U.S. patent application number 09/780093 was filed with the patent office on 2001-09-27 for catalyst compositions for the polymerization of olefins.
Invention is credited to Killian, Christopher Moore, Mackenzie, Peter Borden, McDevitt, Jason Patrick, Moody, Leslie Shane, Ponasik, James Allen JR..
Application Number | 20010025007 09/780093 |
Document ID | / |
Family ID | 27567750 |
Filed Date | 2001-09-27 |
United States Patent
Application |
20010025007 |
Kind Code |
A1 |
Ponasik, James Allen JR. ;
et al. |
September 27, 2001 |
Catalyst compositions for the polymerization of olefins
Abstract
The present invention includes novel ligands which may be
utilized as part of a catalyst system. A catalyst system of the
present invention is a transition metal--ligand complex. In
particular, the catalyst system includes a transition metal
component and a ligand component comprising a Nitrogen atom and/or
functional groups comprising a Nitrogen atom, generally in the form
of an imine functional group. In certain embodiments, the ligand
component may further comprise a phosphorous atom. Preferred ligand
components are bidentate (bind to the transition metal at two or
more sites) and include a nitrogen--transition metal bond. The
transition metal--ligand complex is generally cationic and
associated with a weakly coordinating anion. A catalyst system of
the present invention may further comprise a Lewis or Bronsted
acid. The Lewis or Bronsted acid may be complexed with the ligand
component of the transition metal-ligand complex.
Inventors: |
Ponasik, James Allen JR.;
(Kingsport, TN) ; McDevitt, Jason Patrick; (Wake
Forest, NC) ; Killian, Christopher Moore; (Gray,
TN) ; Mackenzie, Peter Borden; (Kingsport, TN)
; Moody, Leslie Shane; (Johnson City, TN) |
Correspondence
Address: |
Bernard J. Graves, Jr.
KILPATRICK STOCKTON LLP
3500 One First Union Center
301 South College Street
Charlotte
NC
28202-6001
US
|
Family ID: |
27567750 |
Appl. No.: |
09/780093 |
Filed: |
February 9, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09780093 |
Feb 9, 2001 |
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09222614 |
Dec 29, 1998 |
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6200925 |
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09222614 |
Dec 29, 1998 |
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09028315 |
Feb 24, 1998 |
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60040754 |
Mar 13, 1997 |
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60044691 |
Apr 18, 1997 |
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60045337 |
May 1, 1997 |
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60045358 |
May 2, 1997 |
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60045357 |
May 2, 1997 |
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60045697 |
May 6, 1997 |
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Current U.S.
Class: |
502/167 ;
502/103; 502/162; 526/141; 526/147 |
Current CPC
Class: |
C07C 251/36 20130101;
C07F 15/025 20130101; C07F 15/045 20130101; C07D 231/12 20130101;
C07D 233/56 20130101; C07D 319/12 20130101; C07F 15/04 20130101;
C07F 15/06 20130101; C07F 15/006 20130101; C08F 10/00 20130101;
C07F 9/5022 20130101; C08F 2500/10 20130101; C08F 2500/02 20130101;
C08F 2500/10 20130101; C08F 4/7006 20130101; C08F 2500/03 20130101;
C08F 2500/09 20130101; C08F 2500/09 20130101; C08F 2500/03
20130101; C08F 210/14 20130101; C08F 2500/10 20130101; C07D 233/96
20130101; C07D 285/10 20130101; C07F 9/5031 20130101; C08F 210/16
20130101; C07F 15/065 20130101; C07C 257/14 20130101; C08F 210/16
20130101; C08F 110/02 20130101; C07D 241/06 20130101; C08F 110/02
20130101; C07D 265/30 20130101; C08F 10/00 20130101; C07D 339/08
20130101; C07F 15/02 20130101; C07D 513/04 20130101; C07F 15/0066
20130101; C08F 110/02 20130101; C07D 249/08 20130101 |
Class at
Publication: |
502/167 ;
502/103; 502/162; 526/141; 526/147 |
International
Class: |
B01J 023/38; B01J
023/40; B01J 023/74; B01J 023/755 |
Claims
We claim:
1. A batch or continuous process for the polymerization of olefins,
comprising contacting one or more monomers selected from compounds
of the formula RCH=CHR.sup.1 with a Group 8-10 transition metal
complex of a ligand of the formula VI, XIII, IX, XIII, XIV, XV, or
XXII and optionally a Bronsted or Lewis acid, 42wherein R and
R.sup.1 are independently H, hydrocarbyl, fluoroalkyl, or R and
R.sup.1 may be linked to form a cyclic olefin; R.sup.3 is
hydrocarbyl or substituted hydrocarbyl; R.sup.4 is H, hydrocarbyl,
substituted hydrocarbyl, or silyl, R.sup.5 is hydrocarbyl or
substituted hydrocarbyl: Z is O or S; U is -OR.sup.10, -SR.sup.10,
-SeR.sup.10 or -NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are
each independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen; G.sup.1 is hydrocarbyl or
substituted hydrocarbyl and may comprise a carbocyclic or
heterocyclic ring, thereby forming a 5-membered or 6-membered
heterocyclic ring comprising G.sup.1, C, and N; G.sup.2 is
hydrocarbyl or substituted hydrocarbyl and may comprise a
carbocyclic or heterocyclic ring, thereby forming a 5-membered or
6-membered heterocyclic ring comprising G.sup.2, V, N, and N; V is
-CR.sup.6, N, or -PR.sup.6R.sup.9; wherein, R.sup.6 and R.sup.9 are
each independently selected from H, hydrocarbyl, substituted
hydrocarbyl, silyl or heteroatom connected hydrocarbyl, and in
addition, R.sup.6 and R.sup.9 may collectively form a ring with
phosphorus, .OMEGA. is hydrocarbyl or substituted hydrocarbyl; and,
n is an integer between 2 and 6.
2. The process of claim 1 wherein the monomer of the formula
RCH=CHR.sup.1 is selected from ethylene, propylene, 1-butene,
1-hexene, and 1 -octene.
