
[0503] To a suspension of FeCl.sub.2.x THF (2.2 mg; 9.4 .mu.mol) in
ca. 2 mL dichloromethane was added a solution of h28 (5.4 mg; 9.7
.mu.mol) in 4 mL CH.sub.2Cl.sub.2. The yellow solution turned green
within 30 min. Additional CH.sub.2Cl.sub.2 was added to reach a
concentration of 0.53 .mu.mol/mL.
Example 133
[0504] Polymerization of Ethylene Using the Iron Dichloride Complex
of h28 Prepared in Example 132
[0505] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 45.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron complex as prepared in
Example 132 (1.1 .mu.mol Fe) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. The product was isolated by performing a liquid-liquid
extraction on the reaction mixture with toluene. The organic layers
were combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 3.56 g
(120K TO) polyethylene (.sup.1H NMR: M.sub.n=2082, <1 BP/1000 C,
78% terminal olefin; GPC: M.sub.n=1800, M.sub.w/M.sub.n=1.6;
T.sub.m=128.degree. C.).
Example 134
[0506] Preparation of the Iron Trichloride Complex of h17
[0507] Under an inert nitrogen atmosphere, a solution of h17 (5.6
mg; 0.016 mmol) in 2 mL dichloromethane was added to a suspension
of FeCl.sub.3.6 H.sub.2O (4.5 mg; 0.017 mmol) in dichloromethane,
leading to an immediate color change from yellow to dark brown. The
solution was stirred at room temperature for about 18 hours before
use as polymerization catalyst.
Example 135
[0508] Ethylene Polymerization Using the Iron Trichloride Complex
of h17 Generated as in Example 134
[0509] Under nitrogen, a 300-mL pear-shaped flask was charged with
100 mL toluene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solvent. The flask was evacuated and backfilled with
ethylene. The iron complex (0.014 mmol) was added with vigorous
stirring. The solution was agitated for 15 min and the reaction was
then quenched by addition of methanol and 6M HCl. The product was
extracted with toluene. The volatiles were then removed to give
0.03 g (76 TO) solid material. .sup.1H NMR: M.sub.n=653; 63 BP/1000
C; >99% terminal olefin.
Example 136
[0510] Preparation of the Iron Bis(tetrafluoroborate) Complex of
h17
[0511] To a suspension of iron(II) bis(tetrafluoroborate)
hexahydrate (4.9 mg; 15 .mu.mol) in dichloromethane was added a
solution of h17 (5.0 mg; 14 .mu.mol) in a few milliliters of
dichloromethane. The solution turned from light yellow to dark
orange with time within 18 hours. The solution was used as is in
further polymerization study.
Example 137
[0512] Ethylene Polymerization Using the Iron
Bis(tetrafluoroborate) Complex of h17 as Prepared in Example
136
[0513] Under nitrogen, a 300-mL pear-shaped flask was charged with
100 mL toluene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solvent. The flask was evacuated and backfilled with
ethylene. The iron complex (0.014 mmol) was added with vigorous
stirring. The solution was agitated for 7 min and the reaction was
then quenched by addition of methanol and 6M HCl. The product was
isolated by performing a liquid extraction with toluene. The
organic layers were combined and the volatiles removed in vacuo to
give 2.17 g (119,000 TO; .sup.1H NMR: M.sub.n=993, 4 BP/1000 C,
>99% terminal olefin; GPC: M.sub.n=630, M.sub.w/M.sub.n=7.7;
T.sub.m=124.degree. C.).
Example 138
[0514] Preparation of an Iron Complex of h17
[0515] To a solution of h17 (5.0 mg; 0.014 mmol) in dichloromethane
was added tris(pentafluorophenyl)borane (72.1 mg; 0.141 mmol) in
dichloromethane, with subsequent addition of FeCl.sub.3 (2.3 mg;
0.014 mmol). The solution was stirred at room temperature for about
18 hours before being used in the polymerization of ethylene.
Example 139
[0516] Preparation of an Iron Complex of h25
[0517] To a suspension of FeCl.sub.3 (2.6 mg; 16 .mu.mol) in
dichloromethane was added tris(pentafluorophenyl)borane (71.6 mg;
0.140 mmol), with subsequent addition of a solution of h25 (8.0 mg;
13 .mu.mol) in dichloromethane. The solution was stirred at room
temperature and stored at room temperature before being used in the
polymerization of ethylene.
Example 140
[0518] Ethylene Polymerization Using the Iron Complex of h25 as
Prepared in Example 139
[0519] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 600 psi with
vigorous stirring. A solution of the iron complex as prepared in
Example 139 (0.34 .mu.mol Fe) was added under pressure through an
injection loop. The reaction mixture was agitated under 600 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (5.88 g;
polymer could not be analyzed by GPC; T.sub.M=91.degree. C.).
Additional material was isolated by performing a liquid-liquid
extraction on the filtrate using toluene. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 7.62 g
polyethylene (GPC: M.sub.n=170, M.sub.w/M.sub.n=1.2;
T.sub.m=53.degree. C.), for a total combined yield of 13.50 g (1.4M
TO). The combined fractions were further analyzed by NMR to give an
M.sub.nvalue of 477 (99% terminal olefin) with 4 BP/1000 C.
Example 141
[0520] Preparation of a Cobalt Complex of h25
[0521] To a solution of ca. 3 mL dichloromethane containing
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (15.4 mg; 16.7 .mu.mol) and
Co(acac).sub.2 (4.2 mg; 16.3 .mu.mol) was added h25 (9.5 mg; 16.5
.mu.mol) in dichloromethane (ca. 2 mL). The resulting solution was
used as is in Example 142.
Example 142
[0522] Polymerization of Ethylene Using the Cobalt Complex of h25
Prepared in Example 141
[0523] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of a dichloromethane solution
of the cobalt complex of h25 (16.3 .mu.mol) prepared in Example
141. The reaction solution was stirred at room temperature for 3
min and then quenched with 6M HCl. The product was isolated by
extraction with toluene (296 mg, 640 TO; NMR: M.sub.n>50,000,
<1 BP/1000 C; T.sub.m=141.degree. C.).
Example 143
[0524] Preparation of the Iron Bis(tetrafluoroborate) Complex of
h25
[0525] A solution of h25 (5.1 mg; 8.9 .mu.mol) in about 2 mL
dichloromethane was added to a suspension of iron
bis(tetrafluoroborate) hexahydrate (3.0 mg; 8.9 .mu.mol) in
dichloromethane. The mixture was stirred at room temperature for
about 18 hours before being used in the polymerization of
ethylene.
Example 144
[0526] Polymerization of Ethylene Using the Iron Complex of h25 as
Prepared in Example 143
[0527] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of a dichloromethane solution
of the iron complex of h25 (1.1 .mu.mol), as prepared in Example
143. The reaction solution was stirred at room temperature for 10
min and then quenched with 6M HCl. The product was isolated by
extraction with toluene (1.78 g, 7160 TO; NMR: M.sub.n=786, 4
BP/1000 C, 94% terminal olefin; GPC: M.sub.n=440,
M.sub.w/M.sub.n=1.8; T.sub.m=122.degree. C.).
Example 145
[0528] Polymerization of Ethylene and 1-hexene Using the Iron
Dichloride Complex of h16
[0529] A 300-mL oven-dried flask was charged with toluene (90 mL)
and 1-hexene (10 mL) under ethylene. MAO (Aldrich, 10 wt % in
toluene; 2.0 mL) was added to the solution, followed by addition of
a dichloromethane solution of iron dichloride complex of h16 (1.1
.mu.mol). The reaction solution was stirred at room temperature for
20 min and then quenched with 6M HCl. The product was isolated by
extraction with toluene (5.2 g; NMR: M.sub.n=472, 48 BP/1000 C, 85%
terminal olefin; GPC: M.sub.n=330, M.sub.w/M.sub.n=2.1;
T.sub.m=88.degree. C.). Analysis of NMR data suggests 18 mol %
incorporation of 1-hexene.
Example 146
[0530] Polymerization of Ethylene and 1-hexene Using the Iron
Dichloride Complex of h16
[0531] A 1000-mL Parre reactor was charged with 270 mL toluene and
2.0 mL MAO (10 wt % in toluene). The resulting solution was heated
to 60.degree. C. and then pressurized to 200 psi with vigorous
stirring. A solution of the iron dichloride complex of h16 (6.0
nmol Fe) was added under pressure through an injection loop by
slightly depressurizing the reactor. Upon injection, the internal
temperature rose to 69.degree. C. The reaction mixture was agitated
under 200 psi ethylene for 60 min and then quenched with MeOH under
elevated pressure. The reactor was vented and the mixture further
treated with 6M HCl. Solid material was isolated by filtration
(7.62 g; NMR: M.sub.n=1590, 2 BP/1000 C, 98% terminal olefin; GPC:
M.sub.n=540, M.sub.w/M.sub.n=1.8; T.sub.m=91.degree. C.).
Additional material was isolated by performing a liquid-liquid
extraction on the filtrate using toluene. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 6.92 g
polyethylene (NMR: M.sub.n=364, 20 BP/1000 C, >99% terminal
olefin; GPC: M.sub.n=210, M.sub.w/M.sub.n=1.2; T.sub.m=55.degree.
C.), for a total combined yield of 14.54 g (86M TO).
Example 147
[0532] Polymerization of 1-hexene Using the Iron Dichloride Complex
of h16
[0533] A 300-mL oven-dried flask was charged with toluene (90 mL)
and 1-hexene (10 mL) under nitrogen. MAO (Aldrich, 10 wt % in
toluene; 2.0 mL) was added to the solution, followed by addition of
a dichloromethane solution of iron dichloride complex of h16 (0.28
.mu.mol). The reaction solution was stirred at room temperature for
24 min and then quenched with methanol and 6M HCl. The product was
isolated by extraction with toluene (0.07 g; M.sub.n=408, 137
BP/1000 C, >99% terminal olefin; M.sub.n (GPC) =240,
M.sub.w/M.sub.n=1.3).
Example 148
[0534] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16 in the Presence of Dichlorophenyl Ethyl Acetate
(PhCl.sub.2CCO.sub.2Et)
[0535] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron dichloride complex of h16
(6.0 nmol Fe) was added under pressure through an injection loop by
slightly depressurizing the reactor. The reaction mixture was
agitated under 200 psi ethylene for 5 min and then quenched with
MeOH under elevated pressure. The reactor was vented and the
mixture further treated with 6M HCl. Solid material was isolated by
filtration (12.58 g; NMR: M.sub.n=804, 2 BP/1000 C, 98% terminal
olefin; GPC: M.sub.n=650, M.sub.w/M.sub.n=1.5; T.sub.m=92.degree.
C.). Additional material was isolated by performing a liquid-liquid
extraction on the filtrate using toluene. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 5.73 g
polyethylene (NMR: M.sub.n=390, 5 BP/1000 C, >99% terminal
olefin; GPC: M.sub.n=9000, M.sub.w/M.sub.n=1.2; T.sub.m=60.degree.
C.), for a total combined yield of 18.31 g (75M TO).
Example 149
[0536] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0537] A 1000-mL Parr.RTM. reactor was charged with 270 mL toluene
and 0.5 mL triisobutylaluminum (25 wt % in toluene). The resulting
solution was heated to 60.degree. C. and then pressurized to 200
psi with vigorous stirring. A solution of the iron dichloride
complex of h16 (77 nmol Fe) was added under pressure through an
injection loop by slightly depressurizing the reactor. A solution
of trityl tetrakis(perfluorophenyl- )borate (0.46 .mu.mol) in
dichloromethane was subsequently added under pressure. Upon
injection, the internal temperature rose to 73.degree. C. The
reaction mixture was agitated under 200 psi ethylene for 60 min and
then quenched with MeOH under elevated pressure. The reactor was
vented and the mixture further treated with 6M HCl. Solid material
was isolated by filtration (43.38 g; NMR: M.sub.n=697, 3 BP/1000 C,
>99% terminal olefin; GPC: M.sub.n=360, M.sub.w/M.sub.n=1.9;
T.sub.m=101.degree. C.). Additional material was isolated by
performing a liquid-liquid extraction on the filtrate using
toluene. The organic layers were combined and the volatiles removed
on a rotary evaporator. The solid residue was further dried in a
vacuum oven to give 2.72 g polyethylene (NMR: M.sub.n=263, 2
BP/1000 C, >99% terminal olefin; GPC: M.sub.n=110,
M.sub.w/M.sub.n=1.1; T.sub.m=35.degree. C.), for a total combined
yield of 46.10 g (21M TO).
Example 150
[0538] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0539] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 1.7 mL diethylaluminum chloride (25 wt % in toluene). The
resulting solution was heated to 60.degree. C. and then pressurized
to 200 psi with vigorous stirring. A solution of the iron
dichloride complex of h16 (1.0 nmol Fe) was added under pressure
through an injection loop by slightly depressurizing the reactor.
The reaction mixture was agitated under 200 psi ethylene for 60 min
and then quenched with MeOH under elevated pressure. The reactor
was vented and the mixture further treated with 6M HCl. Solid
material was isolated by performing a liquid-liquid extraction on
the reaction mixture, using toluene. The organic layers were
combined and the volatiles removed on a rotary evaporator. The
solid residue was further dried in a vacuum oven to give 0.05 g
polyethylene (NMR: M.sub.n=876, 95 BP/1000 C, 69% terminal olefin;
T.sub.m=138.degree. C.).
Example 151
[0540] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0541] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 0.22 mL triisobutylaluminum (25 wt % in toluene). The resulting
solution was heated to 60.degree. C. and then pressurized to 200
psi with vigorous stirring. A solution of the iron dichloride
complex of h16 (1.34 .mu.mol Fe) was added under pressure through
an injection loop by slightly depressurizing the reactor. The
reaction mixture was agitated under 200 psi ethylene for 60 min and
then quenched with MeOH under elevated pressure. The reactor was
vented and the mixture further treated with 6M HCl. The mixture was
filtered to give 5.37 g (NMR: M.sub.n=935, 2 BP/1000 C, >99%
terminal olefin; GPC: M.sub.n=580, M.sub.w/M.sub.n=1.4;
T.sub.m=98.degree. C.) of white solid. Additional solid material
was isolated by performing a liquid-liquid extraction on the
filtrate, using toluene. The organic layers were combined and the
volatiles removed on a rotary evaporator. The solid residue was
further dried in a vacuum oven to give 10.8 g (430K TO)
polyethylene (NMR: M.sub.n=329, 5 BP/1000 C, >99% terminal
olefin; GPC: M.sub.n=120, M.sub.w/M.sub.n=1.6; T.sub.m=60.degree.
C.).
Example 152
[0542] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0543] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and a solution of solid MAO (3.0 mmol) in 2.0 mL toluene. The
resulting solution was heated to 60.degree. C. and then pressurized
to 200 psi with vigorous stirring. A solution of the iron
dichloride complex of h16 (0.011 .mu.mol Fe) was added under
pressure through an injection loop by slightly depressurizing the
reactor. The reaction mixture was agitated under 200 psi ethylene
for 60 min and then quenched with MeOH under elevated pressure. The
reactor was vented and the mixture further treated with 6M HCl. The
mixture was filtered to give 3.44 g (NMR: M.sub.n=5090, 21 BP/1000
C, >99% terminal olefin; GPC: M.sub.n=580, M.sub.w/M.sub.n=1.5;
T.sub.m=89.degree. C.) of white solid. Additional solid material
was isolated by performing a liquid-liquid extraction on the
filtrate, using toluene. The organic layers were combined and the
volatiles removed on a rotary evaporator. The solid residue was
further dried in a vacuum oven to give 14.46 g (58M TO)
polyethylene (NMR: M.sub.n=5118, 64 BP/1000 C, 99% terminal olefin;
GPC: M.sub.n=130, M.sub.w/M.sub.n=1.8; T.sub.m=55.degree. C.).
Example 153
[0544] Polymerization of Ethylene Using the Iron Dichloride Complex
of h16
[0545] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and modified MAO (Akzo Nobel,
-[(CH.sub.3).sub.0.7(i-C.sub.4H.sub.9).sub.0.3A- lO]-, 7.18 wt %
Al). The resulting solution was heated to 60.degree. C. and then
pressurized to 200 psi with vigorous stirring. A solution of the
iron dichloride complex of h16 (0.011 .mu.mol Fe) was added under
pressure through an injection loop by slightly depressurizing the
reactor. The reaction mixture was agitated under 200 psi ethylene
for 60 min and then quenched with MeOH under elevated pressure. The
reactor was vented and the mixture further treated with 6M HCl. The
mixture was filtered to give 7.97 g (NMR: M.sub.n=664, 2 BP/1000 C,
99% terminal olefin; GPC: M.sub.n=370,
M.sub.w/M.sub.n=1.7;T.sub.m=88.degree. C.) of white solid.
Additional solid material was isolated by performing a
liquid-liquid extraction on the filtrate, using toluene. The
organic layers were combined and the volatiles removed on a rotary
evaporator. The solid residue was further dried in a vacuum oven to
give 7.49 g polyethylene (GPC: M.sub.n=150, M.sub.w/M.sub.n=1.3;
T.sub.m=55.degree. C.). Total yield: 15.46 g (50.times.10.sup.6
TO).
Example 154
[0546] Preparation of a Cobalt Complex of h29
[0547] A solution of ligand h29 (3.1 mg; 5.8 .mu.mol) in
dichloromethane was added to a suspension of Co(acac).sub.2 (1.7
mg; 6.6 .mu.mol). Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (5.7 mg; 6.2
.mu.mol) was subsequently added, followed by dichloromethane to
reach a total volume of 3.0 mL.
Example 155
[0548] Ethylene Polymerization Using the Cobalt Complex of h29 as
Prepared in Example 154
[0549] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the cobalt complex as prepared in
Example 154 (0.20 .mu.mol Co) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (8.77 g;
GPC: M.sub.n=323,000; M.sub.w=953,000; .sup.1H NMR: M.sub.n=15,251,
<1 BP/1000 C, 17% terminal olefin; T.sub.m=91.degree. C.).
Example 156
[0550] Preparation of a Cobalt Complex of h30
[0551] A solution of ligand h30 (3.5 mg; 7.6 .mu.mol) in
dichloromethane was added to Co(acac).sub.3 (2.9 mg; 8.1 .mu.mol).
Trityl tetrakis(pentafluorophenyl)borate (15.0 mg; 16.3 .mu.mol) in
dichloromethane was then added to the solution. The resulting
solution was further diluted with dichloromethane to give a
concentration of 88 nmol/mL.
Example 157
[0552] Ethylene Polymerization Using the Cobalt Complex of h30 as
Prepared in Example 156
[0553] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the cobalt complex as prepared in
Example 156 (0.18 .mu.mol Co) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (7.38 g;
1.5M TO; .sup.1H NMR: M.sub.n>50K, <1 BP/1000 C;
T.sub.m=138.degree. C. GPC: M.sub.n=346,000; M.sub.w=978,000).
Example 158
[0554] Ethylene Polymerization in the Presence of Hydrogen Using
the Cobalt Complex of h30 as Prepared in Example 156
[0555] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene,
50 mL hydrogen and 2.0 mL MAO (10 wt % in toluene). The resulting
solution was heated to 60.degree. C. and then pressurized to 200
psi with vigorous stirring. A solution of the cobalt complex as
prepared in Example 156 (0.17 .mu.mol Co) was added under pressure
through an injection loop. The reaction mixture was agitated under
200 psi ethylene for 60 min and then quenched with MeOH under
elevated pressure. The reactor was vented and the mixture further
treated with 6M HCl. Solid material was isolated by filtration
(1.51 g; .sup.1H NMR: M.sub.n=51K, 2 BP/1000 C, 83% terminal
olefin; GPC: M.sub.n=22,600; M.sub.w=60,600; T.sub.m=139.degree.
C.). A second fraction was isolated by performing an organic
extraction on the filtrate. The combined organic fractions were
dried over sodium sulfate and the volatiles were then removed in
vacuo. The residue was further dried in a vacuum oven at
100.degree. C. to give 0.13 g. The combined isolated yield amounted
to 1.64 g (3.51.times.10.sup.5 TO).
Example 159
[0556] Preparation of a Cobalt Complex of h22
[0557] A solution of ligand h22 (6.3 mg; 13 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (13.0 mg; 14.1 .mu.mol) in
dichloromethane was added to a solution of Co(acac).sub.2 (3.4 mg;
14 .mu.mol) in dichloromethane to give a resulting concentration of
4.3 .mu.mol/mL.
Example 160
[0558] Ethylene Polymerization Using the Cobalt Complex of h22 as
Prepared in Example 159
[0559] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 600 psi with
vigorous stirring. A solution of the cobalt complex as prepared in
Example 159 (0.17 .mu.mol Co) was added under pressure through an
injection loop. The reaction mixture was agitated under 600 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (3.44 g;
710K TO; NMR: M.sub.n>50,000, <1 BP/1000 C, 51% terminal
olefin; T.sub.m=139.degree. C.; GPC: M.sub.n=372,000;
M.sub.n=859,000).
Example 161
[0560] Preparation of an Iron Complex of h22
[0561] A solution of ligand h22 (3.7 mg; 7.6 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (7.5 mg; 8.13 .mu.mol) in
dichloromethane was added to a solution of Fe(acac).sub.2 (2.0 mg;
7.9 .mu.mol) in dichloromethane to give a resulting concentration
of 1.7 .mu.mol/mL.
Example 162
[0562] Ethylene Polymerization Using the Cobalt Complex of h22 as
Prepared in Example 161
[0563] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the cobalt complex as prepared in
Example 161 (0.17 .mu.mol Fe) was added under pressure through an
injection loop. The reaction mixture was agitated under 200 psi
ethylene for 60 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (2.22 g;
645K TO; .sup.1H NMR: M.sub.n>50K, 1 BP/1000 C;
T.sub.m=140.degree. C.; GPC: M.sub.n=24,600; M.sub.w=96,700).
Example 163
[0564] Preparation of Stock Solution of the Iron Complex of h31
[0565] A solution of ligand h31 (3.8 mg; 9.1 .mu.mol) in
dichloromethane was added to Fe(acac).sub.2 (2.3 mg; 9.1 .mu.mol)
and Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (8.5 mg; 9.2 .mu.mol). The
resulting solution was used in Example 164.
Example 164
[0566] Ethylene Polymerization Using the Iron Complex of h31 as
Prepared in Example 163
[0567] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of a dichloromethane solution
of the iron complex of h31 (9.1 .mu.mol), as prepared in Example
163. The reaction solution was stirred at room temperature for 2
min and then quenched with 6M HCl. The product was isolated by
extraction with toluene (2.70 g, 11,000 TO; T.sub.m=132.degree. C.;
.sup.1H NMR: M.sub.n=6190; 18 BP/1000 C; 17% terminal olefin; GPC:
M.sub.n=5110; M.sub.n=31,600).
Example 165
[0568] Ethylene Polymerization Using an Iron Complex of h31
Prepared in a Similar Way as that Described in Example 163
[0569] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron complex (0.16 .mu.mol Fe)
was added under pressure through an injection loop. The temperature
immediately rose to 75.degree. C. The reaction was ran at
66.degree. C. for 10 min and then quenched with MeOH under elevated
pressure. The reactor was vented and the mixture further treated
with 6M HCl. Solid material was isolated by filtration (14.45 g;
3.2M TO). .sup.1H NMR: M.sub.n=19 600, <1 BP/1000 C, 92%
terminal olefin; GPC: M.sub.n=16,100, M.sub.w/M.sub.n=7.1;
T.sub.m=138.degree. C.
Example 166
[0570] Ethylene Polymerization Using an Iron Complex of h29
Prepared in a Similar Way as that Described in Example 163
[0571] A 1000-mL Parr.RTM. reactor was charged with 300 mL toluene
and 2.0 mL MAO (10 wt % in toluene). The resulting solution was
heated to 60.degree. C. and then pressurized to 200 psi with
vigorous stirring. A solution of the iron complex (0.27 .mu.mol Fe)
was added under pressure through an injection loop. The reaction
mixture was agitated for 60 min and then quenched with MeOH under
elevated pressure. The reactor was vented and the mixture further
treated with 6M HCl. Solid material was isolated by filtration
(7.52 g; 985K TO). (.sup.1H NMR: M.sub.n>75K, <1 BP/1000 C;
GPC: M.sub.n=63.9K, M.sub.w/M.sub.n=10; T.sub.m=142.degree. C.)
Example 167
[0572] Preparation of a Stock Solution of the Cobalt Complex of
h31
[0573] A solution of h31 (2.8 mg; 6.7 .mu.mol) in dichloromethane
was added to Co(acac).sub.2 (1.9 mg; 7.4 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub- .5).sub.4 (6.1 mg; 6.6 .mu.mol). The
resulting solution was used in Example 168.
Example 168
[0574] Ethylene Polymerization Using the Cobalt Complex of h31 as
Prepared in Example 167
[0575] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of the dichloromethane
solution of the cobalt complex of prepared in Example 167. The
reaction solution was stirred at room temperature for 2 min and
then quenched with 6M HCl. The product was isolated by extraction
with toluene (1.65 g, 8790 TO; .sup.1H NMR: M.sub.n>50K, <1
BP/1000 C; T.sub.m=139.degree. C.; GPC: M.sub.n=99,300;
M.sub.w=196,000).
Example 169
[0576] Preparation of a Stock Solution of the Iron Complex of
h32
[0577] A solution of ligand h32 (9.0 mg; 17 .mu.mol) in
dichloromethane was added to Fe(acac).sub.2 (4.4 mg; 17 .mu.mol)
and Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (16 mg; 17 .mu.mol). The
resulting solution was used in Example 170.
Example 170
[0578] Ethylene Polymerization Using the Iron Complex of h32 as
Prepared in Example 169
[0579] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of the dichloromethane
solution of the iron complex of h32 prepared in Example 169. The
reaction solution was stirred at room temperature for 3 min and
then quenched with 6M HCl. The product was isolated by extraction
with toluene (1.05 g, 2200 TO; NMR: M.sub.n>50,000, 14 BP/1000
C; GPC: M.sub.n=4150, M.sub.w/M.sub.n=13; T.sub.m=133.degree.
C.).
Example 171
[0580] Ethylene Polymerization Using a Cobalt Complex of h33
Prepared in a Similar Way as that Described in Example 167
[0581] A 300-mL oven-dried flask was charged with toluene (100 mL)
under ethylene. MAO (Aldrich, 10 wt % in toluene; 1.0 mL) was added
to the solution, followed by addition of the dichloromethane
solution of the cobalt complex (5.5 .mu.mol). The reaction solution
was stirred at room temperature for 3 min and then quenched with 6M
HCl. The product was isolated by filtration and further dried in a
vacuum oven (1.11 g, 7000 TO; .sup.1H NMR: M.sub.n>50K, 1
BP/1000 C; GPC: M.sub.n=134K,
M.sub.w/M.sub.n=2.3;T.sub.m=139.degree. C.).
Example 172
[0582] Synthesis of b20
[0583] To a 20 mL test tube were added 500 mg (2.13 mmol) of
3,5-di-tert-butyl-2-hydroxybenzaldehyde, 218 mg (2.13 mmol) of
4-aminomorpholine, and 8 mL of CH.sub.2Cl.sub.2. The mixture was
sonicated until a solution was obtained and 2 drops of formic acid
were added. The solution was heated with a heat gun to a gentle
reflux and swirled for 5 min. The solution was allowed to cool to
room temperature and crystals began to form. After 1 h, the
crystals were collected by vacuum filtration and washed with cold
methanol to give 600 mg of b20.
Example 173
[0584] Synthesis of h32
[0585] To a flame-dried, 2 L round-bottomed flask equipped with a
Dean-Stark trap were added 300 mL of o-xylene and 50 g (248.6 mmol)
of chelidamic acid monohydrate. The resulting slurry was heated to
reflux and stirred for 4 h then allowed to cool to room
temperature. To the mixture was added 207.1 g (994.4 mmol) of
PCl.sub.5 in several small quantities. The resulting solution was
stirred for 30 min at 25.degree. C. then heated to reflux and
stirred for an additional 1.5 h. The solution was allowed to cool
to room temperature then cooled to 0.degree. C. and quenched by
adding 300 mL of anhydrous methanol slowly over 1 h. The solution
was heated to reflux for 45 min and the excess methanol was removed
by distillation. Once complete, the mixture was cooled to 0.degree.
C. and dimethyl-4-chloro-2,6-pyridinedicarboxylate crystallized out
of solution. The product was collected by vacuum filtration and
washed with 50 mL of cold methanol to give 29.9 g of
dimethyl-4-chloro-2,6-pyridinedicarboxylate. .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta.4.03 (s, 6H), 8.30 (s, 2H). To a 500
mL round-bottomed flask were added 900 mg (3.9 mmol) of
dimethyl-4-chloro-2,6-pyridinedicarboxyla- te, 1.4 mL (13.3 mmol)
of N,N'-dimethylethylenediamine, and 100 mL of anhydrous toluene.
The resulting solution was cooled to 0.degree. C. and 20.0 mL of a
2 M solution of trimethylaluminum (40.0 mmol) in toluene was added
dropwise. The solution was heated to reflux and stirred for 14 h
then cooled to 0.degree. C. The reaction was quenched by adding a
solution of 1.65 g (11.0 mmol) of tartaric acid in 44 mL of 0.5 N
NaOH. Stirring was continued for 1 h and the resulting slurry was
filtered through Celite. The filtrate was transferred into a
separatory funnel. Two layers formed and the organic material. was
collected, dried over anhydrous K.sub.2CO.sub.3, filtered, and
concentrated in vacuo to an oil. Silica gel chromatography (50%
methylene chloride in hexane) of the oil provided 128 mg of
4-chloro-2,6-diacetylpyridine. .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta.2.77 (s, 6H), 8.16 (s, 2H). To a 50 mL round-bottomed flask
equipped with a Dean-Stark trap were added 20 mL of anhydrous
toluene, 130 mg (0.66 mmol) of 4-chloro-2,6-diacetylpyridine, 235
mg (1.30 mmol) of 1-amino-2-tert-butyl-5-isopropylpyrrole, and 0.1
mg of p-toluenesulfonic acid monohydrate. The reaction mixture was
stirred and heated to reflux. After 6 h, the resulting solution was
allowed to cooled to room temperature and concentrated in vacuo to
an oil. Silica gel chromatography (33% methylene chloride in
hexane) of the oil provided 166 mg of h32. .sup.1H NMR (CDCl.sub.3,
300 MHz) .delta.1.05 (d, J=6.5 Hz, 3H), 1.26 (d, J=6.8 Hz, 3H),
1.29 (s, 9H), 2.29 (s, 6H), 2.41 (qu, J=6.8 Hz, 2H), 5.93 (d, J=3.9
Hz, 2H), 5.98 (d, J=4 Hz, 2H), 8.53 (s, 2H).
Example 174
[0586] Synthesis of Monohydrazone 1 97
[0587] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 10 mL of anhydrous toluene, 3.17 g (19.44 mmol) of
2,6-diacetylpyridine, 700 mg (3.89 mmol) of
1-amino-2-tert-butyl-5-isopro- pylpyrrole, and 0.1 mg of
p-toluenesulfonic acid monohydrate. The reaction mixture was
stirred and heated to reflux. After 30 min, the resulting solution
was allowed to cool to room temperature and concentrated in vacuo
to an oil. Silica gel chromatography (10% ethyl acetate in hexane)
of the oil provided 959 mg of monohydrazone 1. .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta.1.03 (d, J=6.5 Hz, 3H), 1.27 (s, 9H),
1.27 (d, J=6.6 Hz, 3H), 2.30 (s, 3H), 2.44 (qu, J=6.8 Hz, 1H), 2.79
(s, 3H), 5.91 (dd, J=3.8, 0.8 Hz, 1H), 5.96 (dd, J=3.8, 1H), 7.99
(t, J=7.9 Hz, 1H), 8.18 (dd, J=7.6, 1.0 Hz, 1H), 8.58 (dd, J=7.8,
1.2 Hz, 1 H).
Example 175
[0588] Synthesis of h29
[0589] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 10 mL of anhydrous toluene, 115 mg (0.35 mmol) of
monohydrazone 1, 95 mg (0.42 mmol) of
1-amino-2-tert-butyl-4-ethoxycarbon- yl-5-methylpyrrole, and 0.1 mg
of p-toluenesulfonic acid monohydrate. The reaction mixture was
stirred and heated to reflux. After 12 h, the resulting solution
was allowed to cool to room temperature and concentrated in vacuo
to an oil. Silica gel chromatography (66% methylene chloride in
hexane) of the oil provided 150 mg of h29. .sup.1H NMR (CDCl.sub.3,
300 MHz) .delta.1.03 (d, J=6.6 Hz, 3H), 1.27 (ovrlp, 3H), 1.27 (s,
9H), 1.28 (s, 9H), 1.36 (t,J=7.2 Hz, 3H), 2.28 (s, 6H), 2.32 (s,
3H), 2.43 (qu, J=6.6 Hz, 1H), 4.28 (q, J=7.2, 1.5 Hz, 2H), 5.91 (d,
J=3.6 Hz, 1H), 5.96 (d, J=3.6 Hz, 1H), 6.43 (s, 1H), 8.0 (t,J=8.0
Hz, 1H), 8.49 (d, J=7.8 Hz, 1H), 8.57 (d, J=7.3 Hz, 1H).
Example 176
[0590] Synthesis of h33
[0591] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 20 mL of anhydrous toluene, 150 mg (0.46 mmol) of
monohydrazone 1, 77 mg (0.46 mmol) of
1-amino-2-tert-butyl-4,5-dimethylpy- rrole, and 2.0 mg of
p-toluenesulfonic acid monohydrate. The reaction mixture was
stirred and heated to reflux. After 6 h, the resulting solution was
allowed to cool to room temperature and concentrated in vacuo to an
oil. Silica gel chromatography (33% methylene chloride in hexane)
of the oil provided 78 mg of h33. .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta.1.04 (d, J=6.5 Hz, 3H), 1.25 (d, J=6.5 Hz, 3H), 1.27 (s,
18H), 1.90 (s, 3H), 2.05 (s, 3H), 2.28 (s, 3H), 2.36 (s, 3H), 2.43
(qu, J=6.5 Hz, 1H), 5.83 (s, 1H), 5.91 (d, J=3.9 Hz, 1H), 5.96 (d,
J=3.7 Hz, 1H), 7.96 (t, J=7.9 Hz, 1H), 8.47 (dd, J=7.7, 0.7 Hz,
1H), 8.52 (dd, J=8.0, 0.8 Hz, 1H).
Example 177
[0592] Synthesis of h31
[0593] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 10 mL of anhydrous toluene, 138 mg (0.42 mmol) of
monohydrazone 1, 56 mg (0.51 mmol) of 1-amino-2,5-dimethylpyrrole,
and 2.0 mg of p-toluenesulfonic acid monohydrate. The reaction
mixture was stirred and heated to reflux. After 12 h, the resulting
solution was allowed to cool to room temperature and concentrated
in vacuo to an oil. Silica gel chromatography (5% ethyl acetate in
hexane) of the oil provided 78 mg of h31. .sup.1H NMR (CDCl.sub.3,
300 MHz) .delta.1.07 (d, J=6.7 Hz, 3H), 1.29 (d, J=6.7 Hz, 3 H),
1.30 (s, 9H), 2.11 (s, 6H), 2.32 (s, 3H), 2.39 (s, 3H), 2.46 (m,
1H), 5.92 (s, 2H), 5.93 (d, J=3.7 Hz, 1H), 5.98 (d, J=3.7 Hz, 1H),
7.97 (t, J=7.7 Hz, 1H), 8.51 (dd, J=7.9, 0.8 Hz, 1H), 8.56 (dd,
J=7.6, 0.9 Hz, 1H).
Example 178
[0594] Synthesis of a51
[0595] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 10 mL of anhydrous toluene, 400 mg (1.70 mmol) of
1-amino-2,5-di-iso-propyl-4-ethoxycarbonylpyrrole, 74 .mu.L (0.85
mmol) of 2,3 butanedione, and 5.0 mg of p-toluenesulfonic acid
monohydrate. The resulting solution was stirred at room temperature
for 30 min then heated to 60.degree. C. After 12 h, the solution
was heated to reflux for 1 h, allowed to cool to room temperature,
and concentrated in vacuo to an oil. Silica gel chromatography (10%
ethyl acetate in hexane) of the oil provided 442 mg of a51. .sup.1H
NMR (CDCl.sub.3, 300 MHz) .delta.1.07 (d, J=4.8 Hz, 6H), 1.17 (d,
J=7.1 Hz, 6 H), 1.27 (d, J=6.8 Hz, 6H), 1.32 (d, J=7.2 Hz, 6H),
1.34 (t, J=7.0 Hz, 3H), 2.18 (s, 6H), 2.39 (qu, J=6.7 Hz, 2H), 3.75
(qu, J=7.3 Hz, 2H), 4.24 (q, J=7.2 Hz, 4H), 6.40 (d, J=0.5 Hz,
2H).
Example 179
[0596] Synthesis of a52
[0597] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 20 mL of anhydrous toluene, 330 mg (0.99 mmol) of
1-amino-2,5-di(1-naphthyl)pyrrole, 37 .mu.L (0.42 mmol) of 2,3
butanedione, and 2.0 mg of p-toluenesulfonic acid monohydrate. The
resulting solution was stirred at room temperature for 30 min then
heated to 60.degree. C. After 6 h, the solution was heated to
reflux for 1 h, allowed to cool to room temperature, and
concentrated in vacuo to an oil. Silica gel chromatography (10%
ethyl acetate in hexane) of the oil provided 266 mg of a52. .sup.1H
NMR (CDCl.sub.3, 300 MHz) .delta.0.93 (s, 6H), 6.49 (s, 4H), 7.09
(dd, J=7.2, 1.2 Hz, 4H), 7.24 (m, 4H), 7.37 (m, 4H), 7.59 (m, 4H),
7.76 (d, J=8.1 Hz, 4H), 7.82 (d, J=8.0 Hz, 4H), 8.01 (d, J=8.5 Hz,
4H).
Example 180
[0598] Synthesis of Monohydrazone 2 98
[0599] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 10 mL of DMF, 5 mL of anhydrous toluene, 1.75 g
(6.47 mmol) of 1-amino-2,5-diphenylpyrrole, 5.7 mL (64.7 mmol) of
2,3 butanedione, and 10.0 mg of p-toluenesulfonic acid monohydrate.
The resulting solution was stirred at room temperature for 30 min
then heated to 70.degree. C. After 12 h, the solution was heated to
reflux and the excess diketone and toluene were removed by
distillation. Toluene (15 mL) was added to the reaction vessel and
removed by distillation. The solution was allowed to cool to room
temperature and concentrated in vacuo to an oil. Silica gel
chromatography (10% ethyl acetate in hexane) of the oil provided
1.94 g of monohydrazone 2. .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta.1.45 (s, 3H), 2.57 (s, 3H), 6.48 (s, 2H), 7.24 (m, 2H), 7.35
(m, 4H), 7.48 (m, 4H).
Example 181
[0600] Synthesis of a53
[0601] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 15 mL of anhydrous toluene, 255 mg (0.84 mmol) of
monohydrazone 2, 145 mg (0.84 mmol) of
1-amino-2-methyl-5-phenylpyrrole, and 5.0 mg of p-toluenesulfonic
acid monohydrate. The resulting solution was heated to reflux and
stirred. After 12 h, the solution was allowed to cool to room
temperature and concentrated in vacuo to an oil. Silica gel
chromatography (10% ethyl acetate in hexane) of the oil provided
208 mg of a53. .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta.1.72 (s,
3H), 1.86 (s, 3H), 2.05 (s, 3H), 6.01 (d, J=3.7 Hz, 1H), 6.26 (d,
J=4.0 Hz, 1H), 6.47 (s, 2H), 7.26 (m,12H), 7.44 (m,3H).
Example 182
[0602] Synthesis of a54
[0603] To a 50 mL round-bottomed flask equipped with a Dean-Stark
trap were added 7 mL of DMF, 16 mL of anhydrous toluene, 1.25 g
(4.62 mmol) of 1-amino-2,5-diphenylpyrrole, 203 .mu.L (2.31 mmol)
of 2,3 butanedione, and 2.0 mg of p-toluenesulfonic acid
monohydrate. The resulting solution was heated to 70.degree. C. and
stirred. After 4 h, the solution was heated to reflux for 1-24 h.