3. The process of claim 1 wherein the group 8-10 transition metal
is nickel.
4. The process of claim 3 wherein a Lewis acid is used, and said
Lewis acid is methylaluminoxane.
5. The process of claim 4 wherein the ligand of formula VI is
selected from: 43wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl; R.sup.5, R.sup.6 and R.sup.11 are independently H,
hydrocarbyl, or substituted hydrocarbyl; R.sup.7 is H, hydrocarbyl,
substituted hydrocarbyl, or NO.sub.2.
6. The process of claim 5 wherein the ligand of formula VI is
selected from: 44wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl; and, R.sup.5 and R.sup.11 are independently H, hydrocarbyl,
or substituted hydrocarbyl.
7. The process of claim 6 wherein the ligand of formula VI is
45wherein Ar.sup.1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl;
and, Ar.sup.2 is phenyl or 1-naphthyl.
8. The process of claim 4 wherein the ligand of formula XII is
selected from: 46wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen; R.sup.5, R.sup.6 and
R.sup.11 are independently H, hydrocarbyl, or substituted
hydrocarbyl; R.sup.7 is H, hydrocarbyl, substituted hydrocarbyl, or
-NO.sub.2.
9. The process of claim 8 wherein the ligand of formula XII is
selected from: 47wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen; R.sup.5 and R.sup.11 are
independently H, hydrocarbyl, or substituted hydrocarbyl.
10. The process of claim 4 wherein the ligand of formula IX is
selected from: 48wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; R.sup.11 is hydrocarbyl, or substituted hydrocarbyl; U
is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or -NR.sup.10R.sup.8,
wherein R.sup.10 and R.sup.8 are each independently selected from
H, hydrocarbyl, substituted hydrocarbyl, or silyl, and in addition
R.sup. and R.sup.8 may collectively form a ring with nitrogen, and
Z is oxygen or sulfur.
11. The process of claim 4 wherein the ligand is of formula XXII
and .OMEGA. is selected from 49
12. The process of claim 11 wherein the ligand of formula XXII is
selected from 50wherein, R.sup.3 is 2,6-disubstituted phenyl.
13. A process for the polymerization of olefins comprising
contacting one or more monomers of the formula RCH=CHR.sup.1 with a
binucleating or multinucleating ligand complexed to a Group 8-10
transition metal M and one or more Lewis acids, wherein the Lewis
acid or acids are bound to one or more heteroatoms which are
.pi.-conjugated to the donor atom or atoms bound to the transition
metal M; and R and R.sup.1 are each, independently selected from
hydrogen, hydrocarbyl, fluoroalkyl, or may be linked to form a
cyclic olefin.
14. The process of claim 13 wherein the transition metal M is
nickel.
15. The process of claim 14 wherein the Lewis acid is a boron or
aluminum containing Lewis acid.
16. The process of claim 4 wherein the polymerization is conducted
in an inert solvent.
17. The process of claim 5, 8, 10 or 11 wherein the polymerization
is conducted in an inert solvent.
18. The process of claim 4 wherein the transition metal olefin
polymerization catalyst system is attached to a solid support.
19. The process of claim 5, 8, 10, or 11 wherein the transition
metal olefin polymerization catalyst system is attached to a solid
support.
20. The process of claim 18 wherein the polymerization is conducted
in an inert solvent.
21. The process of claim 19 wherein the polymerization is conducted
in an inert solvent.
22. The process of claim 18 wherein the polymerization is conducted
in the gas phase.
23. The process of claim 19 wherein the polymerization is conducted
in the gas phase.
24. An olefin polymerization catalyst comprising (a) a Group 8-10
transition metal, (b) a ligand of the formula VI, XII, IX, XIII,
XIV, XV, or XXII and optionally (c) a Bronsted or Lewis acid,
51wherein R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or silyl;
R.sup.5 is hydrocarbyl or substituted hydrocarbyl; Z is O or S; U
is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or -NR.sup.10R.sup.8,
wherein R.sup.10 and R.sup.8 are each independently selected from
H, hydrocarbyl), substituted hydrocarbyl, or silyl, and in addition
R.sup.10 and R.sup.8 may collectively form a ring with nitrogen,
G.sup.1 is hydrocarbyl or substituted hydrocarbyl and may comprise
a carbocyclic or heterocyclic ring, thereby forming a 5-membered or
6-membered heterocyclic ring comprising G.sup.1, C, and N; G.sup.2
is hydrocarbyl or substituted hydrocarbyl and may comprise a
carbocyclic or heterocyclic ring, thereby forming a 5-membered or
6-membered heterocyclic ring comprising G.sup.2, V, N, and N; V is
-CR.sup.6, N, or -PR.sup.6R.sup.9, wherein, R.sup.6 and R.sup.9 are
each independently selected from H, hydrocarbyl, substituted
hydrocarbyl, silyl or heteroatom connected hydrocarbyl, and in
addition, R.sup.6 and R.sup.9 may collectively form a ring with
phosphorus; .OMEGA. is hydrocarbyl or substituted hydrocarbyl; and,
n is an integer between 2 and 6.
25. The catalyst of claim 24 wherein the Group 8-10 transition
metal is Ni.
26. The catalyst of claim 25 wherein a Lewis acid is used, and said
Lewis acid is methylaluminoxane.
27. The catalyst of claim 26 wherein the ligand of formula VI
selected from: 52wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl; R.sup.5, R.sup.6 and R.sup.11 are independently H,
hydrocarbyl, or substituted hydrocarbyl; R.sup.7 is H, hydrocarbyl,
substituted hydrocarbyl, or NO.sub.2.
28. The catalyst of claim 27 wherein the ligand of formula VI is
selected from: 53wherein R.sup.3 is nydrocarbyl or substituted
hydrocarbyl; R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl; and, R.sup.5 and R.sup.11 are independently H, hydrocarbyl,
or substituted hydrocarbyl.
29. The catalyst of claim 28 wherein the ligand of formula VI is
54wherein Ar.sup.1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl,
and Ar.sup.2 is phenyl or 1-naphthyl.
30. The catalyst of claim 26 wherein the ligand of formula XII is
selected from 55wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen, R.sup.5, R.sup.6 and
R.sup.11 are independently H, hydrocarbyl, or substituted
hydrocarbyl; R.sup.7 is H, hydrocarbyl, substituted hydrocarbyl,
or-NO.sub.2.
31. The catalyst of claim 30 wherein the ligand of formula XII is
selected from: 56wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl, U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen, R.sup.5 and R.sup.11 are
independently H, hydrocarbyl, or substituted hydrocarbyl.
32. The catalyst of claim 26 wherein the ligand of formula IX is
selected from: 57wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl; R.sup.11 is hydrocarbyl or substituted hydrocarbyl; U
is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or -NR.sup.10R.sup.8,
wherein R.sup.10 and R.sup.8 are each independently selected from
H, hydrocarbyl, substituted hydrocarbyl, or silyl, and in addition
R.sup.10 and R.sup.8 may collectively form a ring with nitrogen;
and Z is oxygen or sulfur.
33. The catalyst of claim 26 wherein the ligand is of formula XXII
and .OMEGA. is selected from: 58
34. The catalyst of claim 33 wherein the ligand of formula XXII is
selected from: 59wherein, R.sup.3 is 2,6-disubstituted phenyl.
35. A composition comprising (a) a group 8-10 transition metal M,
(b) one or more Lewis acids, and (c) a binucleating or
multinucleating ligand of the formula VI 60wherein the Lewis acid
or acids are bound to one or more heteroatoms which are
.pi.-conjugated to the donor atoms bound to the transition metal M;
R.sup.3 is hydrocarbyl or substituted hydrocarbyl; R.sup.4 is H,
hydrocarbyl, substituted hydrocarbyl, or silyl, G.sup.2 is
hydrocarbyl or substituted hydrocarbyl and may comprise a
carbocyclic or heterocyclic ring, thereby forming a 5-membered or
6-membered heterocyclic ring comprising G.sup.2, V, N and N, V is
-CR.sup.6, N, or -PR.sup.6R.sup.9; wherein, R.sup.6 and R.sup.9 are
each independently selected from H, hydrocarbyl, substituted
hydrocarbyl, silyl or heteroatom connected hydrocarbyl, and in
addition, R.sup.6 and R.sup.9 may collectively form a ring with
phosphorus.
36. The composition of claim 35 wherein the transition metal M is
Ni(II), and the Lewis acid is a boron or aluminum containing
acid.
37. The composition of claim 36 wherein the compound of formula VI
is selected from: 61wherein the Lewis acid or acids are bound to
one or more heteroatoms which are .pi.-conjugated to the donor atom
or atoms bound to the transition metal M, R.sup.3 is hydrocarbyl or
substituted hydrocarbyl, R.sup.4 is H, hydrocarbyl, substituted
hydrocarbyl, or silyl; R.sup.5 and R.sup.6 are independently H,
hydrocarbyl, or substituted hydrocarbyl; R.sup.7 is H, hydrocarbyl,
substituted hydrocarbyl, or -NO.sub.2.
38. The composition of claim 37 wherein the ligand of formula VI is
62wherein R.sup.3 is hydrocarbyl or substituted hydrocarbyl, and,
R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or silyl.
39. The composition of claim 38 wherein the ligand of formula VI is
63wherein Ar.sup.1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl;
and, Ar.sup.2 is phenyl or 1-naphthyl.
40. The catalyst of claim 24 wherein the catalyst is attached to a
solid support.
41. The catalyst of claim 27 wherein the catalyst is attached to a
solid support.
42. The catalyst of claim 30 wherein the catalyst is attached to a
solid support.
43. The catalyst of claim 32 wherein the catalyst is attached to a
solid support.
44. The catalyst of claim 33 wherein the catalyst is attached to a
solid support.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part application of
U.S. Ser. No. 09/028,315, filed on Feb. 24, 1998, the disclosure of
which is incorporated herein by reference, and claims the benefit
of the following provisional applications under 35 USC .sctn. 119:
Provisional application Ser. No. 60/040,754, filed Mar. 13, 1997;
Provisional application Ser. No. 60/044,691, filed Apr. 18, 1997;
Provisional application Ser. No. 60/045,337, filed May 1,1997;
Provisional application Ser. No. 60/045,358, filed May 2, 1997;
Provisional application Ser. No. 60/045,357, filed May 2, 1997; and
Provisional application Ser. No. 60/045,697, filed May 6, 1997.
FIELD OF THE INVENTION
[0002] The present invention relates to catalyst compositions for
olefin polymerization and processes for preparing polyolefins
utilizing the catalysts. More particularly, the present invention
relates to catalyst compositions comprising ligand complexes
comprising nitrogen, for example, heterocycle groups.
BACKGROUND OF THE INVENTION
[0003] 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.
[0004] 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
[0005] Recent advances in non-Ziegler-Natta olefin polymerization
catalysis include the following.
[0006] L. K. Johnson et al., WO patent application 96/23010,
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.
[0007] European patent application Ser. No. 381,495 describes the
polymerization of olefins using palladium and nickel catalysts that
contain selected bidentate phosphorous containing ligands.
[0008] 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 ethylene, Pd complexes act as catalysts for the
polymerization and copolymerization of olefins and methyl
acrylate.
[0009] G. F. Schmidt et al., J. Am. Chem. Soc. 1985, 107,1443,
describe a cobalt(III) cyclopentadienyl catalytic system having the
structure [C.sub.5Me.sub.5(L)CoCH.sub.2CH.sub.2-.mu.-H].sup.+,
which provides for the "living" polymerization of ethylene.
[0010] M. Brookhart et al., Macromolecules 1995, 28, 5378, disclose
using such "living" catalysts in the synthesis of
end-functionalized polyethylene homopolymers.
[0011] 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
[0012] 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.