The solution was allowed to cool to room temperature and
concentrated in vacuo to an oil. Silica gel chromatography (10%
ethyl acetate in hexane) of the oil provided a54. .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta.1.76 (s, 6H), 6.49 (s, 4H), 7.30 (m,
12H), 7.40 (m, 8H).
Example 183
[0604] Synthesis of b21
[0605] 1-Amino-pyrrole (500 mg, 6.25 mmol) and salicylaldehyde (610
mg, 5 mmol) were weighed to a 50-ml round bottom flask with a
septum. The flask was purged with dry argon gas. Methanol (10 ml)
and 4 drops of formic acid were then added to the flask. The
reaction was stirred at 50.degree. C. for 60 minutes. After 1 hour,
the mixture was cooled to 0.degree. C. giving a crystalline solid.
The crystalline product that separated was collected cold by vacuum
filtration. The crystals were washed with cold methanol on the
filter and then dried several hours in vacuo to yield 562 mg (68%
yield). .sup.1H NMR: s (OH) .delta.10.75, s (N.dbd.CH) .delta.8.45,
m (aryl 4H) .delta.6.8-7.4, s (pyrrolyl 4H) .delta.6.25.
Example 184
[0606] Synthesis of b22
[0607] 1-Amino-2,5-diisopropylpyrrole (693 mg, 4.2 mmol) and
3-(anthracen-9-yl)-2-hydroxybenzaldehyde (1.04 g, 3.5 mmol) were
independently weighed to a 100-ml round bottom flask with a septum.
1-Amino-2,5-diisopropylpyrrole was dissolved in 2-ml of
CH.sub.2Cl.sub.2 and 2-ml methanol and then transferred onto a
suspension of compound 3-(anthracen-9-yl)-2-hydroxybenzaldehyde in
methanol (10-ml). The reaction was stirred at 55.degree. C. for 60
minutes. After 1 hour, the mixture was cooled to 0.degree. C.
giving a yellow crystalline solid. The crystalline product that
separated was collected cold by vacuum filtration. The crystals
were washed with cold methanol on the filter and then dried several
hours in vacuo to yield 1.01 g (65% yield). .sup.1H NMR: s (OH)
.delta.11.42, s (N.dbd.CH) .delta.8.70, m (aryl 12H)
.delta.7.2-8.6, s (pyrrolyl 4H) .delta.5.95, septet
[CH(CH.sub.3).sub.2] .delta.3.0, [CH(CH.sub.3).sub.2]
.delta.1.2.
Example 185
[0608] Synthesis of b23
[0609] 1-Amino-pyrrole (750 mg, 9.375 mmol) was added to a 50-ml
round bottom flask that contained a suspension
3-(anthracen-9-yl)-2-hydroxybenz- aldehyde (1.49 g, 5 mmol) in
50-ml of methanol. The flask was sealed with a septum and purged
15-20 minutes with argon. An additional 20-ml of methanol was added
and the mixture was stirred at 50.degree. C. for 90 minutes. After
1.5 hours, the mixture was cooled to 0.degree. C. giving a yellow
crystalline solid. The crystalline product that separated was
collected cold by vacuum filtration. The crystals were washed with
cold methanol on the filter and then dissolved in CH.sub.2Cl.sub.2
and combined in a round bottom flask with 0.883 g of a trisamine
scavenging resin from Argonaut Technology to remove unreacted
aldehyde. The mixture was gently stirred overnight and the resin
collected by suction filtration. The CH.sub.2Cl.sub.2 was removed
in vacuo to yield 1.35 g (75% yield). .sup.1H NMR: s (OH)
.delta.11.08, s (N.dbd.CH) .delta.8.65, m (aryl 12H)
.delta.7.2-8.6, s (pyrrolyl 4H) .delta.6.
Example 186
[0610] Synthesis of b6
[0611] 1-Amino-pyrrole (990 mg, 12.4 mmol) and
3,5-di-t-butylsalicylaldehy- de (2.54 g, 10.8 mmol) were weighed to
a 50-ml round bottom flask and dissolved in 35-ml of warm methanol.
Formic acid (4 drops) was then added to the flask. The reaction was
stirred at 50.degree. C. for 30 minutes. After 30 minutes, the
mixture was cooled to 0.degree. C. giving a crystalline solid. The
crystalline product that separated was collected cold by vacuum
filtration. The crystals were washed with cold methanol on the
filter and then dissolved in CH.sub.2Cl.sub.2 and combined in a
round bottom flask with 0.89 g of a trisamine scavenging resin from
Argonaut Technology to remove unreacted aldehyde. The mixture was
gently stirred overnight and the resin collected by suction
filtration. The CH.sub.2Cl.sub.2 was removed in vacuo to yield 2 g
of product. .sup.1H NMR: s (OH) .delta.10.75, s (N.dbd.CH)
.delta.8.45, m (aryl 4H) .delta.6.8-7.4, s (pyrrolyl 4H)
.delta.6.25.
Example 187 to Example 197
[0612] Polymerization of Ethylene Starting From
Ni(COD).sub.2/ligand/B(C.s- ub.6F.sub.5).sub.3
[0613] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene. In
an inert atmosphere glove box, a flame dried Schlenk flask equipped
with a magnetic stir bar and a rubber septum was charged with
between 0.015 mmol and 0.036 mmol of
bis(1,5-cyclooctadiene)nickel(0), between 0.015 mmol and 0.036 mmol
of tris(pentafluorophenyl)borane, and between 0.015 mmol and 0.036
mmol of the ligand in a 1:1:1 ratio. The flask was removed from the
box and evacuated and refilled with ethylene. Toluene (25-50 ml)
was added. After 5-60 minutes of premix time, the contents of the
reaction flask were transferred via SS cannula to the autoclave.
The reactor was sealed and pressurized up to 400-psig ethylene and
left to stir at room temperature for 30-120 minutes at 25.degree.
C. After the desired reaction reactor was vented and the contents
poured into a beaker containing a acetone/mixture. The polymer was
collected by suction filtration and the vacuum oven overnight at
-100.degree. C.
5 Rxn time/ PE Branching/ mmol premix yield M.sub.w 1000 C T.sub.m
Example Ligand cat time (min) (g) (.times. 10.sup.-3) (.sup.1H NMR)
(.degree. C.) 187 b22 0.036 120/15 4.0 422 7 131 188 b22 0.036 60/4
0.8 213 13 128 189 b22 0.036 120/15 8.7 798 2 133 190 b22 0.036
90/15 11.5 352 3 139 191 b22 0.036 90/30 18.8 380 4 131 192 b22
0.036 60/60 12 390 3 135 193 b22 0.018 90/30 9.1 393 2 134 194 b24
0.018 90/15 5.9 483 3 133 195 b24 0.018 90/30 4.5 475 2 133 196 b25
0.018 90/15 3.8 287 3 132 197 b25 0.015 90/30 1.7 271 4 131
Example 198
[0614] Polymerization of Ethylene with d4 99
[0615] A Parr.RTM. stirred autoclave (600-ml) is heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor is cooled and charged with 150 ml of dry toluene. The
reactor is pressurized to 200-psig ethylene and vented. The
catalyst solution (2 mg of d4 in 2 ml of toluene) is added to the
reactor and the autoclave is sealed and pressurized to 200-psig
ethylene. After 30 minutes, the reactor is vented and the contents
poured into a beaker containing a methanol/acetone mixture. The
polymer is collected by suction filtration and dried in the vacuum
oven overnight at -100.degree. C. giving polyethylene.
Example 199
[0616] Ethylene Polymerization with d5 100
[0617] A Parr.RTM. stirred autoclave (600-ml) is heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor is cooled and charged with 150 ml of dry toluene. The
reactor is pressurized to 200-psig ethylene and vented. The
catalyst solution (2 mg of d5 in 2 ml of toluene) is added to the
reactor and the autoclave is sealed and pressurized to 200-psig
ethylene. After 30 minutes, the reactor is vented and the contents
poured into a beaker containing a methanol/acetone mixture. The
polymer is collected by suction filtration and dried in the vacuum
oven overnight at -100.degree. C. giving polyethylene.
Example 200
[0618] Polymerization of Norbornene with
Ni(COD).sub.2/b6/B(C.sub.6F.sub.5- ).sub.3
[0619] In an inert atmosphere glove box, a flame dried Schlenk
flask equipped with a magnetic stir bar and a rubber septum was
charged with 17 mg (0.062 mmol) of
bis(1,5-cyclooctadiene)nickel(0), 31.6mg (0.062 mmol) of
tris(pentafluorophenyl)borane, and 18.4 mg (0.062 mmol) of the
ligand of formula b6. The flask was removed from the box and
evacuated and refilled with argon. Toluene (25 ml) was added,
resulting in a orange solution. To the polymerization mixture was
added a toluene solution containing 3 g of norbornene. In seconds,
the norbornene had been converted to polynorbornene. Methanol and
acetone were added to quench the reaction and a white flocculent
polynorbornene precipitated. The polymer was collected by suction
filtration and dried in the vacuum oven overnight at -100.degree.
C. resulting in 2.8 grams of polynorbornene. M.sub.n=127,000.
Example 201
[0620] 101
[0621] Preparation of i1 and i2
[0622] Two flame dried Schlenk flasks, each equipped with a stir
bar and a rubber septum, were taken into the inert atmosphere glove
box. One of the flasks was charged with 446 mg (2 eq) of b6, while
to the second flask was added 200 mg of Zr(NMe.sub.2).sub.4. The
flasks were removed from the glove box, attached to the
vacuum/argon manifold, evacuated and refilled with argon. Methylene
chloride was added giving two clear solutions. While stirring the
ligand solution, the methylene chloride solution of
Zr(NMe.sub.2).sub.4 was transferred via SS cannula onto the ligand
giving a yellow/orange solution. The mixture was left to stir for 2
hours. For 5-10 minutes of that 2 hours a vent needle was place
through the septum to help carry away the dimethylamine in the
argon stream. After 2 hours, the solvent was removed in vacuo
giving i2 as a yellow powder (498 mg isolated, 86% yield). 200 mg
of i2 was added to a Schlenk flask and dissolved in toluene. While
stirring, 66 .mu.L of trimethylchlorosilane was added drop wise and
the mixture left to stir for 15 hours. The solvent was removed in
vacuo giving a glassy solid. The solid was dissolved in hexane,
followed by removal of hexane in vacuo 3 times yielding 150 mg (78%
yield) of i1 as a dry yellow solid. .sup.1H NMR is consistent with
the desired complex.
Example 202 to Example 211
[0623] 102
[0624] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and
an appropriate amount of cocatalyst (e.g. mMAO). In an inert
atmosphere glove box, a septum-capped vial was charged with the
desired procatalyst. The vial was removed from the box, placed
under 1 atmosphere of argon and dissolved in toluene. The reactor
was sealed and pressurized up to 300-350 psig ethylene. The
procatalyst was added to the reactor as a stock solution (2-ml) via
the high-pressure sample loop while pressurizing the autoclave to
400 psig. After the 15 minutes of stirring at 400-psig ethylene,
the reaction was quenched upon addition of 2-ml of methanol at high
pressure. The reactor was vented and the contents poured into a
beaker containing a methanol acetone/mixture. The polymer was
collected by suction filtration and dried in vacuo at -100.degree.
C.
6 PE kg PE/ cocatalyst .mu.mol T yield mmol M.sub.w T.sub.m Ex
complex (equiv.) catalyst (.degree. C.) (g) catalyst (10.sup.-3)
(.degree. C.) 202 i1 mMAO.sup.a 0.13 40 7.0 53 4,540 128 (2000) 203
i1 MMAO 0.33 70 6.4 19 108 133 (10,000) 204 i3 MMAO 0.28 70 0.13
0.46 781 134 (10,000) 205 i2 MMAO 0.32 70 0.27 0.83 127 132
(10,000) 206 i2 TMA/MAO 0.32 70 0.31 0.98 320 136 (100/10K) 207 i3
MMAO 0.27 70 0.14 0.5 525 -- (10,000) 208 i1 MMAO 0.33 70 5.8 18 81
-- (10,000) 209 i1 MMAO 0.13 40 8.8 68 147 -- (2000) 210 i1 MMAO
0.13 70 4.4 34 44 -- (2000) 211 i4 MMAO 0.13 40 0.92 7 -- -- (2000)
.sup.amMAO-3A from Akzo Nobel
Example 212
[0625] Copolymerization of Ethylene and 1-hexene with i1
[0626] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 100 ml of dry toluene, 50
ml of deoxygenated 1-hexene and 3-ml of mMAO. In an inert
atmosphere glove box, a septum-capped vial was charged with i1. The
vial was removed from the glove box placed under 1 atmosphere argon
and dissolved in toluene (2 mg in 16-ml). The reactor was sealed
heated to 50.degree. C. (allow 20.degree. C. for exotherm) and
pressurized up to 300-350 psig ethylene. The procatalyst was added
to the reactor as a stock solution (2-ml) via the high-pressure
sample loop while pressurizing the autoclave to 400 psig. After the
30 minutes of stirring at 400-psig ethylene and 70.degree. C., the
reaction was quenched by addition of 2-ml of methanol at high
pressure. The reactor was vented and the contents poured into a
beaker containing a methanol acetone/mixture. The polymer was
collected by suction filtration and dried in the vacuum oven
overnight at -100.degree. C. giving 1.8 grams of LLDPE. .sup.1H NMR
10 branches/1000 carbon atoms; M.sub.w=46,000.
Example 213
[0627] Polymerization of Ethylene with the Reaction Product of
Ti(NMe.sub.2).sub.4, b6, and Me.sub.3SiCl
[0628] A flame dried Schlenk flask equipped with a stir bar and
rubber septum was taken into the inert atmosphere glove box along
with a septum-capped vial. The flask was charged with 516 mg (2 eq)
of b6, while 250 mg of Ti(NMe.sub.2).sub.4 was added to the vial.
The flask and vial were removed from the glove box, attached to the
vacuum /argon manifold, and placed under an argon atmosphere.
Methylene chloride (10-ml) was added to both the flask and the
septum-capped vial. While stirring the ligand solution, the
methylene chloride solution of Ti(NMe.sub.2).sub.4 was transferred
via SS cannula onto the ligand giving a deep red/orange solution.
The mixture was left to stir for 1 hour. After 1 hour, the solvent
was removed in vacuo giving a burgundy solid. The resulting
burgundy solid was dissolved in toluene. While stirring, 109
.quadrature.1 of trimethylchlorosilane was added drop wise and the
mixture left to stir for 15 hours. The solvent was removed in vacuo
giving a glassy burgundy solid. After drying the solid in vacuo for
several hours, 1 mg of the material was dissolved in 20-ml of
toluene. A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene,
0.14-ml of mMAO. The reactor was sealed heated to 30.degree. C.
(allow 10.degree. C. for exotherm) and pressurized up to 300-350
psig ethylene. The procatalyst was added to the reactor as a stock
solution (2-ml, 0.1 mg of burgundy solid isolated above) via the
high-pressure sample loop while pressurizing the autoclave to 400
psig. After the 30 minutes of stirring at 400-psig ethylene and
40.degree. C., the reaction was quenched by addition of 2-ml of
methanol at high pressure. The reactor was vented and the contents
poured into a beaker containing a methanol acetone/mixture. The
polymer was collected by suction filtration and dried in the vacuum
oven overnight at -100.degree. C. giving grams of polyethylene.
Example 214
[0629] Synthesis of b3
[0630] A solution of
1-Amino-5-tert-butyl-2-methyl-1H-pyrrole-3-carboxylic acid ethyl
ester (258 mg, 1.15 mmol) in toluene (20.8 mL) was treated with
pyridinium p-toluenesulfonate (PPTS) (2.5 mg) and
3,5-di-t-butyl-2-hydroxybenzaldehyde (234 mg, 1.0 mmol). A Dean
Stark trap and reflux condenser were attached, and the resulting
solution was refluxed, with the azeotropic removal of water for --7
h. The reaction was cooled to rt, and allowed to stand under Ar
overnight. TLC indicated the reaction had not gone to completion,
therefore heating was continued for an additional 2.25 h, after
which a second portion of 3,5-di-t-butyl-2-hydroxybenzaldehyde (70
mg, 0.299 mmol) was added, and heating continued for another 2.5 h.
The resulting solution was concentrated in vacuo. The residue was
purified by flash chromatography (SiO.sub.2, 2-15% EtOAC/Hexanes)
to afford b3 (326 mg, 74%): .sup.1H NMR (CDCl.sub.3, chemical
shifts in ppm relative to TMS): 1.326 (s, 9H), 1.330 (s, 9H), 1.359
(t, 3H, J=6.9 Hz), 4.286 (q, 2H, J=7.1Hz), 7.124 (d, 1H, J=2.5 Hz),
7.552 (d, 2H, J=2.2 Hz), 8.422 (s, 1H), 11.447 (s, 1H); Field
Desorption Mass Spectrometry: m/z 440.
Example 215
[0631] Synthesis of b24
[0632] 3-Anthracen-9-yl-2-hydroxy-benzaldehyde (394 mg, 1.32 mmol)
was treated with a solution of
1-Amino-2,5-diisopropyl-1H-pyrrole-3-carboxyli- c acid ethyl ester
(436 mg, 1.83 mmol) in toluene, followed by MP-TsOH (Argonaut
Technologies, 22 mg, 3 mol% H+). The reaction was heated to
111.degree. C. under Ar, and agitated for 1.5 h. TLC indicated that
no reaction had occurred. The mixture was treated with p-TsOH (11
mg, 2.5 wt %) and heated to 111.degree. C. for an additional 1.5 h,
then treated with PS-Trisamine resin (5 mol equiv NH.sub.2) and
allowed to agitate for an additional 2 h. The mixture was filtered
and concentrated in vacuo. .sup.1H NMR indicated that the residue
contained an approximately 5:1 ratio of b24 to starting amino
pyrrole. Therefore, the crude mixture was dissolved in toluene (5
mL), treated with 3-Anthracen-9-yl-2-hydroxy-benz- aldehyde (106
mg, 0.355 mmol) and p-TsOH (2.8 mg) and heated to 110.degree. C.
for 1.5 h, after which the reaction was cooled to rt and treated
with PS-Trisamine resin (5 equiv based on starting aldehyde). The
resulting slurry was stirred at rt overnight, filtered and
concentrated in vacuo. The residue was purified by crystallization
(hexanes/CH.sub.2Cl.sub.2) to afford b24 (341 mg) contaminated with
a small amount of hexanes: .sup.1H NMR (CDCl.sub.3, chemical shifts
in ppm relative to TMS): 0.861-0.905 (m, hexanes), 1.181 (d, 6H,
J=6.6 Hz), 1.26 (bs, hexanes), 1.316 (d, 6H, J=6.9 Hz), 1.350 (t,
3H, J=7.1 Hz), 2.837 (sep, 1H, J=6.9 Hz), 3.650 (sep, 1H, J=7.1
Hz), 4.265 (q, 2H, J=7.1 Hz), 6.374 (s, 1H), 7.379-7.595 (m, 7H),
7.688(d, 2H, J=8.5 Hz), 8.082 (d, 2H, J=8.5 Hz), 8.561 (s, 1H),
8.604 (s, 1H), 11.157 (s, 1H).
Example 216
[0633] Representative Synthesis of Substituted
Salicylaldehyde-derived Ligands. Synthesis of b26
[0634] A solution of
1-amino-2-methyl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester
(238 mg, 0.975 mmol) in toluene (17.6 mL) was treated with PPTS
(2.4 mg, 1 wt %) and 3,5-di-t-butyl-2-hydroxybenzaldehyde (208 mg,
0.89 mmol). A reflux condenser was attached, and the resulting
solution was heated at reflux for 1.5 h. The reaction was cooled to
rt, and concentrated in vacuo. The residue was flash chromatography
(SiO.sub.2, 30-60% CH.sub.2Cl.sub.2/hexanes) to afford b26 (190 mg,
46%): .sup.1H NMR (DMSO): 1.231 (s, 9H), 1.284 (t, 3H, J=7.1 Hz),
1.379 (s, 9H), 2.557 (s 3H), 4.224 (q, 2H, J=6.9 Hz), 6.673 (s,
1H), 7.257-7.439 (m, 7H), 8.789 (s, 1H), 11.73 (s, 1H); Field
Desorption Mass Spectrometry: m/z 460.