[0013] 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
[0014] 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;
G. Wilke, Angew. Chem. Int. Ed. Engl. 1988, 27, 185, describes a
nickel allyl phosphine complex for the polymerization of
ethylene.
[0015] 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.
[0016] WO patent application 97/02298 discloses the polymerization
of olefins using a variety of neutral N, O, P, or S donor ligands,
in combination with a nickel(O) compound and an acid.
[0017] Brown et al., WO 97/17380, describes the use of Pd
.alpha.-diimine catalysts for the polymerization of olefins
including ethylene in the presence of air and moisture.
[0018] Fink et al., U.S. Pat. No., 4,724,273, have described the
polymerization of .alpha.-olefins using aminobis(imino)phosphorane
nickel catalysts and the compositions of the resulting
poly((.alpha.-olefins).
[0019] Recently Vaughan et al. WO 9748736, Denton et al. WO
9748742, and Sugimura et al. WO 9738024 have described the
polymerization of ethylene using silica supported .alpha.-diimine
nickel catalysts.
[0020] Recently Canich et al. WO 9748735, and Mecking (Germ. Offr.
DE 19707236 A1 980827) described the use of mixed .alpha.-diimine
catalysts with group IV transition metal catalysts for the
polymerization of olefins.
[0021] Additional recent developments are described by Sugimura et
al., in JP96-84344, JP96-84343, by Yorisue et al., in JP96-70332,
McLain et al. WO 9803559, Weinberg et al. WO 9803521 and by
Matsunaga et al. WO 9748737.
[0022] Notwithstanding these advances in non-Ziegler-Natta
catalysis, there remains a need for efficient and effective Group
8-10 transition metal catalysts for effecting polymerization of
olefins In addition, there is a need for novel methods of
polymerizing olefins employing such effective Group 8-10 transition
metal catalysts. In particular, there remains a need for Group 8-10
transition metal olefin polymerization catalysts with both improved
temperature stability and functional group compatibility. Further,
there remains a need for a method of polymerizing olefins utilizing
effective Group 8-10 transition metal catalysts in combination with
a Lewis acid so as to obtain a catalyst that is more active and
more selective.
SUMMARY OF THE INVENTION
[0023] The present invention includes novel ligands, which may be
utilized as part of a catalyst system. A catalyst system of the
present invention is a transition metal--ligand complex. In
particular, the catalyst system is comprised of a transition metal
component and a ligand component comprising a nitrogen atom,
generally in the form of an imine or heterocycle group. Preferred
ligand components are bidentate and include a nitrogen--transition
metal bond. The transition metal--ligand complex is generally
cationic and associated with a weakly coordinating anion.
[0024] A catalyst system of the present invention may further
comprise a Lewis or Bronsted acid. The Lewis or Bronsted acid may
be complexed with the transition metal component and/or the ligand
component of the transition metal-ligand complex.
[0025] In one aspect of the present invention, the transition metal
component of the catalyst system is Group 8-10 transition metals.
In another aspect, the catalyst system further comprises a Lewis or
Bronsted acid and the transition metal component is Group 8-10
transition metals. Preferred transition metal components include
iron (Fe), cobalt (Co), nickel (Ni) and palladium (Pd). The choice
of a particular transition metal may be made in view of the end use
of the catalyst system.
[0026] The present invention provides a batch or continuous process
for the polymerization of olefins, comprising contacting one or
more monomers selected from compounds of the formula RCH=CHR.sup.1
with a Group 8-10 transition metal complex of a ligand of the
formula VI, XII, IX, XIII, XIV, XV, or XXII and optionally a
Bronsted or Lewis acid, 1
[0027] wherein R and R.sup.1 are independently H, hydrocarbyl,
fluoroalkyl, or R and R.sup.1 may be linked to form a cyclic
olefin;
[0028] R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0029] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl;
[0030] R.sup.5 is hydrocarbyl or substituted hydrocarbyl,
[0031] Z is O or S;
[0032] U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen,
[0033] G.sup.1 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.1, C,
and N;
[0034] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0035] V is -CR.sup.6, N, or -PR.sup.6R.sup.9; wherein, R.sup.6 and
R.sup.9 are each independently selected from H, hydrocarbyl,
substituted hydrocarbyl, silyl or heteroatom connected hydrocarbyl,
and in addition, R.sup.6 and R.sup.9 may collectively form a ring
with phosphorus;
[0036] .OMEGA. is hydrocarbyl or substituted hydrocarbyl; and,
[0037] n is an integer between 2 and 6.
[0038] The present invention also provides novel catalysts useful
for the polymerization of olefins comprising (a) a Group 8-10
transition metal, (b) a ligand of the formula VI, XII, IX, XIII,
XIV, XV, or XXII and optionally (c) a Bronsted or Lewis acid, 2
[0039] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0040] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl;
[0041] R.sup.5 is hydrocarbyl or substituted hydrocarbyl;
[0042] Z is O or S;
[0043] U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen,
[0044] G.sup.1 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.1, C,
and N;
[0045] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0046] V is -CR.sup.6, N, or -PR.sup.6R.sup.9; wherein, R.sup.6 and
R.sup.9 are each independently selected from H, hydrocarbyl,
substituted hydrocarbyl, silyl or heteroatom connected hydrocarbyl,
and in addition, R.sup.6 and R.sup.9 may collectively form a ring
with phosphorus;
[0047] .OMEGA. is hydrocarbyl or substituted hydrocarbyl; and,
[0048] n is an integer between 2 and 6.
[0049] In the above process, it should be appreciated that the
Group 8-10 transition metal has coordinated thereto a ligand having
the formula VI, XII, IX, XIII, XIV, or XXII, and that component (c)
is optionally reacted with this metal-ligand complex.
[0050] Preferred catalysts are those wherein the ligand of formula
VI is selected from: 3
[0051] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0052] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl;
[0053] R.sup.5, R.sup.6 and R.sup.11 are independently H,
hydrocarbyl, or substituted hydrocarbyl;
[0054] R.sup.7 is H, hydrocarbyl, substituted hydrocarbyl, or
NO.sub.2. In a further preferred embodiment, the ligand of formula
VI is selected from: 4
[0055] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0056] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl; and,
[0057] R.sup.5 and R.sup.11 are independently H, hydrocarbyl, or
substituted hydrocarbyl. Further preferred ligands of formula VI
include 5
[0058] wherein Ar.sup.1 is 2,6-dimethylphenyl or
2,6-diisopropylphenyl; and,
[0059] Ar.sup.2 is phenyl or 1-naphthyl.
[0060] Preferred ligands of the formula XII include 6
[0061] wherein R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.11 and U
are defined as above.
[0062] The catalyst system of this invention is extremely versatile
in that changes in the ligand or changes to the transition metal
itself can be made to obtain a "tailor made" catalyst to suit a
particular set of requirements for a particular monomer and
polymer. Also, the catalyst of the present invention may be used
under a variety of reaction conditions including temperatures
between about -100 and 200 .degree. C. and pressures between about
1 and 100 atmospheres. Additionally, the catalysts of the present
invention may be used in solution, slurry or gas phase
polymerizations. Further, the catalysts may be attached to a solid
support. In certain embodiments of the present invention, a Lewis
or Bronsted acid may be used as a co-catalyst to render the
transition metal more electron deficient, and therefore more active
and/or selective, and/or act as a site to bind the catalyst to a
surface.
[0063] Further features and advantages of the catalyst system and
processes of the present invention will become more apparent from
the following more detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0064] The novel ligand components of the present invention are
broadly described as comprising a nitrogen atom, preferably in the
form of an imine or heterocyclic functional group.
[0065] A catalyst system of the present invention may further
comprise a Lewis or Bronsted acid, which may be complexed with the
ligand component or the transition metal component. While not
wishing to be bound by theory, it is believed that the Lewis acid
complexation can render the transition metal more electron
deficient, and therefore more active and/or selective, and/or act
as a site to bind the catalyst to a surface. Although this strategy
may be implemented in a variety of ways, ligands in which the Lewis
acid is bound to one or more heteroatoms which are .pi.-conjugated
to the donor atom or atoms bound to the transition metal are
preferred.
[0066] In one aspect of the present invention, the transition metal
component of the catalyst system is a Group 8-10 transition metal.
In another aspect, the catalyst system further is a Lewis or
Bronsted acid and the transition metal component is a Group 8-10
transition metal. A catalyst system of the present invention may
advantageously be utilized in a process for the polymerization of
olefins, including ethylene and .alpha.-olefins such as propylene
and 1-hexene and cyclic olefins such as cyclopentene and
norbornene. Accordingly, a process of the present invention is
contacting one or more monomers comprising RCH=CHR.sup.1 with a
catalyst system of the present invention at a temperature and a
pressure sufficient to effect polymerization, preferably a
temperature of -100 to 200 .degree. C., more preferably a
temperature from 25 to 150.degree. C., and a pressure of from about
1 atmosphere to 100 atmospheres, wherein R and R.sup.1 are
independently hydrogen, hydrocarbyl, fluoroalkyl, or R and R.sup.1
may be linked to form a cyclic olefin. The possible embodiments of
a process of the present invention for the production of
polyolefins include processes utilizing the catalyst systems of the
present invention described herein.
[0067] The embodiments of a catalyst system of the present
invention are described in detail below utilizing the following
terms defined as follows:
[0068] Symbols ordinarily used to denote elements in the Periodic
Table take their ordinary meaning, unless otherwise specified.
Thus, N, O, S, P, and Si stand for nitrogen, oxygen, sulfur,
phosphorus and silicon, respectively.
[0069] Examples of neutral Lewis bases include, but are not limited
to, organic ethers, organic nitrites or organic sulfides.
[0070] Examples of Lewis acids include, but are not limited to,
methylaluminoxane (hereinafter MAO) and other aluminum
sesquioxides, R.sup.7.sub.3Al, R.sup.7.sub.2AlCl, R.sup.7AlCl.sub.2
(where R.sup.7 is alkyl), organoboron compounds, boron halides,
B(C.sub.6F.sub.5).sub.3, R.sup.9.sub.3Sn[BF.sub.4], (where R.sup.9
is alkyl or aryl), MgCl.sub.2, and H.sup.+X.sup.-, where X.sup.- is
a weakly coordinating anion.
[0071] 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 or 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 or 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 or aryl. As used
herein, the term "aryl" preferably denotes a phenyl, napthyl, or
anthracenyl group. When the above groups are substituted, they are
preferably substituted from one to four times with the listed
groups. Examples of divalent (bridging hydrocarbyls) include:
-CH.sub.2-, -CH.sub.2CH.sub.2-, -C.sub.6H.sub.4-, and
-CH.sub.2CH.sub.2CH.sub.2-.
[0072] Specific examples of G.sup.2 as used herein include, but are
not limited to: -CH.sub.2-CH.sub.2-, -CH.sub.2-O-,
-N(CH.sub.3)-CH.sub.2-. -CH.sub.2-CH.sub.2-O-,
-N(CH.sub.3)-CH.sub.2-CH.sub.2-, -S-CH.sub.2-,
-S-CH.sub.2-CH.sub.2-, -CH=CH-, -CH=N-, -CH=CH-CH.sub.2-,
-CH=N-CH.sub.2-, and -C.sub.6H.sub.4-.
[0073] A "silyl" group refers to a SiR.sub.3 group where Si is
silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl,
as in Si(SiR.sub.3).sub.3
[0074] A "heteroatom" refers to an atom other than carbon or
hydrogen. Preferred heteroatoms include oxygen, nitrogen,
phosphorus, sulfur, selenium, arsenic, chlorine, bromine, and
fluorine.
[0075] The term "fluoroalkyl" as used herein refers to a
C.sub.1-C.sub.20 alkyl group substituted with one or more fluorine
atoms.
[0076] A "substituted hydrocarbyl" refers to a monovalent or
divalent hydrocarbyl substituted with one or more heteroatoms.