Example 217
[0635] Synthesis of b25
[0636] b25 was prepared from
1-Amino-5-(2,4-dimethoxy-phenyl)-2-isopropyl--
1H-pyrrole-3-carboxylic acid ethyl ester (1.0 equiv),
3-Anthracen-9-yl-2-hydroxy-benzaldehyde (1.2 equiv), and p-TsOH (3
wt %) in toluene according to the method of Example 216. The excess
aldehyde was removed by reaction with PS-Trisamine resin (Argonaut
Technologies) at rt for 7 h, followed by filtration and
concentration in vacuo. The residue was purified by flash
chromatography (SiO.sub.2, 5-25% Trisamine EtOAc/hexane) to afford
b25. .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm relative to
TMS): 1.298 (d, 6H, J=7.1 Hz), 1.335 (t, 3H, J=7.1 Hz), 3.601 (s,
3H), 3.856 (s, 3H), 3.953 (sep, 1H, J=7.1 Hz), 4.261 (q, 2H, J=7.1
Hz), 6.410 (d, 1H, J=2.2 Hz), 6.576 (dd, 1H, J=2.2 Hz, J=8.2 Hz),
6.606 (s, 1H), 7.025-7.107 (m, 2H), 7.333-7.394 (m, 4H),
7.441-7.495 (m, 2H), 7.607 (d, 2H, J=8.2 Hz), 8.070 (d, 2H, J=8.5
Hz), 8.142 (s, 1H), 8.542 (s, 1H), 11.229 (s, 1H).
Example 218
[0637] Synthesis of h28
[0638] A solution of 2-Isopropyl-5-o-tolyl-pyrrol-1-ylamine (60 mg,
0.279 mmol) in toluene (5.76 mL) was treated with
2,6-diacetylpyridine (21.7 mg, 0.133 mmol) and p-TsOH (1.2 mg). The
resulting solution was stirred at reflux in an oil bath under Ar
for 4.5 h, then cooled to rt. The solvent was removed in vacuo, and
the residue was purified by flash chromatography (SiO.sub.2, 5-25%
EtOAc/hexanes) to afford h28 (41 mg, 56%) contaminated with a small
amount of EtOAc and hexane: .sup.1H NMR (CDCl.sub.3, chemical
shifts in ppm relative to TMS): 1.222 (d, 12H, J=6.9 Hz), 1.825 (s,
6H), 2.330 (s, 6H), 2.864 (sep, 2H, J=6.9 Hz), 6.068 (d, 2H, J=3.8
Hz), 6.146 (d, 2H, J=3.8 Hz), 7.039-7.200 (m, 8H), 7.827 (t, 1H,
J=7.7 Hz), 8.26 (d, 2H, J=7.7 Hz); Field Desorption Mass
Spectrometry: m/z 555.
Example 219
[0639] Representative Diketoester Synthesis. Preparation of Ethyl
2-acetyl-5,5-dimethyl-4-oxo-hexanoate
[0640] Ethyl acetoacetate (1 g, 7.68 mmol) was added dropwise to a
suspension of NaH (60% in mineral oil, 338 mg, 8.45 mmol) in
toluene (20 mL). The resulting suspension was stirred at rt for 10
min, then treated with 1-bromopinacolone (1.3 g, 7.32 mmol). The
mixture was immersed in a 75.degree. C. oil bath, and stirred under
Ar for 1 h. The reaction was cooled to rt, diluted with toluene and
washed with H.sub.2O (2.times.50 mL). The organic layer was dried
over Na.sub.2SO.sub.4, filtered and concentrated in vacuo to afford
crude ethyl 2-acetyl-5,5-dimethyl-4-oxo-h- exanoate (1.46 g) which
was not purified: .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm
relative to TMS): 1.166 (s, 9H), 1.277 (t, 3H, J=7.1 Hz), 2.368 (s,
3H), 3.000 (dd, 1H, J=5.8 Hz, J=18.4 Hz), 3.231 (dd, 1H, J=8.2 Hz,
J=18.4 Hz), 4.010 (dd, 1H, J=5.8 Hz, J=8.2 Hz), 4.191 (q, 2H, J=7.1
Hz); Field Desorption Mass Spectrometry: m/z 229 (M+1).
Example 220
[0641] Representative Synthesis of Protected 1-aminopyrrole
Derivative. Preparation of o1 103
[0642] A solution of 2-Acetyl-5,5-dimethyl-4-oxo-hexanoic acid
ethyl ester (1.29 g, 5.65 mmol), hydrazinecarboxylic acid
2-trimethylsilanyl-ethyl ester (1 g, 5.67 mmol) and p-TsOH (21 mg)
in toluene (10.2 mL) was heated to reflux with azeotropic removal
of water for 2 h, then cooled to rt and concentrated in vacuo. The
residue was purified by flash chromatography (SiO.sub.2,
CH.sub.2Cl.sub.2) to afford o1 (1.28 g, 62%) as a white solid:
.sup.1H NMR (CDCl.sub.3, chemical shifts in ppm relative to TMS):
-0.019 & 0.066 (two broad singlets, mixture of isomers, 9H),
0.913-1.094 (m, 2H), 1.297 (s, 9H), 2.375 & 2.383 (two
singlets, mixture of isomers, 3H), 4.177-4.341 (m, 4H), 6.237 &
6.247 (two singlets, mixture of isomers, 1H), 7.007 & 7.060
(two singlets, mixture of isomers, 1H).
Example 221
[0643] Representative LAH Reduction of 4-ethoxycarbonyl-substituted
Protected Pyrrole. Preparation of o2 104
[0644] A solution of o1 (241.2 mg, 0.65 mmol) in anhydrous THF (1.5
mL) was treated with LAH (74 mg, 1.95 mmol). The resulting
suspension was stirred at rt under Ar for 2 days, diluted with
Et.sub.2O (5 mL) and quenched with H.sub.2O (74 .mu.L), NaOH (15%
w/v in H.sub.2O, 74 .mu.L) and H.sub.2O (222 .mu.L). The resulting
suspension was stirred at rt for 30 min then filtered through a
polyethylene frit. The filtrate was concentrated in vacuo, and the
residue was purified by flash chromatography (SiO.sub.2, 5-25%
EtOAc/hexane) to afford o2 (142 mg, 70%): .sup.1H NMR (CDCl.sub.3,
chemical shifts in ppm relative to TMS): -0.003 & 0.077 (two
singlets, 9H, mixture of isomers), 0.962-1.091 (m, 2H), 1.299 (s,
9H), 1.971 (s, 3H), 2.002 (s, 3H), 4.233-4.337 (m, 4H), 5.670 (s,
1H), 7.038 & 7.341 (two singlets, 1H, mixture of isomers).
Example 222
[0645] Representative Deprotection of Trimethylsilyl
Ethoxycarbonyl-protected 1-aminopyrrole Derivative. Preparation of
1-amino-2-tert-butyl-4,5-dimethylpyrrole
[0646] o2 (141 mg, 0.45 mmol) was treated with a solution of TBAF
(where TBAF refers to tetrabutylammonium fluoride) in THF (1M
solution, 0.90 mL, 0.90 mmol). The resulting solution was stirred
at rt overnight, quenched with glacial acetic acid (51.5 .mu.L) and
concentrated in vacuo. The residue was dissolved in toluene (5 mL)
and treated with PS-TsOH (where PS-TsOH refers to a polystyrene
resin with arene sulfonic acid functionality from Argonaut
Technologies, 1.45 mmol H.sup.+/g, 1g). The suspension was stirred
at rt for 1 hour, then filtered through a short plug of silica gel
eluting with toluene (50 mL). The filtrate was concentrated in
vacuo to afford 1-amino-2-tert-butyl-4,5-dimethylpyrrole as a white
solid (45 mg, 60%). .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm
relative to TMS): 1.426 (s, 9H), 2.029 (s, 3H), 2.148 (s, 3H),
4.255 (s, 2H), 5.621 (s, 1H).
Example 223
[0647] Synthesis of h30
[0648] 2,6-Diacetylpyridine (79.9 mg, 0.49 mmol) and
5-tert-Butyl-2,3-dimethyl-pyrrol-1-ylamine (159 mg, 0.956 mmol)
were dissolved in toluene (10.6 mL) and treated with p-TsOH (-8
mg). The resulting solution was stirred under Ar at rt for 10 min,
then heated to reflux in an oil bath. The mixture was stirred at
reflux, with azeotropic removal of water, for 2 h, then cooled to
rt and concentrated in vacuo. The residue was purified by flash
chromatography (SiO.sub.2, 5% EtOAc/heptane) to afford h30 (116 mg,
51%). .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm relative to
TMS): 1.278 (s, 18H), 1.911 (s, 6H), 2.059 (s, 6H), 2.375 (s, 6H),
5.831 (s, 2H), 7.928 (t, 1H, J=8.0 Hz), 8,456 (d, 2H, J=8.0
Hz).
Example 224
[0649] Preparation of h19
[0650] 2,6-diacetylpyidine (176 mg) and
1-amino-2-phenyl-5-methylpyrrole (420 mg) were dissolved in mixture
of methanol (10 mL) and dichloromethane (4 drops) in a 20 mL
scintillation vial. One drop of formic acid was added, then the
solvent volume was reduced to 6 mL under a stream of nitrogen gas.
A dark-colored oil settled. The vial was gently warmed to give a
clear solution and then allowed to stand at room temperature. After
16 h, yellow crystals and a dark oil had separated. The solvent was
removed in vacuo and the residue was chromatographed over silica
(EtOAc/hexane) to give the product as a yellow crystalline powder
(285 mg).
Example 225
[0651] Synthesis of 3-Naphthalen-1-yl-3-oxo-propionic Acid Ethyl
Ester
[0652] A suspension of ethyl potassium malonate (3.4 g, 20.0 mmol)
in acetonitrile (30.6 mL) was treated with Et.sub.3N (3.11 mL, 22.3
mmol) and MgCl.sub.2 (2.38 g, 25.0 mmol). The resulting suspension
was stirred at rt for 2.5 h, then treated with 1-naphthoylchloride
(1.55 mL, 10.3 mmol) and stirred under Ar at rt overnight. The
acetonitrile was removed in vacuo, toluene (14 mL) was added and
the suspension was concentrated again. The residue was suspended in
toluene (14 mL) and washed with 12% Aq. HCl (14.1 mL). The organic
layer was removed, dried over Na.sub.2SO.sub.4, filtered and
concentrated in vacuo. The residue was purified via flash
chromatography (SiO.sub.2, 10% EtOAc/Heptane) to afford
3-Naphthalen-1-yl-3-oxo-propionic acid ethyl ester (1.65 g, 66%) as
a 3.5:1 mixture of keto/enol isomers: 1.sup.1H NMR (CDCl.sub.3,
chemical shifts in ppm relative to TMS): 1.21 (t, 3H, ketone
isomer, J=7.1 Hz), 1.36 (3 h, enol isomer, J=7.1 Hz), 4.11 (s, 2H,
ketone isomer), 4.20 (q, 2H, ketone isomer, J=7.4 Hz), 4.32 (q, 2H,
enol isomer, J=7.4 Hz), 5.50 (s, 1H, enol isomer), 7.46-7.68 (m,
3H), 7.88 (d, 1J=8.1 Hz), 7.92 (d, 1H, J=7.3 Hz), 8.03 (d, 1H,
J=8.1 Hz), 8.36 (d, 1H, enol isomer, J=8.1 Hz), 8.76 (d, 1H, J=8.1
Hz); Field Desorption Mass Spectrometry: m/z 242.
Example 226
[0653] Synthesis of
2-(Naphthalene-1-carbonyl)-4-oxo-4-phenyl-butvric Acid Ethyl Ester
105
[0654] A suspension of NaH (60% in mineral oil, 323 mg, 8.07 mmol)
in toluene (20 mL) was treated with
3-Naphthalen-1-yl-3-oxo-propionic acid ethyl ester (1.63 g, 6.7
mmol). The resulting suspension was stirred at rt under Ar for 1 h,
then treated with 2-bromocetophenone (1.61 g, 8.07 mmol). The
suspension was immersed in a 70.degree. C. oil bath and stirred
under Ar for 4 h, cooled to rt, diluted with toluene and washed
with H.sub.2O and brine. The organic layer was dried over
Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue
was purified via flash chromatography (SiO.sub.2, 10-20%
EtOAc/Heptane) to afford
2-(Naphthalene-1-carbonyl)-4-oxo-4-phenyl-butyric acid ethyl ester
(1.2 g) contaminated with a small amount of unidentified aromatic
impurity: 1.sup.1H NMR (CDCl.sub.3, chemical shifts in ppm relative
to TMS): 1.03 (t, 3H, J=7.25Hz), 3.72 (dd, 1H, J=18.8 Hz, J=5.4
Hz), 3.96 (dd, 1H, J=18.8 Hz, J=8.05 Hz), 4.09 (m, 2H), 5.16 (m,
1H), 7.45-7.63 (m, 6H), 7.88 (d, 1H, J=7.9 Hz), 8.0-8.07 (m, 3H),
8.24 (d, 1H, J=7.2 Hz)), 8,48 (d, 1H, J=8.7 Hz).
Example 227
[0655] Synthesis of
2-Naphthalen-1-yl-5-phenyl-1-(2-trimethylsilanyl-ethox-
ycarbonylamino)-1H-pyrrole-3-carboxylic Acid Ethyl Ester 106
[0656] A solution of
2-(Naphthalene-1-carbonyl)-4-oxo-4-phenyl-butyric acid ethyl ester
(1 g, 2.77 mmol) in toluene (6.5 mL) was treated with
Hydrazinecarboxylic acid 2-trimethylsilanyl-ethyl ester (599 mg,
3.34 mmol) and p-toluene sulfonic acid (33 mg). The resulting
solution was heated to reflux, with the azeotropic removal of water
(Dean Stark trap), under Ar for 6 h, cooled to rt and concentrated
in vacuo to afford
2-Naphthalen-1-yl-5-phenyl-1-(2-trimethylsilanyl-ethoxycarbonylamino)-1H--
pyrrole-3-carboxylic acid ethyl ester (1.33 g), which was not
purified, but used immediately in the next reaction.
Example 228
[0657] Synthesis of
1-Amino-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carbox- ylic acid
ethyl ester 107
[0658]
2-Naphthalen-1-yl-5-phenyl-1-(2-trimethylsilanyl-ethoxycarbonylamin-
o)-1H-pyrrole-3-carboxylic acid ethyl ester (608 mg, 1.3 mmol) was
treated with a solution of TBAF in THF (2.66 mL of a 1 M solution,
2.7 mmol). The resulting solution was stirred at rt under Ar
overnight. The reaction was quenched with glacial acetic acid (145
.mu.L, 2.5 mmol), and passed through a short plug of silica gel
eluting with toluene. The filtrate was concentrated in vacuo to
afford 1-Amino-2-naphthalen-1-yl-5-phenyl-1H-pyr- role-3-carboxylic
acid ethyl ester (434 mg), which was not purified, but was used
immediately for the next reaction.
Example 229
[0659] Synthesis of
1-[2-(2,5-Diphenyl-pyrrol-1-ylimino)-1-methyl-propylid-
eneamino]-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic Acid
Ethyl Ester a66 108
[0660] A solution of
1-Amino-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carbo- xylic acid
ethyl ester (434 mg, 1.22 mmol) in toluene (7.2 mL) was treated
with 3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one (308 mg, 1.02
mmol) and p-toluene sulfonic acid (8 mg). A Dean Stark trap was
attached, and the resulting solution heated to reflux under Ar with
the azeotropic removal of water for 18 h, then another portion of
p-toluene sulfonic acid (8 mg) was added and the azeotropic removal
of water was continued for an additional 75 min. The solution was
cooled to rt and concentrated in vacuo. The residue was dissolved
in THF/Acetic acid (10/1) and treated with PS-TsNHNH.sub.2 resin
(Argonaut Technologies, 1.039 g, 2.6 mmol). The suspension was
stirred under Ar overnight, then filtered through a polyethylene
frit, and concentrated in vacuo. The residue was purified by flash
chromatography (SiO.sub.2, 50-100% CH.sub.2Cl.sub.2/heptane) to
afford
1-[2-(2,5-Diphenyl-pyrrol-1-ylimino)-1-methyl-propylideneamino]-2--
naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester
a66 (240 mg, 37%): 1.sup.1H NMR (DMSO, chemical shifts relative to
TMS, 80.degree. C.): 0.82 (t, 3H, J=7.3 Hz), 1.08 (s, 3H), 1.74 (s,
3H), 3.91 (q, 2H, J=6.9 Hz), 6.42 (s, 2H), 7.03 (s, 1H), 7.11 (d,
4H, J=7.3 Hz), 7.18 (t, 4H, J=7.3 Hz), 7.22-7.25 (m, 2H), 7.32-7.37
(m, 5H), 7.39-7.41 (m, 2H), 7.44-7.47 (m, 2H), 7.53 (d, 1H, J=8.2
Hz), 7.93 (t, 2H, J=8.7 Hz).
Example 230
[0661] Synthesis of
4,4"-Bis-trifluoromethyl-[1,1';3',1"]terphenyl-2'-ylam- ine 109
[0662] A suspension of tetrakis(triphenylphosphine) palladium(0)
(66 mg, 0.06 mmol) in toluene (8 mL) was treated with
2,6-dibromoaniline (500 mg, 2.0 mmol), aqueous Na.sub.2CO.sub.3
(2M, 3.98 mL), and 4-trifluoromethylphenyl boronic acid (831 mg,
4.4 mmol). The resulting suspension was immersed in a 110.degree.
C. oil bath, and stirred under Ar for 22 h. The suspension was
cooled to rt, and extracted with ether. The organic layer was
washed with brine, dried over Na.sub.2SO.sub.4 and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
2.5-5.0% EtOAc/Heptane) to afford 4,4"-Bis-trifluoromethyl-[1-
,1';3',1"]terphenyl-2'-ylamine (713 mg, 93%): .sup.1H NMR
(CDCl.sub.3, chemical shifts in ppm relative to TMS): 6.93 (t, 1H,
J=7.3 Hz), 7.14 (d, 2H, J=7.3 Hz), 7.64 (d, 4H, J=8.0 Hz), 7.74 (d,
4H, J=8.0 Hz).
Example 231
[0663] Synthesis of
N.sup.1,N.sup.2-Bis-(4,4"-bis-trifluoromethyl-[1,1';3'-
,1"]terphenyl-2'-yl)-oxalamide 110
[0664] A solution of 4,4"-Bis-trifluoromethyl-
[1,1';3',1"]terphenyl-2'-yl- amine (700 mg, 1.84 mmol) in pyridine
(5 mL) was treated with oxalyl chloride (73 gL, 0.837 mmol). The
resulting suspension was stirred at rt overnight under Ar, then
poured into H.sub.2O. The precipitate was filtered, washed with
H.sub.2O and dried in vacuo. The resulting solid was crystallized
from toluene/heptane, then recrystallized from toluene to afford
N,N'-Bis-(4,4"-his-trifluoromethyl-[1,1 ';3',1"]terphenyl-2'-yl-
)-oxalamide (430 mg).
Example 232
[0665] Synthesis of
N.sup.1,N.sup.2-Bis-(4,4"-bis-trifluoromethyl-[1,1';3'-
,1"]terphenyl-2'-yl)-oxalodiimidoyl Dichloride 111
[0666] A suspension of
N,N'-Bis-(4,4"-bis-trifluoromethyl-[1,1';3',1"]terp-
henyl-2'-yl)-oxalamide (419 mg, 0.513 mmol) in toluene (4.1 mL) was
treated with PCl.sub.5 (408 mg, 1.96 mmol) at rt. The resulting
suspension was immersed in a 60.degree. C. oil bath, and stirred
under Ar for 6.5 h, then heated to 80.degree. C. for an additional
1 h. The yellow solution was cooled to rt, diluted with ether (5
mL) and washed with H.sub.2O (10 mL) and Aq. sat'd NaHCO.sub.3. The
organic layer was dried over Na.sub.2SO.sub.4, filtered and
concentrated in vacuo to afford
N.sup.1,N.sup.2-Bis-(4,4"-bis-trifluoromethyl-[1,1';3',1"]terphenyl-2'-yl-
)-oxalodiimidoyl dichloride (401 mg, 92%) as a yellow solid: 7.33
(d, 4H, J=8.4 Hz), 7.38 (m, 3H), 7.50 (d, 4H, J=8.4 Hz); Field
Desorption Mass Spectrometry: m/z 852.