Examples of monovalent substituted hydrocarbyls include:
trifluoromethyl, 2,6-dimethyl-4-methoxyphenyl,
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-nitrophenyl, 2,6-dimethyl4-trifluoromethylphenyl,
2,6-dimethyl-4-trimethylammoniumphen- yl (associated with a weakly
coordinating anion), 2,6-dimethyl-4-hydroxyph- enyl,
9-hydroxyanthr-10-yl, 2-chloronapth-1-yl, 4-methoxyphenyl,
4-nitrophenyl, and 9-nitroanthr-10-yl. Examples of divalent
substituted hydrocarbyls include 4-methoxy-1,2-phenylene,
1-methoxymethyl-1,2-ethaned- iyl, 1,2-bis(benzyloxymethyl
)-1,2-ethanediyl, and 1-(4-methoxyphenyl)-1,2- -ethanediyl.
[0077] A "mono-olefin" means a hydrocarbyl group having one
carbon-carbon double bond.
[0078] The term "polymer" as used herein is meant a species
comprised of monomer units and having a degree of polymerization
(DP) of ten or higher.
[0079] 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. Suitable weakly
coordinating anions include, but are not limited to,
PF.sub.6.sup.-, BF.sub.4.sup.-, SbF.sub.6.sup.-, (Ph).sub.4B.sup.-
where Ph=phenyl, .sup.-BAr.sub.4 where
.sup.-BAr.sub.4=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The
coordinating ability of such anions is known and described in the
literature (Strauss, S. et al, Chem. Rev. 1993, 93, 927).
[0080] As used herein, the terms "monomer" or "olefin monomer"
refer to the olefin or other monomer compound before it has been
polymerized. The term "monomer units" refers to the moieties of a
polymer that correspond to the monomers after they have been
polymerized.
[0081] In some cases, a compound Y is required as a cocatalyst.
Suitable compounds Y include a neutral Lewis acid capable of
abstracting Q.sup.- or W.sup.- (as defined below) 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. Preferred compounds Y include:
methylaluminoxane (hereinafter MAO) and other aluminum
sesquioxides, R.sup.7.sub.3Al, R.sup.7.sub.2AlCl, R.sup.7AlCl.sub.2
(where R.sup.7 is alkyl), organoboron compounds, boron halides,
B(C.sub.6F.sub.5).sub.3, R.sup.9.sub.3Sn[BF.sub.4], (where R.sup.9
is alkyl or aryl), MgCl.sub.2, and H.sup.+X.sup.-, where X.sup.- is
a weakly coordinating anion.
[0082] Examples of "solid support" include inorganic oxide support
materials, 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 solid supports such as polystyrene and
functionalized polystyrene. (See, for example, Roscoe, S. B.;
Frechet, J. M. J.; Walzer, J. F.; Dias, A. J.; "Polyolefin Spheres
from Metallocenes Supported on Non-interacting Polystyrene", 1998,
Science, 280, 270-273 (1998).) An especially preferred solid
support is one which has been pre-treated with Y compounds as
described herein, most preferably with MAO. 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) which has been pre-treated with
a compound Y. Alternatively, the catalyst, the compound Y, and the
solid support can be combined in any order, and any number of Y
compounds can be utilized; in addition, the supported catalyst thus
formed, may be treated with additional quantities of compound(s) Y.
In an especially preferred embodiment, the compounds of the present
invention are attached to silica which has been pre-treated with
MAO. 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 catalysts. Examples of substantially inert solvents
include toluene, mineral spirits, hexane, CH.sub.2Cl.sub.2 and
CHCl.sub.3.
[0083] Preferred polyolefin products will have a degree of
polymerization (DP) of at least 10. A preferred olefin monomer is
RCH=CHR.sup.1 wherein R and R.sup.1 are independently H,
hydrocarbyl, fluoroalkyl, or R and R.sup.1 may be linked to form a
cyclic olefin. Especially preferred olefin monomers include
ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
cyclopentene, and norbornene.
[0084] The preferred temperature range for the polymerization
reaction is about -100 to 200.degree. C., more preferably a
temperature from about 25 to 150.degree. C.; a preferred pressure
is about 1 atmosphere to 100 atmospheres
[0085] The present invention provides a catalyst system comprising
a transition metal complex of bidentate ligands having a
five-membered ring, formed by the metal complex, and preferably
comprising one metal atom, one carbon atom, and three nitrogen
atoms.
[0086] The olefin polymerization catalysts of the present invention
comprise transition metal complexes of bidentate ligands that can
be referred to as imino-substituted heterocycles, more specifically
imino-substituted pyrazoles, triazoles and other related
heterocycles. The transition metal component is a Group 8-10
transition metal. Nickel, cobalt and palladium are preferred
transition metals. The ligands may also be referred to using a
"imine/heterocycle" or "heterocycle/imine" nomenclature, which
describes the two components of the bidentate ligand, e.g.,
imine/triazole. The five-membered ring formed by the transition
metal complex preferably contains one transition metal atom, one
carbon atom, and three nitrogen atoms (two of which are provided by
the heterocycle component of the bidentate ligand).
[0087] While not wishing to be bound by theory, the inventors
believe that the active catalytic specie of the present invention
is a transition metal complex of the formula I 7
[0088] wherein M is Group 8-10 transition metal, preferably Ni, Pd,
Fe or Co;
[0089] T is H, or hydrocarbyl;
[0090] L is a mono-olefin, or a neutral lewis base wherein the
coordinated atom is nitrogen, oxygen, or sulfur;
[0091] X.sup.- is a weakly coordinating anion; and, 8
[0092] is a bidentate N,N donor imine/heterocycle ligand selected
from ligands of the formula VI, XII, IX, XIII, XIV, XV, and XXII
9
[0093] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0094] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl,
[0095] wherein:
[0096] R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0097] R.sup.4 is hydrogen, hydrocarbyl, substituted hydrocarbyl,
or silyl;
[0098] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0099] V is CR.sup.6, N, or PR.sup.6R.sup.9;
[0100] R.sup.6 and R.sup.9 are each independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl or heteroatom
connected hydrocarbyl, and in addition, R.sup.6 and R.sup.9 may
collectively form a ring with phosphorus;
[0101] T is hydrogen, hydrocarbyl, or substituted hydrocarbyl.
[0102] L is a monoolefin or a neutral Lewis base where the donating
atom is nitrogen, oxygen, sulfur;
[0103] M is Ni(II), Pd(II), or Co(II); and
[0104] X.sup.- is a weakly coordinating anion.
[0105] Further, with regard to active species utilizing ligands of
the formula XXII, the present invention provides a catalyst system
comprising a transition metal-ligand complex of the formula XXIII:
10
[0106] wherein:
[0107] R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0108] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0109] V is CR.sup.6, N, or PR.sup.6R.sup.9;
[0110] R.sup.6 and R.sup.9 are each independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl or heteroatom
connected hydrocarbyl, and in addition, R.sup.6 and R.sup.9 may
collectively form a ring with phosphorus;
[0111] .OMEGA. is hydrocarbyl or substituted hydrocarbyl;
[0112] n is an integer between 2 and 6;
[0113] T is hydrogen, hydrocarbyl, or substituted hydrocarbyl;
[0114] L is a monoolefin or a neutral Lewis base where the donating
atom is nitrogen, oxygen, sulfur;
[0115] M is Ni(II), Pd(II), or Co(II); and
[0116] X.sup.- is a weakly coordinating anion.
[0117] Preferred ligands of formula VI include the following:
11
[0118] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0119] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl;
[0120] R.sup.5, R.sup.6 and R.sup.11 are independently H,
hydrocarbyl, or substituted hydrocarbyl;
[0121] R.sup.7 is H, hydrocarbyl, substituted hydrocarbyl, or
NO.sub.2.
[0122] Further preferred ligands of formula VI include 12
[0123] wherein Ar.sup.1 is 2,6-dimethylphenyl or
2,6-diisopropylphenyl; and, Ar.sup.2 is phenyl or 1-naphthyl.
[0124] Preferred ligands of formula XII include the following:
13
[0125] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0126] U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen;
[0127] R.sup.5, R.sup.6 and R.sup.11 are independently H,
hydrocarbyl, or substituted hydrocarbyl;
[0128] R.sup.7 is H, hydrocarbyl, substituted hydrocarbyl, or
NO.sub.2.
[0129] Further preferred ligands of formula XII include: 14
[0130] Preferred ligands of formula IX include 15
[0131] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0132] R.sup.11 is hydrocarbyl, or substituted hydrocarbyl;
[0133] U is OR.sup.10, SR.sup.10, SeR.sup.10 or NR.sup.10R.sup.8,
wherein R.sup.10 and R.sup.8 are each independently selected from
H, hydrocarbyl, substituted hydrocarbyl, or silyl, and in addition
R.sup.10 and R.sup.8 may collectively form a ring with nitrogen,
and Z is oxygen or sulfur.
[0134] In formula XXII, preferred .OMEGA. groups include the
following 16
[0135] We recognize that there are numerous methodologies available
to prepare the catalytically active complex of formula I. The
methodologies include reacting a catalyst precursor complex of
formula I (described below) with a Lewis acid (such as
methylaluminoxane) in the presence of a mono-olefin (such as
ethylene) to generate in situ a catalytically active specie of
formula I. The catalyst precursor complex of formula II has a
formula of: 17
[0136] wherein M is Group 8-10 transition metal, preferably Ni, Pd,
Fe or Co:
[0137] Q is hydrocarbyl, chloride, iodide, or bromide;
[0138] W is hydrocarbyl, chloride, iodide, or bromide; and, 18
[0139] is a bidentate N,N donor imine/heterocycle ligand selected
from ligands of the formula VI, XII, IX, XIII, XIV, XV, and XXII
19
[0140] wherein R.sup.3 is hydrocarbyl or substituted
hydrocarbyl;
[0141] R.sup.4 is H, hydrocarbyl, substituted hydrocarbyl, or
silyl;
[0142] R.sup.5 is hydrocarbyl or substituted hydrocarbyl;
[0143] Z is O or S;
[0144] U is -OR.sup.10, -SR.sup.10, -SeR.sup.10 or
-NR.sup.10R.sup.8, wherein R.sup.10 and R.sup.8 are each
independently selected from H, hydrocarbyl, substituted
hydrocarbyl, or silyl, and in addition R.sup.10 and R.sup.8 may
collectively form a ring with nitrogen.
[0145] G.sup.1 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.1, C,
and N;
[0146] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0147] V is CR.sup.6, N, or PR.sup.6R.sup.9; wherein, R.sup.6 and
R.sup.9 are each independently selected from H, hydrocarbyl,
substituted hydrocarbyl, silyl or heteroatom connected hydrocarbyl,
and in addition, R.sup.6 and R.sup.9 may collectively form a ring
with phosphorus;
[0148] .OMEGA. is hydrocarbyl or substituted hydrocarbyl; and, n is
an integer between 2 and 6. Specific examples of this methodology
are detailed in the example section below.
[0149] Preferred catalysts of formula II are those which comprise a
ligand of the formula VI or XXII.
[0150] Thus, in the case of a ligand of formula VI, the present
invention provides a catalyst system formed by contacting a first
compound Y with a second compound V having the formula: 20
[0151] wherein:
[0152] R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0153] R.sup.4 is hydrogen, hydrocarbyl, substituted hydrocarbyl,
or silyl;
[0154] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0155] V is CR.sup.6, N, or PR R.sup.9;
[0156] R.sup.6 and R.sup.9 are each independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl or heteroatom
connected hydrocarbyl, and in addition, R.sup.6 and R.sup.9 may
collectively form a ring with phosphorus;
[0157] Q is hydrocarbyl, chloride, iodide, or bromide;
[0158] W is hydrocarbyl, chloride, iodide, or bromide;
[0159] M is Ni(II), Pd(II), or Co(II); and Y is selected from 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.