Example 233
[0667] Synthesis of
2,3-bis-(2,6-bis-(4-trifluoromethylphenyl)-phenylimino-
)-[1,4]dithiane V10 112
[0668] Ethane dithiol (264 .mu.L, 3.15 mmol) was added via syringe
to a suspension of NaH (75.6 mg, 60% in oil, 1.89 mmol) in THF (5
mL). The resulting suspensiuon was stirred under Ar at rt for 15
min, then treated with a solution of
N.sup.1,N.sup.2-Bis-(4,4"-bis-trifluoromethyl-[1,1';3'-
,1"]terphenyl-2'-yl)-oxalodiimidoyl dichloride (401 mg, 0.471 mmol)
in THF (5 mL). The suspension was stirred overnight under Ar, then
heated to 65.degree. C. until not bis-imidoyl chloride remained (45
min) as determined by TLC. The reaction was cooled to rt, quenched
with H.sub.2O, and extracted with toluene. The organic layer was
dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo.
The residue was crystallized from heptane/CH.sub.2Cl.sub.2 to
afford
2,3-bis-(2,6-bis-(4-trifluoromethylphenyl)-phenylimino)-[1,4]dithiane
V10 (260 mg, 63%) as a yellow solid: 1.sup.1H NMR (CDCl.sub.3,
chemical shifts in ppm relative to TMS): 2.06 (bs, 4H), 7.32-7.42
(m, 8H), 7.49 (bs, 7H); Field Desorption Mass Spectrometry: m/z
875.
Example 234
[0669] Synthesis of
2,3-bis-(2,6-diphenyl-phenylimino)-[1,4]dithiane V9 113
[0670] 2,3-bis-(2,6-diphenyl-phenylimino)-[1,4]dithiane V9 was
prepared using similar reaction conditions as described in Example
233 and was purified via washing with heptane and hot ethanol to
afford 2,3-bis-(2,6-diphenyl-phenylimino)-[1,4]dithiane V9: .sup.1H
NMR (DMSO, 80.degree. C., chemical shifts in ppm relative to TMS):
2.21 (s, 4H), 7.21-7.39 (m, 26H).
Examples 235-241
[0671] Synthesis of Ligands V1, V2, V3, V4, V5, V6, V8, and V12:
114115
[0672] Ligands V1-V6, V8 and V12 were prepared using conditions
similar to those described in Example 233.
7 Example Ligand .sup.1H NMR Data.sup.a,b 235 V5 mixture of
isomers, .delta.2.02(s, 6H), 2.54-2.62(m, 2H), 2.98-3.06(m, 2H),
6.90- 7.06(m, 3H), 7.28-7.50(m, 9H), 7.60-7.76(m, 8H) 236 V6
.delta.2.02(m, 1H), 2.47-2.64(m, 1H), 2.72-3.08(m, 2H),
7.16-7.40(m, 8H), 7.4- 7.54(m, 4H), 7.68-7.82(m, 2H) 237 V2
(CD.sub.2Cl.sub.2) .delta.1.98(m, 2H), 2.62(s, 3H), 2.98(m, 2H),
7.11-7.21(m, 10H), 7.23- 7.35(m, 12H), 7.40(m, 6H), 7.49(t, J=7.9
Hz, 3H), 7.6(d, J=7.9 Hz, 2H), 7.78(d, J=7.9 Hz, 2H) 238 V1
(CD.sub.2Cl.sub.2) .delta.2.16(s, 4H), 7.25-7.41(m, 14H),
7.41-7.53(m, 12H), 7.63(s, 4H), 7.67-7.73(m, 4H) 239 V4
.delta.2.32(s, 6H), 3.40(s, 4H), 7.40(s, 4H) 240 V3
(CD.sub.2Cl.sub.2).delta.2.30(s, 6H), 4.46(s, 4H), 7.39(s, 4H) 241
V12 .delta.2.24(s, 3H), 2.25(s, 3H), 2.35(s, 3H), 2.36(s, 3H),
3.36(s, 4H), 7.22(d, J=8.3 Hz, 2H), 7.68(d, J=8.3 Hz, 2H) .sup.aAll
Spectra Recorded in CDCl.sub.3, Unless Otherwise Indicated
.sup.bAll Chemical Shifts are Reported in ppm Relative to TMS
Example 242
[0673] Preparation of a Pro-catalyst Stock Solution from Ligand V1:
Ligand V1 (34.1 mg, 0.045 mmol), Ni(II) acetylacetonate (9.8 mg,
0.038 mmol) and triphenylcarbenium
tetrakis)pentafluorophenyl)borate (34.8 mg, 0.038 mmol) were
combined in a Schlenk Tube in an inert atmosphere dry box. The
mixture was removed from the dry box and treated with
CH.sub.2Cl.sub.2 (7.0 mL) under an inert atmosphere to provide a
dark red stock solution of the pro-catalyst.
Example 243-319
[0674] Ethylene Polymerization with a Pro-catalyst of the Type
Prepared in Example 242
[0675] A Schlenk flask (200 mL, 500 mL or 1000 mL) equipped with a
magnetic stir bar and capped with a septum was evacuated and
refilled with ethylene, then charged with dry, deoxygenated toluene
(100 mL) and a 10 wt % solution of MAO in toluene (4.0 mL). The
requisite volume of pro-catalyst solution (prepared from the
indicated ligand as in example 242) was added to give the amount of
Ni indicated in the table below. The mixture was stirred under 1
atm ethylene at the temperature indicated in the table below and a
polyethylene precipitate was observed. After the indicated reaction
time, the mixture was quenched by the addition of acetone (50 mL),
methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
polyethylene was isolated by vacuum filtration and washed with
water, methanol and acetone, then dried under reduced pressure at
100.degree. C. for 16 h to obtain the amount of polyethylene
indicated in the table below.
8 Temp Time Branches/ Example Ligand (C.) .mu.mol Ni min g PE
M.sub.n 1000 C's 243 V8 23 0.549 15.00 0.805 38,200 21.0 244 V1 23
0.551 6.00 0.795 782,700 4.7 245 V1 23 0.559.sup.a 14.00 1.629
131,500 1.8 246 V1 23 0.547.sup.b 6.00 0.540 145,300 2.9 247 V7 23
0.552.sup.b 6.00 0.048 82,800 22.6 248 V1 23 0.276.sup.c 24.00
0.539 89,000 3.0 249 V1 23 0.276 8.00 0.371 703,700 4.5 250 V1 23
0.276.sup.c 24.00 0.934 87,800 2.7 251 V1 23 0.276 8.00 0.529
540,700 3.6 252 V1 23 0.276.sup.c 15.00 0.527 88,500 3.2 253 V2 23
2.320 8.00 0.178 92,900 11.3 254 V3 23 1.04.sup.d 8.00 0.351 77,700
16.2 255 V3 23 1.040 8.00 0.776 46,700 19.9 256 V4 23 0.21.sup.e
13.66 0.620 207,000 11.3 257 V4 23 0.405 5.33 0.828 192,200 12.0
258 V4 23 0.405.sup.d 6.00 0.324 177,800 8.4 259 V6 23 0.418 56.75
0.611 97,200 55.4 260 V5 23 0.380 6.00 0.333 103700 22.8 261 V1 60
0.400 5.00 262 V1 60 0.400 30.00 0.219 263 V1 60 0.400 120.00 0.473
421600 264 V1 60 0.400 15.00 0.104 112200 14 265 V1 60 0.400 45.00
0.401 287500 14.7 266 a67 23 0.366 14.00 0.446 115400 3.9 267 a67
23 0.366 6.00 0.518 151100 3.6 268 V12 23 0.373 12.00 0.194 168800
12.5 269 V1 60 0.400.sup.f,h 960.00 4.447 18.5 270 a54 23 0.392
2.50 0.762 132300 3 271 a54 23 0.392.sup.b 70.00 0.207 112500 1.5
272 a54 23 0.392.sup.i 8.00 0.596 157900 2 273 a54 60 0.392.sup.f,h
62.00 1.111 44600 20.2 274 a54 60 0.196.sup.f,h 62.00 0.711 82200
12.5 275 V1 60 0.400 35.00 1.18 276 a52 23 0.401 10.00 0.3 132900
2.3 277 a54 23 0.402.sup.e 5.00 2.973 139900 3.5 278 a54 20
0.401.sup.j,k 20.00 0.426 58000 14.3 279 V1 23 0.384.sup.e 5.00
0.735 280 V1 80 0.384.sup.e 5.00 281 V1 60 0.399.sup.g 10.00 0.097
101000 15.1 282 V1 60 0.200.sup.g 10.00 0.037 62600 14.2 283 V1 60
0.100.sup.g 26.00 0.026 63900 64.1 284 V1 80/0.sup.1 0.399.sup.g
20.00 0.728 368200 2.3 285 V1 80/0/23.sup.m 0.399.sup.g 15.00 0.94
516200 4.4 286 V1 80 0.399.sup.g 45.00 0.253 97800 19.8 287 a53
60/0/23.sup.n 0.398.sup.g 48.00 0.198 288 V10 23 0.400.sup.e 15.00
0.447 513800 5.7 289 V10 23 0.400 8.00 0.284 398800 4.5 290 V10 23
0.400.sup.d 8.00 0.337 195200 2.5 291 V10 23 0.400.sup.c 8.00 0.233
109300 2 292 V10 60 0.400.sup.g 55.00 0.433 204300 13.4 293 a59 23
0.400.sup.g 6.00 1.054 98300 294 a59 23 0.400.sup.d 6.00 0.768
77000 295 a59 60 0.400.sup.g 60.00 0.236 28800 296 V11 23
0.402.sup.g 20.00 0.623 302500 297 V11 23 0.402 20.00 0.146 252200
298 a66 23 0.398.sup.g 9.00 0.706 60700 4.2 299 a66 23 0.398.sup.d
12.00 0.515 43600 3.1 300 a66 60 0.398.sup.g 60.00 301 a59 80/0/23
0.400.sup.g 15.00 302 V9 23 0.400.sup.g 8.00 0.899 5.8 303 a52 60
2.01.sup.g 950.00 10.289 44300 18 304 a52 60 2.01.sup.g 950.00
10.289 42900 11 305 a66 60 1.99.sup.g 315.00 1.518 306 a59 23
0.400.sup.b 12.00 0.295 181100 307 a66 23 0.398.sup.b 24.00 0.973
121100 308 a59 23 0.400.sup.b 60.00 0.503 166900 309 a52 23
0.401.sup.b 14.00 0.47 84400 310 a59 23 0.400.sup.c 60.00 0.239
129000 311 a52 23 0.401.sup.c 28.00 0.674 52700 312 a54 23 0.050
4.00 0.366 210200 313 a54 23 0.201.sup.i 4.00 0.542 529800 314 a54
23 0.020 8.00 0.222 335400 315 a54 23 0.020 16.00 0.391 214500 316
a54 23 0.020 32.00 0.718 317 a52 23 0.401 12.00 0.405 318 a52 23
0.401.sup.b 12.00 0.339 319 a52 23 0.401.sup.c 12.00 0.322 .sup.a60
mL of H.sub.2 injected subsurface before the catalyst injection
.sup.b50 mL of H.sub.2 injected subsurface before the catalyst
injection .sup.c100 mL of H.sub.2 injected subsurface before the
catalyst injection .sup.d25 mL of H.sub.2 injected subsurface
before the catalyst injection .sup.e600 mL of solvent .sup.fDEAC
used as cocatalyst .sup.g300 mL of solvent .sup.hMineral spirits
used as solvent .sup.i10 mL of H.sub.2 injected subsurface before
the catalyst injection .sup.j90 mL of toluene used as solvent
.sup.k10 mL of 1-hexene added to the polymerization .sup.l5 min at
80.degree. C., 15 min at 0.degree. C. .sup.m5 min at 80.degree. C.,
5 min at 0.degree. C., 5 min at 23.degree. C. .sup.n25 min at
60.degree. C., 5 min at 0.degree. C., 18 min at 23.degree. C.
Example 320
[0676] Preparation of Ligand V11 116
[0677] 2,3-bis-(2,6-diphenyl-4-methyl-phenylimino)-[1,4]dithiane
V11 was prepared using similar reaction conditions as described in
Example 233; .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm
relative to TMS): 2.36 (s, 4H), 2.41 (s, 6H), 7.16-7.23 (m,
24H).
Example 321
[0678] Preparation of Ligand a67
[0679]
5-tert-Butyl-1-[2-(2,5-dimethyl-pyrrol-1-ylimino)-1-methyl-propylid-
eneamino]-2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester a67 was
prepared using similar reaction conditions to those described in
example 229; .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm
relative to TMS): 1.28 (s, 9H), 1.37 (t, 3H, J=6.9 Hz), 2.07 (s,
6H), 2.16 (s, 3H), 2.26 (s, 3H), 2.27 (s, 3H), 4.26-4.33 (m, two
isomers, 2H), 5.93 (s, 2H), 6.44 (s, 3H).
Example 322
[0680] Synthesis of aa1. 117
[0681] A flame dried Schlenk flask equipped with a rubber septum
and a stir bar was charged with 128 mg (0.5 mmol) of nickel (II)
acetylacetonate. Methylene chloride (10-ml) was added followed by
the addition of a methylene chloride solution of
2,3-bis(2,6-diphenylimino)-[- 1,4]dithiane [300 mg (0.5 mmol) in
10-ml of CH.sub.2Cl.sub.2] resulting in a brown solution. After 2
minutes of stirring, a methylene chloride solution of
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 was added giving a red solution.
The mixture was allowed to stir for 1.5 hours. The solvent was
removed in vacuo resulting in an oily solid. The oily solid was
taken up in 5-ml of diethyl ether. Addition of 15-ml of hexane
resulted in partial precipitation of the desired compound. The
solvent was removed in vacuo giving a red powder. The red solid was
washed with an Et.sub.2O/hexane solution. The wash was repeated and
the resulting solid taken up in a 1:1 Et.sub.2O/CH.sub.2Cl.sub.2
solution. Hexane was layered onto the red solution and the mixture
cooled to -78.degree. C. and left to sit overnight. Upon sitting
red crystals formed and the supernatent was removed via filter
cannula. The resulting crystalline solid was dried under dynamic
vacuum for several hours giving 374 mg of a red crystalline solid.
.sup.1H NMR was consistent with the desired complex.
Example 323
[0682] Polymerization of Ethylene with aa1+mMAO
[0683] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and
1-ml of mMAO (Akzo Nobel). In an inert atmosphere glove box, a
septum-capped vial was charged with 3 mg of aa1. The vial was
removed from the box and 20-ml of CH.sub.2Cl.sub.2 was added to the
vial. The reactor was sealed and pressurized up to 150 psig
ethylene and heated to 60.degree. C. A 2-ml portion (0.3 mg,
2.1.times.10.sup.-7 mol) of the solution of aa1 was removed from
the vial and added to the autolclave via the high-pressure sample
loop while pressurizing the autoclave to 200 psig. After 15 minutes
of stirring at 200-psig ethylene and 60.degree. C., the reaction
was quenched upon addition of 2-ml of methanol at high pressure.
The reactor was vented and the contents poured into a beaker
containing a methanol acetone/mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
-100.degree. C. giving 8.9 grams of polyethylene (6.1 million
catalyst turnovers per hour).
Example 324
[0684] Polymerization of Ethylene with aa1+mMAO
[0685] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene and
1-ml of mMAO (Akzo Nobel). In an inert atmosphere glove box, a
septum-capped vial was charged with 3 mg of aa1. The vial was
removed from the box and 20-ml of CH.sub.2Cl.sub.2 was added to the
vial. The reactor was sealed and pressurized up to 150-psig
ethylene and heated to 100.degree. C. A 2-ml portion (0.3 mg,
2.1.times.10.sup.-7 mol) of the solution of aa1 was removed from
the vial and added to the autolclave via the high-pressure sample
loop while pressurizing the autoclave to 200 psig. After 15 minutes
of stirring at 200-psig ethylene and 100.degree. C., the reaction
was quenched upon addition of 2-ml of methanol at high pressure.
The reactor was vented and the contents poured into a beaker
containing a methanol acetone/mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
100.degree. C. giving 2.4 grams of polyethylene 1.6 million
catalyst turnovers per hour). GPC analysis M.sub.n=309,000;
PDI=3.16. .sup.1H NMR 13 branches/1000 carbons.
Example 325
[0686] Preparation of Silica Supported Catalyst of aa1
[0687] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged in an inert atmosphere glove box with
14.3 mg (9.94.times.10.sup.-7 mol) of aa1 and 1 gram of Grace
Davison 2402 silica. The flask was removed from the glove box,
attached to the vacuum/argon manifold, evacuated and refilled with
argon. To the solid mixture was added 5-ml of 1,2-difluorobenzene.
The resulting suspension was stirred for 45 minutes at 0.degree. C.
The solvent was removed in vacuo giving 875 mg of the desired
supported catalyst (catalyst loading 10 .mu.mol/gram of
silica).
Example 326
[0688] Preparation of Silica Supported Catalyst of aa1
[0689] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged in an inert atmosphere glove box with 1
gram of Grace Davison 2402 silica. The flask was removed from the
glove box, attached to the vacuum/argon manifold, evacuated and
refilled with argon. To the solid was added 28.6 mg (20 .mu.mol) of
aa1 as a solution in CH.sub.2Cl.sub.2 (5-ml total). The resulting
suspension was stirred for 30 minutes at room temperature. The
solvent was removed in vacuo giving 889 mg of the desired supported
catalyst (catalyst loading 20 .mu.mol/gram of silica).
Example 327
[0690] Preparation of Silica Supported Catalyst of aa1
[0691] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged in an inert atmosphere glove box with 1
gram of Grace Davison 2402 silica. The flask was removed from the
glove box, attached to the vacuum/argon manifold, evacuated and
refilled with argon. To the solid was added 14.3 mg (10 .mu.mol) of
aa1 as a solution in CH.sub.2Cl.sub.2 (5-ml total). The resulting
suspension was stirred for 30 minutes at room temperature. The
solvent was removed in vacuo giving 905 mg of the desired supported
catalyst (catalyst loading 10 .mu.mol/gram of silica).
Example 328
[0692] Preparation of Silica Supported Catalyst of aa1
[0693] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged in an inert atmosphere glove box with 1
gram of Grace Davison 2402 silica. The flask was removed from the
glove box, attached to the vacuum/argon manifold, evacuated and
refilled with argon. To the solid was added 57.2 mg (40 .mu.mol) of
aa1 as a solution in CH.sub.2Cl.sub.2 (5-ml total). The resulting
suspension was stirred for 30 minutes at room temperature. The
solvent was removed in vacuo giving 911 mg of the desired supported
catalyst (catalyst loading 40 .mu.mol/gram of silica).
Examples 329-333
[0694] Gas Phase Polymerization of Ethylene Using in situ
Activation Protocol
[0695] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with -300 grams of NaCl and the
supported procatalyst aa1 in an inert atmosphere glove box. The
reactor was sealed removed from the glove box and placed under an
argon atmosphere. The reactor was heated to 60.degree. C. and
trirnethyl aluminum was added as a solution in toluene or hexame.
The reactor is rapidly pressurized to 200-psig ethylene and left to
stir. The reactor was vented and the contents poured into a beaker.
The polymer was isolated by blending the salt/polymer mixture in
water. The resulting polyethylene was collected dried in the vacuum
oven overnight at -100.degree. C.
9 Conc. Catalyst Rxn Yield TON Productivity .mu.mol Ni/g TMA
Charged time PE mol C.sub.2H.sub.4/ g PE/g supported M.sub.w Ex.
silica mmol (mg) (min) (g) mol Ni catalyst (.times. 10.sup.-3) 329
10 4 100 120 5.9 296K 83 1440 330 10 4 100 60 4.9 176K 49 1490 331
10 4 100 60 7.3 261K 72 1660 332 10 4 50 60 3.5 254K 70 -- 333 40 8
50 60 17.2 307k 344 1800
Examples 334-342
[0696] 118
[0697] Polymerization of Ethylene in the Presence of H.sub.2 to
Control Molecular Weight.
[0698] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene, 1-ml
of mMAO (7.14 wt % Al; Akzo Nobel) and H.sub.2 gas. In an inert
atmosphere glove box, a septum-capped vial was charged with
2.1.times.10.sub.-6 mol of aa1 or z1. The vial was removed from the
box and 20-ml of CH.sub.2Cl.sub.2 was added to the vial. The
reactor was sealed and pressurized up to 150-psig ethylene and
heated to 60.degree. C. A 2-ml portion (2.1.times.10.sup.-7 mol of
catalyst) of the solution of catalyst was removed from the vial and
added to the autoclave via the high-pressure sample loop while
pressurizing the autoclave to 200 psig. After 15 minutes of
stirring at 200-psig ethylene and 60.degree. C., the reaction was
quenched upon addition of 2-ml of methanol at high pressure. The
reactor was vented and the contents poured into a beaker containing
a methanol acetone/mixture. The polymer was collected by suction
filtration and dried in the vacuum oven overnight at -100.degree.
C.
10 H.sub.2 Yield TO TOF added PE mol C.sub.2H.sub.4/mol mol
C.sub.2H.sub.4/ M.sub.n Ex. Catalyst (ml) (g) Ni (.times.
10.sup.-3) mol Ni h (.times. 10.sup.-3) (.times. 10.sup.-3) 334 aa1
0 8.9 1500 6100 1100 335 aa1 25 6.6 1100 4500 1100 336 aa1 50 7.3
1200 4900 524 337 aa1 100 6.1 1000 4100 277 338 aa1 150 7.7 1300
5300 349 339 aa1 100 6.4 1100 4300 576 340 z1 0 2.2 93 371 314 341
z1 50 0.18 6 26 164 342 z1 150 0.18 6 26 41
[0699] These data demonstrate that the catalysts of the present
invention, especially those of the twenty-fourth and higher
aspects, give rise to lower molecular weight polymer when the
polymerization are conducted in the presence of hydrogen, while
exhibiting dramatically less inhibition or deactivation than the
.alpha.-diimine catalyst z1.
Examples 343-346
[0700] Ethylene Polymerization with a Pro-catalyst of the Type
Prepared in Example 242
[0701] A Schlenk flask (200 mL, 500 mL or 1000 mL) equipped with a
magnetic stir bar and capped with a septum was evacuated and
refilled with ethylene, then charged with dry, deoxygenated toluene
(100 mL) and a 10 wt % solution of MAO in toluene (4.0 mL). The
requisite volume of pro-catalyst solution (prepared from the
indicated ligand as in example 242) was added to give the amount of
Ni indicated in the table below. The mixture was stirred under 1
atm ethylene at the temperature indicated in the table below and a
polyethylene precipitate was observed. After the indicated reaction
time, the mixture was quenched by the addition of acetone (50 mL),
methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
polyethylene was isolated by vacuum filtration and washed with
water, methanol and acetone, then dried under reduced pressure at
100.degree. C. for 16 h to obtain the amount of polyethylene
indicated in the table below.
11 Branches/ Temp mmol Time 1000 Example Ligand (C.) Ni min g PE
M.sub.n C's 343 V3 60 1.040 5.00 0.104 26,000 21.1 344 V4 60 0.405
25.00 none 345 V5 60 0.380 25.33 0.492 346 V5 23 0.380.sup.a 6.00
0.175 .sup.a30 mL of H.sub.2 added subsurface prior to pro-catalyst
injection
Example 347
[0702] Ethylene Polymerization at 57 C, 208 psig with the Catalyst
Prepared From Ligand V1, Ni(acac).sub.2,
Ph.sub.3CB(C.sub.6F.sub.5).sub.4- , and MAO
[0703] A 1 L Parr.RTM. autoclave, Model 4520, was dried by heating
under vacuum to 180 C. at 0.6 torr for 16 h, then cooled and
refilled with dry nitrogen. The autoclave was charged with dry,
deoxygenated toluene (450 mL) and 4.0 mL of a 10 wt % solution of
MAO in toluene (Aldrich.RTM.), heated to 50.degree. C. and
pressurized to 80 psig with ethylene. A sample loop was then used
to inject 2.0 mL of a stock solution of pro-catalyst prepared from
9.375 mL dry, deoxygenated CH.sub.2Cl.sub.2 and 0.625 mL of a stock
solution prepared from ligand V1 (29.4 mg), Ni(acac).sub.2 (10.4
mg), Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (36.2 mg) and 5.0 mL of dry,
deoxygenated CH.sub.2Cl.sub.2, and pressurized to about 200 psig
with ethylene. The mixture was stirred under ethylene at an average
pressure of about 208 psig and an average temperature of 57.degree.
C. for 80 min, after which the pressure was vented, the autoclave
was opened, and the polymer treated with MeOH and 6 N aq HCl and
isolated by filtration to obtain 60.3 g (2.1.times.10.sup.6 mol
C.sub.2H.sub.4/mol Ni) of white, partially crystalline
polyethylene.
Example 348
[0704] Ethylene Polymerization at 84 C., 270 psig with the Catalyst
Prepared from Ligand V1, Ni(acac).sub.2,
Ph.sub.3CB(C.sub.6F.sub.5).sub.4- , and MAO
[0705] A procedure similar to that used in Example 347 was
followed, except that the polymerization reaction temperature was
84 C., the pressure was 270 psig ethylene and the reaction was
quenched by sample loop injection of 2.0 mL MeOH at 7.1 min. This
gave 20.0 g polyethylene from 1.0 .mu.mol catalyst (700,000 mol
C.sub.2H.sub.4/mol Ni), corresponding to a rate of
5.9.times.10.sup.6 mol C.sub.2H.sub.4/mol Ni/h. GPC:
M.sub.n=779,000, M.sub.w/M.sub.n=1.88.
Example 349
[0706] Ethylene Polymerization at 64 C, 260 psig with the Catalyst
Prepared from Ligand a54, Ni(acac).sub.2,
Ph.sub.3CB(C.sub.6F.sub.5)4, and MAO
[0707] A procedure similar to that used in Example 348 was
followed, except that the ligand was a54, the polymerization
reaction temperature was 64 C., the pressure was 260 psig ethylene
and the reaction was quenched by sample loop injection of 2.0 mL
MeOH at 5.0 min. This gave 24.3 g polyethylene from 0.4 .mu.mol
catalyst (2.2.times.10.sup.6 mol C.sub.2H.sub.4/mol Ni),
corresponding to a rate of 2.6.times.10.sub.7 mol
C.sub.2H.sub.4/mol Ni/h. GPC: M.sub.n=73,000, M.sub.w/M.sub.n=1.97.
.sup.1H NMR: 2 branches/1000 C; 100% terminal olefin (within
experimental error).
Example 350
[0708] Preparation of a Heterogeneous Catalyst Comprising Ligand
V1
[0709] To a vial charged with V1 (37.8 mg; 50.0 .mu.mol),
Ni(acac).sub.2 (12.8 mg; 49.9 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (46.5 mg; 50.4 .mu.mol) was added
3.0 mL 1,2-difluorobenzene. The resulting solution was stirred
overnight (ca. 18 hours). This solution was then added dropwise to
silica at 0.degree. C. (1.0 g; PQ Corporation, MS-3030 dried at
600.degree. C. under 500 SCCM helium). The flask was then warmed up
to room temperature and vacuum was applied for an hour to remove
volatile. The flask was then cooled back to 0.degree. C. with an
ice-water bath and diethylaluminum chloride (2.7 mL; 1.0M in
hexanes) was added dropwise with proper agitation. Volatiles were
removed in vacuo at 0.degree. C. for 90 min. The resulting brown
solid was stored under nitrogen at -30.degree. C.
Example 351
[0710] Polymerization of Ethylene Using the Catalyst Prepared in
Example 350
[0711] A catalyst delivery device was charged with the catalyst
prepared in Example 350 (58.6 mg; 2.2 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (325 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed,
evacuated and backfilled with nitrogen. The salt was subsequently
treated with trimethylaluminum (10 mL; 2.0 M in toluene) and
agitated at 60.degree. C. for 30 min. The reactor was then
pressurized with 200 psi ethylene and depressurized to atmospheric
pressure four times. The catalyst was then introduced in the
reactor with appropriate agitation. The reaction was allowed to
proceed for 4 hours at 62.degree. C. before the reactor was vented.
The polymer was isolated by washing the contents of the reactor
with water. The isolated polymer was further treated with 6 M HCl
in methanol, rinsed with methanol and dried under vacuum to give
51.2 g (630 K TO, 875 g polymer/g silica; .sup.1H NMR:
M.sub.n>50K, 6 BP/1000 C; T.sub.m=125.degree. C.).
Example 352
[0712] Polymerization of Ethylene Using the Catalyst Prepared in
Example 350 in the Presence of Hydrogen
[0713] A catalyst delivery device was charged with the catalyst
prepared in Example 350 (47.7 mg; 1.8 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (348 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed
and evacuated. The reactor was then pressurized with 200 psi
ethylene and depressurized to atmospheric pressure three times. The
salt was subsequently treated with trimethylaluminum (10 mL; 2.0 M
in hexanes) and agitated at 60.degree. C. for 30 min. The reactor
was again pressurized with 200 psi ethylene and depressurized to
atmospheric pressure three times. Hydrogen (150 mL) was
subsequently added to the reactor. The catalyst was then introduced
in the reactor with appropriate agitation. The reaction was allowed
to proceed for 4 hours at 56.degree. C. before the reactor was
vented. The polymer was isolated by washing the contents of the
reactor with water. The isolated polymer was further treated with 6
M HCl in methanol, rinsed with methanol and dried under vacuum to
give 3.41 g (67.7 K TO, 71 g polymer/g silica; GPC: M.sub.n=159K,
M.sub.w/M.sub.n=3.0; T.sub.m=123.degree. C.).
Example 353
[0714] Preparation of a Heterogeneous Catalyst Comprising Ligand
V1
[0715] A 1,2-difluorobenzene solution (3.0 mL) containing 20.2
.mu.mol of V1, Ni(acac).sub.2 and Ph.sub.3CB(C.sub.6F.sub.5).sub.4
was added dropwise to silica at 0.degree. C. (2.0 g; Grace Davison,
XPO-2402). The flask was then warmed up to room temperature and
vacuum was applied for an hour to remove volatile. The flask was
then cooled back to 0.degree. C. with an ice-water bath and
diethylaluminum chloride (2.7 mL; 1 M in hexanes) was added
dropwise with proper agitation. Volatiles were removed in vacuo at
0.degree. C. for 90 min. The resulting solid was stored under
nitrogen at -30.degree. C.
Example 354
[0716] Polymerization of Ethylene Using the Catalyst Prepared in
Example 353
[0717] A catalyst delivery device was charged with the catalyst
prepared in Example 353 (205 mg; 1.9 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (329 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed,
evacuated and backfilled with nitrogen. The salt was subsequently
treated with trimethylaluminum (10 mL; 2.0 M in toluene) and
agitated at 60.degree. C. for 30 min. The reactor was then
pressurized with 200 psi ethylene and depressurized to atmospheric
pressure four times. The catalyst was then introduced in the
reactor with appropriate agitation. The reaction was allowed to
proceed for 90 min at 63.degree. C. before the reactor was vented.
The polymer was isolated by washing the contents of the reactor
with water. The isolated polymer was further treated with 6 M HCl
in methanol, rinsed with methanol and dried under vacuum to give
45.8 g (857 K TO, 224 g polymer/g silica; .sup.1H NMR:
M.sub.n>50K, 8 BP/1000 C; T.sub.m=122.degree. C.).
Example 355
[0718] Preparation of a Heterogeneous Catalyst Comprising Ligand
V1
[0719] To a vial charged with V1 (37.7 mg; 49.9 .mu.mol),
Ni(acac).sub.2 (12.8 mg; 49.9 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (46.1 mg; 50.0 .mu.mol) was added
3.0 mL 1,2-difluorobenzene. The resulting solution was stirred
overnight (ca. 18 hours). This solution was then added dropwise to
silica at 0.degree. C. (1.02 g; PQ Corporation, MS-3030 dried at
600.degree. C. under 500 SCCM helium). The flask was then warmed up
to room temperature and vacuum was applied for 90 min to remove
volatile. The resulting brick-red solid was stored under nitrogen
at -30.degree. C.
Example 356
[0720] Polymerization of Ethylene Using the Catalyst Prepared in
Example 355
[0721] A catalyst delivery device was charged with the catalyst
prepared in Example 355 (44.1 mg; 2.2 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (328 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed,
evacuated and backfilled with nitrogen. The salt was subsequently
treated with trimethylaluminum (10 mL; 2.0 M in hexane) and
agitated at 60.degree. C. for 30 min. The reactor was then
pressurized with 200 psi ethylene and depressurized to atmospheric
pressure three times. The catalyst was then introduced in the
reactor with appropriate agitation. The reaction was allowed to
proceed for 4 hours at 86.degree. C. before the reactor was vented.
The polymer was isolated by washing the contents of the reactor
with water. The isolated polymer was further treated with 6 M HCl
in methanol, rinsed with methanol and dried under vacuum to give
48.0 g (777 K TO, 1100 g polymer/g silica; GPC: M.sub.n=1,300,000,
M.sub.w/M.sub.n=2.0; T.sub.m=112.degree. C.).
Example 357
[0722] Preparation of a Heterogeneous Catalyst Comprising Ligand
a54
[0723] To a vial charged with a54 (26.0 mg; 50.1 .mu.mol),
Ni(acac).sub.2 (12.8 mg; 49.9 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (46.1 mg; 50.0 .mu.mol) was added
3.0 mL 1,2-difluorobenzene. The resulting solution was stirred
overnight (ca. 18 hours). This solution was then added dropwise to
silica at 0.degree. C. (992 mg; PQ Corporation, MS-3030 dried at
600.degree. C. under 500 SCCM helium). The flask was then warmed up
to room temperature and vacuum was applied for 90 min to remove
volatile. The resulting brick-red solid was stored under nitrogen
at -30.degree. C.
Example 358
[0724] Polymerization of Ethylene Using the Catalyst Prepared in
Example 357
[0725] A catalyst delivery device was charged with the catalyst
prepared in Example 357 (94 mg; 4.7 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (320 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed,
evacuated and backfilled with nitrogen three times. The salt was
subsequently treated with trimethylaluminum (10 mL; 2.0 M in
hexane) and agitated at 60.degree. C. for 30 min. The reactor was
then pressurized with 200 psi ethylene and depressurized to
atmospheric pressure three times. The catalyst was then introduced
in the reactor with appropriate agitation. The reaction was allowed
to proceed for 3.5 hours at 58.degree. C. before the temperature
was increased to 80.degree. C. The reaction was allowed to proceed
for a total of 5.5 hours. The polymer was isolated by washing the
contents of the reactor with water. The isolated polymer was
further treated with 6 M HCl in methanol, rinsed with methanol and
dried under vacuum to give 2.52 g (18,700 TO, 27 g polymer/g
silica; GPC: M.sub.n=45,500; M.sub.w/M.sub.n=4.6;
T.sub.m=118.degree. C.).
Example 359
[0726] Preparation of a Heterogeneous Catalyst Comprising Ligand
V9
[0727] To a vial charged with V9 (30.1 mg; 49.9 .mu.mol),
Ni(acac).sub.2 (13.1 mg; 50.1 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (46.2 mg; 50.1 .mu.mol) was added
3.0 mL 1,2-difluorobenzene. The resulting solution was stirred
overnight (ca. 18 hours). This solution was then added dropwise to
silica at 0.degree. C. (996 mg; PQ Corporation, MS-3030 dried at
600.degree. C. under 500 SCCM helium). The flask was then warmed up
to room temperature and vacuum was applied for 90 min to remove
volatile. The resulting solid was stored under nitrogen at
-30.degree. C.
Example 360
[0728] Polymerization of Ethylene Using the Catalyst Prepared in
Example 359 in the Presence of Hydrogen
[0729] A catalyst delivery device was charged with the catalyst
prepared in Example 359 (54.4 mg; 2.8 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (313 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed
and evacuated. The reactor was then evacuated and backfilled with
nitrogen (1 atm) three times. The salt was subsequently treated
with trimethylaluminum (10 mL; 2.0 M in hexanes) and agitated at
80.degree. C. for 30 min. The reactor was again pressurized with
200 psi ethylene and depressurized to atmospheric pressure three
times. Hydrogen (100 mL) was subsequently added to the reactor. The
catalyst was then introduced in the reactor with appropriate
agitation. The reaction was allowed to proceed for 4 hours at
83.degree. C. before the reactor was vented. The polymer was
isolated by washing the contents of the reactor with water. The
isolated polymer was further treated with 6 M HCl in methanol,
rinsed with methanol and dried under vacuum to give 7.61 g (98 K
TO, 137 g polymer/g silica; .sup.1H NMR: M.sub.n>75K, 12 BP/1000
C; GPC: M.sub.n=52.5K, M.sub.w/M.sub.n=3.3).
Example 361
[0730] Preparation of a Heterogeneous Catalyst Comprising Ligand
a54
[0731] To a vial charged with a54 (7.8 mg; 15 .mu.mol),
Ni(acac).sub.2 (3.9 mg; 15 .mu.mol) and
Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (13.8 mg; 15.0 .mu.mol) was added
0.5 mL 1,2-difluorobenzene. The resulting solution was stirred
overnight (ca. 18 hours). This solution was then added dropwise to
silica at 0.degree. C. (229 mg; Grace Davison XPO-2402). The flask
was then warmed up to room temperature and vacuum was applied for
90 min to remove volatile. The resulting brown solid was stored
under nitrogen at -30.degree. C.
Example 362
[0732] Polymerization of Ethylene Using the Catalyst Prepared in
Example 361
[0733] A catalyst delivery device was charged with the catalyst
prepared in Example 361(44 mg; 2.2 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (348 g) that had
been dried in vacuum at 120.degree. C. for several hours, closed,
evacuated and backfilled with nitrogen three times. The salt was
subsequently treated with trimethylaluminum (8 mL; 2.0 M in hexane)
and agitated at 60.degree. C. for 30 min. The reactor was then
pressurized with ethylene (ca. 200 psi) and depressurized to
atmospheric pressure four times. The catalyst was then introduced
in the reactor with appropriate agitation. The reaction was allowed
to proceed for 4 hours at 60.degree. C. The polymer was isolated by
washing the contents of the reactor with water. The isolated
polymer was further treated with 6 M HCl in methanol, rinsed with
methanol and dried under vacuum to give 15.7 g (254 K TO, 355 g
polymer/g; GPC: M.sub.n=110,000, M.sub.w/M.sub.n=4.2; .sup.1H NMR:
M.sub.n>75,000, 10 BP/1000 C).
Example 363
[0734] Preparation of a Heterogeneous Catalyst Comprising Ligand
V1
[0735] To a vial charged with V1 (37.9 mg; 50.2 .mu.mol),
Ni(acac).sub.2 (12.9 mg; 50.2 .mu.mol) and Ph.sub.3CBF.sub.4 (16.6
mg; 50.3 .mu.mol) was added 1.6 mL 1,2-difluorobenzene. The
resulting solution was stirred overnight (ca. 18 hours). This
solution was then added dropwise to silica at 0.degree. C. (0.985
g; Grace Davison, XPO-2402). The flask was then warmed up to room
temperature and vacuum was applied for 2.5 h to remove volatiles.
The resulting brick-red solid was stored under nitrogen at
-30.degree. C.
Example 364
[0736] Polymerization of Ethylene Using the Catalyst Prepared in
Example 363
[0737] A catalyst delivery device was charged with the catalyst
prepared in Example 363 (45.4 mg; 2.3 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (323 g), which had
been dried in vacuum at 120.degree. C. for several hours, and
closed, evacuated and backfilled with nitrogen. The salt was
subsequently treated with trimethylaluminum (10 mL; 2.0 M in
hexane) and agitated at 80.degree. C. for 20 min. The reactor was
then pressurized with 200 psi ethylene and depressurized to
atmospheric pressure three times. The catalyst was then introduced
in the reactor with appropriate agitation. The reaction was allowed
to proceed for 2.5 hours at 80.degree. C. before the reactor was
vented. The polymer was isolated by washing the contents of the
reactor with water. The isolated polymer was further treated with 6
M HCl in methanol, rinsed with methanol and dried under vacuum to
give 1.84 g of polymer (GPC: M.sub.n=219,000,
M.sub.w/M.sub.n=4.7).
Example 365
[0738] Polymerization of Ethylene Using the Catalyst Prepared in
Example 361
[0739] A catalyst delivery device was charged with the catalyst
prepared in Example 361 (74.2 mg; 3.8 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (345 g), which had
been dried in vacuum at 120.degree. C. for several hours, and
closed, evacuated and backfilled with nitrogen. The salt was
subsequently treated with trimethylaluminum (10 mL; 2.0 M in
hexane) and agitated at 60.degree. C. for 30 min. The reactor was
then pressurized with 200 psi ethylene and depressurized to
atmospheric pressure three times. Hydrogen gas (50 mL) was then
syringed in. The catalyst was then introduced in the reactor with
pressure with appropriate agitation. The reaction was allowed to
proceed under 200 psi C.sub.2H.sub.4 for 4 hours at 59.degree. C.
before the reactor was vented. The polymer was isolated by washing
the contents of the reactor with water. The isolated polymer was
further treated with 6 M HCl in methanol, rinsed with methanol and
dried under vacuum to give 11.2 g (151 g polyethylene/g SiO.sub.2;
106,000 mol C.sub.2H.sub.4/mol Ni; .sup.1H NMR: 8 BP/1000 C; GPC:
M.sub.n=78,000, M.sub.w/M.sub.n=2.5).
Example 366
[0740] Polymerization of Ethylene Using a Catalyst Prepared Using a
Procedure Analogous to that Described in Example 361
[0741] A catalyst delivery device was charged with a 14.9 wt %
dispersion in Sylopol 2100 (92.3 mg; 0.69 .mu.mol Ni) of a catalyst
prepared using a procedure analogous to that described in Example
361. In this case, Grace Davison Sylopol 2100, the actual silica
used, was loaded with a solution containing the individual
components, such that the concentration of nickel was 50 .mu.mol/g
silica. The catalyst delivery device was fixed to the head of a
1000-mL Parr.RTM. reactor. The device was placed under vacuum. The
reactor was then charged with NaCl (278 g), which had been dried in
vacuum at 120.degree. C. for several hours, and then closed,
evacuated and backfilled with nitrogen. The salt was subsequently
treated with trimethylaluminum (10 mL; 2.0 M in hexane) and
agitated at 60.degree. C. for 30 min. The reactor was then
pressurized with 200 psi ethylene and depressurized to atmospheric
pressure three times. With appropriate agitation, the catalyst was
then introduced in the reactor under ethylene pressure, which
resulted in a 17.degree. C. exotherm. The reaction was allowed to
proceed under 200 psi C.sub.2H.sub.4 for 60 minutes at 75.degree.
C. before the reactor was vented. The polymer was isolated by
washing the contents of the reactor with water. The isolated
polymer was further treated with 6 M HCl in methanol, rinsed with
methanol and dried under vacuum to give 19.2 g (1400 g
polyethylene/g supported catalyst; 991,000 mol C.sub.2H.sub.4/mol
Ni; .sup.1H NMR: 7 BP/1000 C; GPC: M.sub.n=89,900,
M.sub.w/M.sub.n=3.0).
Example 367
[0742] Polymerization of Ethylene Using a Catalyst Prepared Using a
Procedure Analogous to that Described in Example 361
[0743] A catalyst delivery device was charged with a 3.0 wt %
dispersion in Sylopol 2100 (55 mg; 82 nmol Ni) of a catalyst
prepared using a procedure analogous to that described in Example
361. In this case, Grace Davison Sylopol 2100, the actual silica
used, was loaded with a solution containing the individual
components, such that the concentration of nickel was 50 .mu.mol/g
silica. The catalyst delivery device was fixed to the head of a
1000-mL Parr.RTM. reactor. The device was placed under vacuum. The
reactor was then charged with NaCl (350 g) that had been dried in
vacuum at 120.degree. C. for several hours. The reactor was closed,
and pressurized with ca. 50 psi nitrogen and depressurized to
atmospheric pressure several times. The salt was subsequently
treated with trimethylaluminum (10 mL; 2.0 M in hexane) and
agitated at 57.degree. C. for 30 min. The reactor was then
pressurized with 200 psi ethylene and depressurized to atmospheric
pressure three times. With appropriate agitation, the catalyst was
then introduced in the reactor under ethylene pressure. The
reaction was allowed to proceed under 100 psi C.sub.2H.sub.4 for 4
hours at 60.degree. C. before the reactor was vented. The polymer
was isolated by washing the contents of the reactor with water. The
isolated polymer was further treated with 6 M HCl in methanol,
rinsed with methanol and dried under vacuum to give 2.49 g (1500 g
polyethylene/g supported catalyst; 1,100,000 mol C.sub.2H.sub.4/mol
Ni; .sup.1H NMR: 12 BP/1000 C; GPC: M.sub.n=72,300,
M.sub.w/M.sub.n=3.2).
Example 368
[0744] Preparation of a Heterogeneous Catalyst Comprising the
Nickel Complex Prepared in Example 322
[0745] A dichloromethane solution of aa1 (0.75 mL; 2.5 .mu.mol) was
added dropwise to Grace Davison XPO-2402 (5.0 g), at 0.degree. C.,
with appropriate agitation. The solid was brought to room
temperature and the flask placed under vacuum for 90 minutes to
remove volatiles. The resulting solid was used as is in subsequent
polymerization reactions.
Example 369
[0746] Polymerization of Ethylene Using the Catalyst Prepared in
Example 368
[0747] A catalyst delivery device was charged with the catalyst
prepared in Example 368 (1.07 g; 0.54 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (354 g) that had
been dried in vacuum at 120.degree. C. for several hours. The
reactor was closed, and pressurized with nitrogen (ca. 40 psi) and
depressurized to atmospheric pressure 10 times. The salt was
subsequently treated with trimethylaluminum (10 mL; 2.0 M in
hexane) and agitated at 86.degree. C. for 30 min. The reactor was
then pressurized with 200 psi ethylene and depressurized to
atmospheric pressure five times. The catalyst was then introduced
in the reactor with appropriate agitation, leading to a 6.degree.
C. exotherm. The reaction was allowed to proceed for 60 minutes at
88.degree. C. before the reactor was vented. The polymer was
isolated by washing the contents of the reactor with water. The
isolated polymer was further treated with 6 M HCl in methanol,
rinsed with methanol and dried under vacuum to give 10.4 g (620,000
mol C.sub.2H.sub.4/mol Ni). .sup.1H NMR (o-dichlorobenzene): 13
branch points/1000 carbons.
Example 370
[0748] Preparation of a Heterogeneous Catalyst Comprising the
Nickel Complex Prepared in Example 322
[0749] A dichloromethane solution of aa1 (0.75 mL; 2.5 .mu.mol) was
added dropwise to Grace Davison XPO-2402 (5.0 g), at 0.degree. C.,
with appropriate agitation. The solid was brought to room
temperature and the flask placed under vacuum for ca. 60 minutes to
remove volatiles. The above was repeated nine more times, leading
to a final nickel loading on silica of 5.0 .mu.mol/g. The resulting
solid was used as is in subsequent polymerization reactions.
Example 371
[0750] Polymerization of Ethylene Using the Catalyst Prepared in
Example 370
[0751] A catalyst delivery device was charged with the catalyst
prepared in Example 370 (540 mg; 2.7 .mu.mol Ni) and fixed to the
head of a 1000-mL Parr.RTM. reactor. The device was placed under
vacuum. The reactor was then charged with NaCl (281 g) that had
been dried in vacuum at 120.degree. C. for several hours. The
reactor was closed, and pressurized with nitrogen (ca. 40 psi) and
depressurized to atmospheric pressure 10 times. The salt was
subsequently treated with trimethylaluminum (10 mL; 2.0 M in
hexane) and agitated at 84.degree. C. for 30 min. The reactor was
then pressurized with 200 psi ethylene and depressurized to
atmospheric pressure five times. The catalyst was then introduced
in the reactor with appropriate agitation, leading to a raise in
temperature to 100.degree. C. The reaction was allowed to proceed
for 30 minutes at 94.degree. C. before the reactor was vented. The
polymer was isolated by washing the contents of the reactor with
water. The isolated polymer was further treated with 6 M HCl in
methanol, rinsed with methanol and dried to give 24.8 g (320 K mol
C.sub.2H.sub.4/mol Ni).
Example 372
[0752] 119
[0753] Synthesis of (2,5-Diphenyl-pyrrol-1-yl)-carbamic Acid
Tert-butyl Ester
[0754] A solution of dibenzoylethane (5g, 21.0 mmol) and t-butyl
carbazate (3.98 g, 30.1 mmol) in EtOH (170 mL) and AcOH (21 mL) was
heated to reflux under Ar for 4.5 h, cooled to rt and diluted with
water (400 mL). The resulting suspension was stirred under Ar at rt
for 3 h, and then allowed to settle overnight at rt. The solid was
filtered, washed with small portions of water and dried in vacuo to
afford (2,5-Diphenyl-pyrrol-1-yl)-carbamic acid tert-butyl ester
(6.72 g, 96%) as a white solid: .sup.1H NMR (CDCl.sub.3, chemical
shifts in ppm relative to TMS): 1.14 (s,3H), 1.38 (s, 6H), 6.35 (s,
2H), 6.84 (bs, 2H), 7.29-7.53 (m, 10H).
Example 373
[0755] Synthesis of 2,5-Diphenyl-pyrrol-1-ylamine
[0756] A suspension of (2,5-Diphenyl-pyrrol-1-yl)-carbamic acid
tert-butyl ester (3.7 g, 11.06 mmol) in anhydrous methanol (25 mL)
was cooled to 0.degree. C. in an ice water bath, then treated with
conc. HCl (9.86 mL). The ice bath was removed, and the resulting
suspension was heated to reflux in an oil bath for 1.5 h. Upon
cooling to rt, a white solid precipitated, which was filtered,
washed with water and dried in vacuo to afford
2,5-Diphenyl-pyrrol-1-ylamine (2.32g, 90%): .sup.1H NMR
(CDCl.sub.3, chemical shifts in ppm relative to TMS): 3.64 (bs,
2H), 6.28 (s, 2H), 7.28-7.33 (m, 2H), 7.42 (t, 4H, J=8.0 Hz), 7.58
(d, 4H, J=8.0 Hz).
Example 374
[0757] 120
[0758] Synthesis of
3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one
[0759] A suspension of 2,5-Diphenyl-pyrrol-1-ylamine (1.91 g, 8.15
mmol) in toluene (5.45 mL) was treated with 2,3-butanedione (7.15
mL, 81.5 mmol), DMF (10.9 mL) and p-toluene sulfonic acid (10.9
mg). The resulting suspension was stirred under Ar at rt for 30
min, then heated to 70.degree. C. in an oil bath. After 2.5 h, the
solution was cooled to rt and concentrated in vacuo. The oily solid
was dissolved in toluene and concentrated in vacuo to remove excess
2,3-butanedione. The residue was purified by flash chromatography
(SiO.sub.2, 10% EtOAc/heptane) to afford
3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one: .sup.1H NMR
(CDCl.sub.3, chemical shifts in ppm relative to TMS): 1.44 (s, 3H),
2.56 (s, 3H), 6.47 (s, 2H), 7.20-7.26 (m, 2H), 7.34 (t, 4H, J=8.0
Hz), 7.47 (d, 4H, J=8.0 Hz).
Example 375
[0760] 121
[0761] Synthesis of
2,3-bis(2,5-Diphenyl-pyrrol-1-ylimino)-butane
[0762] A suspension of
3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one (2.45 g, 8.1 mmol) in
toluene (28 mL) was treated with DMF (14 mL),
2,5-diphenyl-pyrrol-1-ylamine (1.99 g, 8.5 mmol) and p-toluene
sulfonic acid (73 mg). The resulting suspension was fitted with a
Dean Stark trap and heated to reflux in an oil bath for 21 h, then
cooled to rt and allowed to stand under Ar for 4 days. The desired
compound did not crystallize, therefore the solution was
concentrated in vacuo. Approximately half of the residue was
purified by flash chromatography (SiO.sub.2, 5-100% EtOAc/heptane)
to afford some pure desired
2,3-bis(2,5-Diphenyl-pyrrol-1-ylimino)-butane (780 mg) and some
desired contaminated with starting 2,5-diphenyl-pyrrol-1-ylamine.
The remaining crude residue was flash chromatographed (SiO.sub.2,
33-50% CH.sub.2Cl.sub.2/heptane) in an attempt to remove excess
amino pyrrole. No separation was achieved, therefore all of the
fractions were combined, together with the impure material from the
first column and concentrated in vacuo. This mixture was suspended
in toluene (15 mL) and treated with DMF (5 mL), 2,3-butanedione
(0.81 mL, 9.24 mmol) and p-toluene sulfonic acid (7 mg). The
resulting suspension was heated to 70.degree. C. in an oil bath,
and stirred under Ar for 3 h, then cooled to rt and concentrated in
vacuo. The resulting solid was washed with water, heptane and
toluene (to remove 3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one
and 2,3-butanedione) and dried in vacuo to afford
2,3-bis(2,5-Diphenyl-pyrrol- -1-ylimino)-butane (1.42 g) as a
yellow solid. Overall, 2.2 g (52% based on
3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one) of
2,3-bis(2,5-Diphenyl-pyrrol-1-ylimino)-butane was isolated as a
yellow solid: .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm
relative to TMS): 1.71 (s, 6H), 6.44 (s, 4H), 7.22-7.36 (m,
20H).
Example 376
[0763] 122
[0764] Synthesis of
1,4-Bis-(4-tert-butyl-phenyl)-butane-1,4-dione
[0765] A solution of lithium diisopropyl amide (LDA) in THF was
prepared by adding 2.5 M in hexanes n-butyl lithium (6.3 mL, 15.7
mmol) dropwise to a solution of diisopropyl amine (2.2 mL, 15.7
mmol) in THF (16.32 mL) at -78.degree. C. To this solution was
added 4'-t-butyl acetophenone (2.5 g, 14.2 mmol) as a solution in
THF (3 mL) via dropping funnel at -78.degree. C. The resulting
solution was stirred at -78.degree. C. under Ar for 1 h, then
treated with a solution of anhydrous CuCl.sub.2 (2.11 g, 15.7 mmol)
in DMF (15.84 mL). After the completion of the addition, the dry
ice bath was removed, and the reaction allowed to warm to rt over 1
h, then poured into a 0.5 M solution of HCl (120 mL). The aqueous
suspension was extracted with Et.sub.2O. The organic layers were
dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo.
The residue was crystallized from EtOH, to afford
1,4-bis-(4-tert-butyl-phenyl)-butan- e-1,4-dione (377 mg, 16%) as
white crystals. A second crop of crystals (253 mg, 10%) was
recovered by concentration of the filtrate: .sup.1H NMR
(CDCl.sub.3, chemical shifts in ppm relative to TMS): 1.35 (s,
18H), 3.44 (s, 4H), 7.50 (d, 4H, J=8.3 Hz), 7.98 (d, 4H, J=8.3
Hz).
Example 377
[0766] 123
[0767] Synthesis of
[2,5-Bis-(4-tert-butyl-phenyl)-pyrrol-1-yl]-carbamic Acid
2-trimethylsilanyl-ethyl Ester
[0768] A solution of 1,4-bis-(4-tert-butyl-phenyl)-butane-1,4-dione
(377 mg, 1.08 mmol) in toluene (3 mL) was treated with
hydrazinecarboxylic acid 2-trimethylsilanyl-ethyl ester (212 mg,
1.18 mmol) and p-toluene sulfonic acid (11.3 mg). The resulting
solution was heated to reflux under Ar for 1.5 h, then cooled to rt
and concentrated in vacuo to provide crude
[2,5-Bis-(4-tert-butyl-phenyl)-pyrrol-1-yl]-carbamic acid
2-trimethylsilanyl-ethyl ester. The residue was not purified, but
was deprotected immediately as follows.
Example 378
[0769] 124
[0770] Synthesis of
2,5-Bis-(4-tert-butyl-phenyl)-pyrrol-1-ylamine
[0771] [2,5-Bis-(4-tert-butyl-phenyl)-pyrrol-1-yl]-carbamic acid
2-trimethylsilanyl-ethyl ester (681 mg, 1.39 mmol) was treated with
a 1 M solution of TBAF in THF (2.78 mL). The resulting solution was
stirred at rt overnight, then quenched with glacial acetic acid
(0.155 mL). The solution was passed through a short plug of silica
gel, eluting with toluene and concentrated in vacuo to afford
2,5-Bis-(4-tert-butyl-phenyl)- -pyrrol-1-ylamine (299 mg, 80% for
two steps) as a creamy white solid: .sup.1H NMR (CDCl.sub.3,
chemical shifts in ppm relative to TMS): 1.36 (s, 18H), 4.60 (s,
2H), 6.24 (s, 2H), 7.46 (d, 4H, J=8.7 Hz), 7.52 (d, 4H, J=8.7
Hz).
Example 379
[0772] 125
[0773] Synthesis of
2,3-bis(2,5-bis(4-tert-butylphenyl)-pyrrol-1-ylimino)-- butane
[0774] A solution of 2,5-bis-(4-tert-butyl-phenyl)-pyrrol-1-ylamine
(174 mg, 0.502 mmol) in toluene (4.5 mL) was treated with
butanedione (19.7 .mu.L, 0.225 mmol) and p-toluene sulfonic acid
(5.2 mg). The resulting solution was heated to 80.degree. C. in an
oil bath under Ar overnight. The solution was cooled to rt and
concentrated in vacuo. The residue was purified by flash
chromatography (SiO.sub.2, 33% CH.sub.2Cl.sub.2/heptane- ) to
afford 2,3-bis(2,5-bis(4-tert-butylphenyl)-pyrrol-1-ylimino)-butane
(121 mg, 72%):
[0775] .sup.1H NMR (CDCl.sub.3, chemical shifts in ppm relative to
TMS): 1.33 (s, 36H), 1.69 (s, 6H), 6.39 (s, 4H), 7.33-7.39 (m,
16H).
Example 380 to Example 389
[0776] 126
[0777] Ethylene Polymerization in the Presence of Hydrogen as a
Chain Transfer Agent
[0778] A stock solution of aa1 containing 0.75 mg of aa1/ml of
solvent was prepared by dissolving 6 mg of aa1 in 40-ml of
CH.sub.2CL.sub.2 or toluene and then diluting 2-ml of that solution
to 4-ml. A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene, 1-ml
of mMAO (7.14 wt % Al; Akzo Nobel) and optionally H.sub.2 gas (0,
50, 150, 300 or 450-ml of H.sub.2 gas added to the reactor head
space via syringe). The reactor was sealed and pressurized up to
150-psig ethylene and heated to 60.degree. C. A 2-ml portion
(1.04.times.10.sup.-7 mol of catalyst) of the catalyst stock
solution of aa1 was added to the autoclave via the high-pressure
sample loop while pressurizing the autoclave to 200 psig. After 15
minutes of stirring at 200-psig ethylene and 60.degree. C., the
reaction was quenched upon addition of 2-ml of methanol at high
pressure. The reactor was vented and the contents poured into a
beaker containing a methanol/acetone mixture. The polymer was
collected by suction filtration and dried in the vacuum oven
overnight at -100.degree. C.
12 H.sub.2 Yield TO TOF added PE mol C.sub.2H.sub.4/mol Ni mol
C.sub.2H.sub.4/ M.sub.n Example (ml) (g) (.times.10.sup.-3) mol Ni
h (.times.10.sup.-3) (.times.10.sup.-3) 380 0 4.6 1600 6200 790 381
0 4.6 1600 6400 -- 382 50 4.8 1600 6500 171 383 50 4.0 1400 5500 --
384 150 4.9 1700 6700 166 385 150 4.8 1600 6500 -- 386 300 4.5 1500
6200 146 387 300 5.0 1700 6900 -- 388 300 4.7 1600 6500 126 389 450
5.2 1800 7100 108
Example 390 to Example 394
[0779] 127
[0780] Ethylene Polymerization with aa2
[0781] A stock solution was prepared by combining 3.3 mg (12.7
.mu.mol) of Ni(acac).sub.2, 11.7 mg (12.7 .mu.mol)
Ph.sub.3C--B(C.sub.6F.sub.5).sub.4 and 9.3 mg (12.7 .mu.mol) of the
requisite osazone in 5-ml of methylene chloride. The mixture was
allowed to sit for 30 minutes. After 30 minutes, an additional
10-ml of methylene chloride was added followed by removal of 5-ml
(1/3) of the resulting solution. The 5-ml of the solution removed
was diluted to 40-ml with toluene giving a stock solution with
0.0825 mg of aa2/ml solvent. Subsequently, a Parr.RTM. stirred
autoclave (600-ml) was heated to 100.degree. C. under dynamic
vacuum to completely dry the reactor. The reactor was cooled and
charged with 150 ml of dry toluene, 1-ml of mMAO (7.14 wt % Al;
Akzo Nobel) and optionally H.sub.2 gas (0, 50, 150 or 300-ml of
H.sub.2 gas added to the reactor head space via syringe). The
reactor was sealed and pressurized up to 150 psig ethylene and
heated to 60.degree. C. A 2-ml portion (1.04.times.10.sup.-7 mol of
catalyst) of the catalyst stock solution of aa2 was added to the
autoclave via the high-pressure sample loop while pressurizing the
autoclave to 200 psig. After 15 minutes of stirring at 200-psig
ethylene and 60.degree. C., the reaction was quenched upon addition
of 2-ml of methanol at high pressure. The reactor was vented and
the contents poured into a beaker containing a methanol/acetone
mixture. The polymer was collected by suction filtration and dried
in the vacuum oven overnight at -100.degree. C.
13 H.sub.2 Yield TO TOF added PE mol C.sub.2H.sub.4/mol Ni mol
C.sub.2H.sub.4/ Example (ml) (g) (.times.10.sup.-3) mol Ni h
(.times.10.sup.-3) 390 0 3.6 1200 4900 391 0 4.6 1600 6400 392 50
1.9 667 2700 393 150 1.6 545 2200 394 300 1.8 608 2400
Example 395
[0782] 128
[0783] Preparation of z2
[0784] A flame dried Schlenk flask equipped with a rubber septum
and a stir bar was charged with 100 mg (0.39 mmol) of nickel (II)
acetylacetonate, 308 mg (0.39 mmol) of the appropriate
.alpha.-diimine ligand and 360 mg (0.39 mmol)
Ph.sub.3CB(C.sub.6F.sub.5).sub.4. Methylene chloride 20-ml was
added to the solid mixture giving a homogeneous blood red solution
within seconds. The solution was left to stir at room temperature
for 60 minutes. After 60 minutes, the solution was concentrated to
5-ml and 20-ml of dry degassed hexane was added resulting in the
formation of a red precipitate. The supernate was removed via
filter cannula. The resulting solid was then dissolved in 5-ml of
methylene chloride and re-precipitated upon addition of 20-ml of
hexanes. The supernatent was again removed via filter cannula. The
wash procedure was repeated one additional time. The red powder
that resulted was dried in vacuo overnight resulting in 546 mg (86%
yield) of the desired complex. .sup.1H NMR was consistent with the
desired complex.
Example 396
[0785] 129
[0786] Preparation of z3
[0787] A flame dried Schlenk flask equipped with a rubber septum
and a stir bar was charged with 100 mg (0.39 mmol) of nickel (II)
acetylacetonate, 270 mg (0.39 mmol) of the appropriate
.alpha.-diimine ligand and 360 mg (0.39 mmol)
Ph.sub.3C--B(C.sub.6F.sub.5).sub.4. Methylene chloride 20-ml was
added to the solid mixture giving a homogeneous blood red solution
within seconds. The solution was left to stir at room temperature
for 60 minutes. After 60 minutes, the solvent was removed in vacuo
giving a red glassy solid. The resulting solid was washed 4 times
with a 1-part ether and 4-part hexane solution. The supernatent was
removed via filter cannula. The red powder that resulted was dried
in vacuo overnight resulting in 413 mg (69% yield) of the desired
complex. .sup.1H NMR was consistent with the desired complex.
Example 397 to Example 400
[0788] Ethylene Polymerization with z2 or z3
[0789] A Parr.RTM. stirred autoclave (600-ml) was heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor was cooled and charged with 150 ml of dry toluene, 1-ml
of mMAO (7.14 wt % Al; Akzo Nobel) and optionally H.sub.2 gas (0,
50, 150 or 300-ml of H.sub.2 gas added to the reactor head space
via syringe). The reactor was sealed and pressurized up to 150-psig
ethylene and heated to 60.degree. C. A 2-ml portion
(1.04.times.10.sup.-7 mol of catalyst) of a catalyst stock solution
of z2 or z3 was added to the autoclave via the high-pressure sample
loop while pressurizing the autoclave to 200 psig. After 15 minutes
of stirring at 200-psig ethylene and 60.degree. C., the reaction
was quenched upon addition of 2 ml of methanol at high pressure.
The reactor was vented and the contents poured into a beaker
containing a methanol/acetone mixture. The polymer was collected by
suction filtration and dried in the vacuum oven overnight at
-100.degree. C.
14 H.sub.2 Yield TO TOF added PE mol C.sub.2H.sub.4/mol Ni mol
C.sub.2H.sub.4/ Example Catalyst (ml) (g) (.times.10.sup.-3) mol Ni
h (.times.10.sup.-3) 397 z2 0 0.53 180 720 398 z3 0 3.2 1100 4300
399 z3 150 4.2 1400 5800 400 z3 300 4.5 1600 6400
Example 401
[0790] Preparation of v20 130
[0791] A 50 mL round bottom flask was charged with
2,4,6-triphenylaniline (762 mg, 1 eq), 2,3-butanedione (2 mL, 10
eq), p-toluenesulfonic acid hydrate(15 mg), and dry toluene (10
mL). The mixture was heated at 60 C for 10 h under a nitrogen
atmosphere, then allowed to cool to rt overnight. Most of the
solvent and excess butanedione were removed in vacuo to leave the
crude mono imine-mono ketone as an amber oil (Field desorption mass
spectronomy: n/z 389). Toluene (23 mL), sufuric acid (1 drop), and
2,4,6-triphenylaniline (1 g) were added. The solution was refluxed
for 10 h using a Dean-Stark trap (ca. 13 mL capacity) to collect
the water eliminated. After standing at rt for 1 d, some methanol
was added and a light-colored precipitate separated from the dark
solution. After standing 11 d more the yellow crystalline product
was isolated by vacuum filtration, and washed with toluene and
methanol. Yield of v20=1.4 g (85% based on initial charge of the
aniline). .sup.1H NMR (300 MHz, CDCl.sub.3, 295 K): .delta.7.64
(apparent d, 4H), 7.54(apparent s, 4 H), 7.43 (apparent t, 4 H),
7.34 (apparent d, 2 H), 7.31-7.15 (m, 20 H).
Example 402
[0792] Preparation of v21 131
[0793] A 50 mL round bottom flask was charged with
2,4,6-triphenylaniline (1.295 g, 1 eq), acenaphthenequinone (0.294
g, eq), sulfuric acid(1 drop), and dry toluene (20 mL). The
solution was refluxed for 10 h using a Dean-Stark trap (ca. 13 mL
capacity) to collect the water eliminated, then allowed to cool to
rt overnight. After standing at rt 12 d, the orange crystalline
product that had separated from solution was isolated by vacuum
filtration, and washed with toluene and methanol. Yield of v21=0.9
g (71%). .sup.1H NMR (300 MHz, CDCl.sub.3, 295 K): .delta.7.75
(apparent d, 4H), 7.68 (apparent t, 2 H), 7.64 (apparent s, 4 H),
7.47 (apparent t, 4H), 7.40-7.32 (apparent t, 2H), 7.11-7.04 (m, 4
H), 7.01-6.92 (m, 8 H), 6.89 (apparent d, 2 H). Field desorption
mass spectroscopy: m/z=789.
Example 403
[0794] Preparation of v22 132
[0795] Compound v22 was prepared by a procedure similar to that
described in Example 233. 1H NMR (300 MHz, CDCl.sub.3, 295 K),
mixture of isomers: .delta.7.9 (s, 2 H), 7.79 (d, J=7.45 Hz, 2 H),
7.65 (d, J=7.45 Hz, 4 H), 7.57 (d, J=7.45 Hz, 2H), 7.52-7.28(m, 14
H), 2.88-2.64 (m, 2H), 2.34-2.00(m, 2H). The requisite aniline was
prepared by phenylation of the corresponding bromo-substituted
aniline under Suzuki conditions (see Y. Miura et al., Synthesis,
1995, 1419-1422 for a convenient procedure).
Ortho-trifluromethylaniline was dibrominated with bromine in acetic
acid to give the required bromo-substituted aniline (see, for
example, R. G. Pews, et al., Tetrahedron, 1993, 49(22), 4809-4820
for a general procedure for bromination of anilines).
Example 404
[0796] Preparation of v23 133
[0797] Compound v23 was prepared by a procedure similar to that
described in Example 233. .sup.1NMR (300 MHz, CDCl.sub.3, 295 K),
mixture of isomers: .delta.8.19-8.10 (m, 1 H), 8.03-7.89 (m, 3 H),
7.84-7.75 (m, 2 H), 7.68-7.39 (m, 20 H), 7.39-7.27 (m, 4 H),
2.85-2.73 (m, 2 H), 2.53-2.44 (m, 1H), 2.32-2.19 (m, 1 H). The
requisite amine was prepared starting from 1-naphthylamine similar
to the procedure described in Example 403.
Example 405 to Example 407
[0798] Ethylene Polymerization with a Pro-Catalyst of the Type
Prepared in Example 242
[0799] A Schlenk flask (200 mL, 500 mL or 1000 mL) equipped with a
magnetic stir bar and capped with a septum was evacuated and
refilled with ethylene, then charged with dry, deoxygenated toluene
(100 mL) and a 10 wt % solution of MAO in toluene (4.0 mL). The
requisite volume of pro-catalyst solution (prepared from the
indicated ligand as in example 242) was added to give the amount of
Ni indicated in the table below. The mixture was stirred under 1
atm ethylene at the temperature indicated in the table below and a
polyethylene precipitate was observed. After the indicated reaction
time, the mixture was quenched by the addition of acetone (50 mL),
methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
polyethylene was isolated by vacuum filtration and washed with
water, methanol and acetone, then dried under reduced pressure at
100.degree. C. for 16 h to obtain the amount of polyethylene
indicated in the table below (M.sub.n determined in this case by
.sup.1NMR).
15 Branches/ Li- Temp .mu.mol Time 1000 Example gand (C.) Ni min g
PE M.sub.n C's 405 V22 23 0.352 215.00 1.42 93,000 51.5 406 V22 60
0.352 35.00 2.3 26,000 96.4 407 V23 23 0.407 10.17 .456 21,000
20.3
Example 408 and Example 409
[0800] A stock procatalyst solution of the type prepared in Example
242 was prepared from ligand v22 at the concentration of 0.51
.mu.mol/mL. Subsequently, a Parr.RTM. stirred autoclave (600-ml)
was heated to 100.degree. C. under dynamic vacuum to completely dry
the reactor. The reactor was cooled and charged with 150 ml of dry
toluene, 1-ml of mMAO (7.14 wt % Al; Akzo Nobel) and optionally
H.sub.2 gas (0, 50, 150 or 300-ml of H.sub.2 gas added to the
reactor head space via syringe). The reactor was sealed and
pressurized up to 150 psig ethylene and heated to 60.degree. C. A
2-ml portion (1.02.times.10.sup.-6 mol of catalyst) of the catalyst
stock solution from ligand v22 was added to the autoclave via the
high-pressure sample loop while pressurizing the autoclave to 200
psig. After 15 minutes of stirring at 200-psig ethylene and
60.degree. C., the reaction was quenched upon addition of 2-ml of
methanol at high pressure. The reactor was vented and the contents
poured into a beaker containing a methanol/acetone mixture. The
polymer was collected by suction filtration and dried in the vacuum
oven overnight at -100.degree. C.
16 H.sub.2 Yield TO TOF added PE mol C.sub.2H.sub.4/mol Ni mol
C.sub.2H.sub.4/ Example (ml) (g) (.times.10.sup.-3) mol Ni h
(.times.10.sup.-3) 408 0 6.4 234 938 409 50 .096 3.5 14
Example 410
[0801] Synthesis of (2,5-Di-pyridin-3-yl-pyrrol-1-yl)-carbamic acid
2-trimethylsilanyl-ethyl ester: A solution of
1,4-Di-pyridin-3-yl-butane-- 1,4-dione (1 g, 4.2 mmol) in toluene
(40 mL) is treated with hydrazinecarboxylic acid
2-trimethylsilanyl-ethyl ester (888 mg, 5.0 mmol) and
p-toluenesulfonic acid (30 mg). The reaction vessel is fitted with
a Dean Stark trap, and the resulting solution is heated to reflux,
with azeotropic removal of water until no starting materials are
detected by TLC. The solution is cooled to rt, and washed with
water. The organic layer is dried over Na.sub.2SO.sub.4, filtered
and concentrated to afford
(2,5-di-pyridin-3-yl-pyrrol-1-yl)-carbamic acid
2-trimethylsilanyl-ethyl ester, which is not purified further.
Example 411
[0802] Synthesis of 2,5-Di-pyridin-3-yl-pyrrol-1-ylamine:
(2,5-di-pyridin-3-yl-pyrrol-1-yl)-carbamic acid
2-trimethylsilanyl-ethyl ester (1 g, 2.6 mmol) is treated with a 1M
solution of TBAF in THF (5.2 ml, 5.2 mmol). The resulting solution
is stirred overnight under Ar at rt, then quenched with glacial
acetic acid (0.3 ml, 5.2 mmol) and diluted with toluene. The
resulting solution is passed through a short plug of silica gel and
concentrated in vacuo to afford 2,5-Di-pyridin-3-yl-pyrrol-
-1-ylamine.
Example 412
[0803] Synthesis of
2-(2,5-Diphenyl-pyrrol-1-ylimino)-3-(2,5-dipyridine-3--
yl-pyrrol-1-ylimino)-butane: A suspension of
3-(2,5-Diphenyl-pyrrol-1-ylim- ino)-butan-2-one (1.0 g, 3.4 mmol)
in toluene (12 ml) is treated with DMF (6 ml),
2,5-di-pyridin-3-yl-pyrrol-1-ylamine (850 mg, 3.6 mmol) and
p-toluene sulfonic acid (30 mg). The resulting suspension is fitted
with a Dean Stark trap and heated to reflux with azeotropic removal
of water in an oil bath until no starting materials remain by TLC.
The solution is cooled to rt and concentrated in vacuo. The residue
is purified by flash chromatography to afford
2-(2,5-diphenyl-pyrrol-1-ylimino)-3-(2,5-dipyrid-
ine-3-yl-pyrrol-1-ylimino)-butane.
Example 413
[0804] Preparation of z4 134
[0805] A flame dried Schlenk flask equipped with a rubber septum
and a stir bar is charged with 100 mg (0.39 mmol) of nickel (II)
acetylacetonate, 203 mg (0.39 mmol) of
2-(2,5-diphenyl-pyrrol-1-ylimino)--
3-(2,5-dipyridine-3-yl-pyrrol-1-ylimino)-butane and 360 mg (0.39
mmol) Ph.sub.3C--B(C.sub.6F.sub.5).sub.4. Methylene chloride (20
ml) is added to the solid mixture giving a homogeneous blood red
solution within seconds. The solution is left to stir at room
temperature for 60 minutes. After 60 minutes, the solvent is
removed in vacuo giving a red glassy solid. The resulting solid is
washed 4 times with a 1-part ether and 4-part hexane solution. The
supernatent is removed via filter cannula. The red powder is dried
in vacuo overnight to afford z4.
Example 414
[0806] Ethylene polymerization with z4
[0807] A Parr.RTM. stirred autoclave (600-ml) is heated to
100.degree. C. under dynamic vacuum to completely dry the reactor.
The reactor is cooled and charged with 150 ml of dry toluene and
1-ml of mMAO (7.14 wt % Al; Akzo Nobel). The reactor is sealed and
pressurized up to 150-psig ethylene and heated to 60.degree. C. A
2-ml portion (1.04.times.10.sup.-7 mol of catalyst) of a catalyst
stock solution of z4 is added to the autoclave via the
high-pressure sample loop while pressurizing the autoclave to 200
psig. After 15 minutes of stirring at 200-psig ethylene and
60.degree. C., the reaction is quenched upon addition of 2 ml of
methanol at high pressure. The reactor is vented and the contents
poured into a beaker containing a methanol/acetone mixture. The
polymer is collected by suction filtration and dried in the vacuum
oven overnight at -100.degree. C.
Example 415
[0808] Polymerization of Ethylene Using a Catalyst Prepared as in
Example 368
[0809] A catalyst delivery device was charged with a catalyst
prepared as in Example 368, wherein aa1 (73.8 mg) was dissolved in
1.5 mL dichloromethane and added to Grace Davison XPO-2402 (1.0 g).
The device containing 10.2 mg of the catalyst dispersed in 200 mg
XPO-2402 was then fixed to the head of a 1000-mL Parr.RTM. reactor.
The device was placed under vacuum. The reactor was then charged
with NaCl (304 g) that had been dried in vacuum at 120.degree. C.
for several hours. The reactor was closed, and pressurized with
nitrogen (ca. 40 psi) and depressurized to atmospheric pressure 10
times. The salt was subsequently treated with trimethylaluminum (10
mL; 2.0 M in hexane) and agitated at 86.degree. C. for 30 min. The
reactor was then pressurized with 200 psi ethylene and
depressurized to atmospheric pressure five times. The catalyst was
then introduced in the reactor with appropriate agitation. The
reaction was allowed to proceed for 60 minutes at 86.degree. C.
before the reactor was vented. The polymer was isolated by washing
the content of the reactor with water. The isolated polymer was
further treated with 6 M HCl in methanol, rinsed with methanol and
dried under vacuum to give 7.4 g (520,000 mol C.sub.2H.sub.4/mol
Ni).
Example 416
[0810] Polymerization of Ethylene Using a Catalyst Prepared from
a54, Co(acac).sub.2 , and Ph.sub.3CB(C.sub.6F.sub.5).sub.4
[0811] A mixture of prepared a54 (20.2 mg), Co(acac).sub.2 (10.1
mg) and Ph.sub.3CB(C.sub.6F.sub.5).sub.4 (36.1 mg) was dissolved in
5.0 mL dry, deoxygenated methylene chloride to afford a deep
reddish-brown catalyst stock solution. A portion of this solution
(54 .mu.L) was added to a vigorously stirred mixture of 300 mL dry,
deoxygenated toluene and 4.0 mL of a 10 wt % solution of MAO in
toluene (Aldrich) under 1 atm ethylene at 23.degree. C., resulting
in weak ethylene uptake. After 9.5 min, an additional 0.46 mL of
the stock solution was added, leading to an increase in ethylene
uptake. After a total of 39 min, the reaction was quenched by
addition of MeOH and 6 N aq HCl. The polymer was recovered by
filtration and dried in vacuo to afford 0.250 g white powdery
polyethylene. GPC: M.sub.n 99,000; M.sub.w 265,800. DSC (2.sup.nd
heat from melt, endothermic maximum): 135.1.degree. C. .sup.1NMR
(o-dichlorobenzene): 4.4 branch points/1000 carbons.
[0812] While the invention has been described with reference to
preferred embodiments and working examples, it is to be understood
that variations and modifications may be resorted to as will be
apparent to those skilled in the art. Such variations and
modifications are to be considered within the purview and scope of
the invention as defined by the claims appended hereto.
* * * * *