[0160] Further, with regard to active species utilizing ligands of
the formula XXII, the present invention provides a catalyst system
formed by contacting a first compound Y with a second compound XXIV
having the formula: 21
[0161] wherein:
[0162] R.sup.3 is hydrocarbyl or substituted hydrocarbyl;
[0163] G.sup.2 is hydrocarbyl or substituted hydrocarbyl and may
comprise a carbocyclic or heterocyclic ring, thereby forming a
5-membered or 6-membered heterocyclic ring comprising G.sup.2, V,
N, and N;
[0164] V is CR.sup.6, N, or PR.sup.6R.sup.9;
[0165] R.sup.6 and R.sup.9 are each independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl or heteroatom
connected hydrocarbyl, and in addition, R.sup.6 and R.sup.9 may
collectively form a ring with phosphorus;
[0166] Q is hydrocarbyl, chloride, iodide, or bromide;
[0167] W is hydrocarbyl, chloride, iodide, or bromide;
[0168] M is Ni(II), Pd(II), or Co(III); .OMEGA. is hydrocarbyl or
substituted hydrocarbyl, n is an integer between 2 and 6: and Y is
selected from 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.
[0169] Preferred neutral Lewis acids include: MAO and other
aluminum sesquioxides, R.sub.3.sup.7Al, R.sup.7.sub.2AlCl, and
R.sup.7AlCl.sub.2 wherein R.sup.7 is alkyl. Complex V and compound
Y may be combined in the liquid phase. The liquid phase may include
solvent or neat monomer. In a process for preparing polyolefins,
complex V and compound Y may be combined in the presence of
monomer. The molar ratio of compound Y to complex V may be from
about 10 to 10,000.
[0170] A second methodology for the in situ generation of an active
complex of the formula I involves contacting a ligand with a
suitable transition metal complex in the presence of a Bronsted
acid and ethylene to provide an active catalyst. An example of
using this methodology to prepare a catalyst of formula I would
involve contacting a ligand of formula VI, XII, IX, XIII, XIV, XV,
or XXII (as described above) with a suitable Ni complex (such as
Ni(1,5-cyclooctadiene).sub.2) and a Bronsted acid (such as
HB(Ar).sub.4 where Ar is 3,5-bis(trifluoromethyl)phenyl) in the
presence of an olefin (such as ethylene) to generate an active
olefin polymerization catalyst of formula I. Specific examples of
this methodology are detailed in the example section below. (See
also, L. K. Johnson et al., WO patent application 96/23010).
[0171] Preferred neutral Lewis acids include: MAO and other
aluminum sesquioxides, R.sub.3.sup.7Al, R.sup.7.sub.2AlCl, and
R.sup.7AlCl.sub.2 wherein R.sup.7 is alkyl.
[0172] The skilled artisan, in possession of this disclosure, could
make the present compounds without undue experimentation. Methods
of synthesizing complexes I and II, and compounds VI, XII, IX,
XIII, XIV, XV, and XXII are also illustrated in the following
examples.
[0173] Preferred ligand components for use in complex I or II and
preferred catalyst systems utilizing complex I or II are also set
forth in the following examples.
[0174] The present invention also provides processes for preparing
polyolefins utilizing complexes I, II, and compounds VI, XII, IX,
XIII, XIV, XV, and XXII.
[0175] The present invention also provides a class of olefin
polymerization catalysts based on late transition metal complexes
of bidentate ligands comprising one imidate ester, thioimidate
ester, selenoimidate ester, or amidine N-donor fragment, and one
heterocyclic N-donor fragment, the two fragments together
comprising a neutral bidentate, N,N-donor ligand. In one aspect,
the catalyst "system" further comprises a Lewis or Bronsted
acid.
[0176] An electron deficient metal center is advantageous for
efficient olefin polymerization. A further embodiment of the
present invention provides catalyst systems wherein a binucleating
or multinucleating ligand is complexed to a transition metal and
one or more Lewis acids to obtain an active olefin polymerization
catalyst. While not wishing to be bound by any theory, it is
believed that the Lewis acid complexation renders the transition
metal more electron deficient rendering the transition metal
catalyst more active and/or selective, and/or potentially providing
a site to bind the catalyst system to a surface. Thus, broadly,
catalyst systems of this embodiment of the present invention
comprise ligand components, such as the ligand components described
above, complexed with a transition metal and a Lewis acid.
Preferred catalyst systems of this embodiment of the present
invention include catalyst systems wherein the Lewis acid is bound
to one or more heteroatoms which are .pi.-conjugated to the donor
atom or atoms bound to the transition metal.
[0177] Thus, in a further preferred embodiment, the invention
provides a process for the polymerization of olefins comprising
contacting one or more monomers of the formula RCH=CHR.sup.1 with a
binucleating or multinucleating ligand complexed to a Group 8-10
transition metal M and one or more Lewis acids, wherein the Lewis
acid or acids are bound to one or more heteroatoms which are
.pi.-conjugated to the donor atom or atoms bound to the transition
metal M; and R and R.sup.1 are each, independently selected from
hydrogen, hydrocarbyl, fluoroalkyl, or may be linked to form a
cyclic olefin.
[0178] Examples of catalyst systems comprising a Lewis
acid--ligand--transition metal complex of the present invention
include XIX: 22
[0179] wherein
[0180] R.sup.3, R.sup.4, L, and T are defined as above.
[0181] Complex XIX may be produced by synthesizing the transition
metal--ligand complex in the manner described above and exemplified
in the example herein, and then combining the transition
metal--ligand complex with the Lewis acid component.
[0182] The present invention also describes a process for preparing
polyolefins comprising contacting one or more olefin monomers with
a catalyst system at a temperature and a pressure sufficient to
effect polymerization, wherein the catalyst system comprises a
transition metal-ligand-Lewis acid complex, e.g. complex XIX of the
above embodiment of the present invention.
[0183] As noted above, it is preferred that certain of the
compounds of the present invention be attached to a solid support
which has been pre-treated with a compound Y, for example, MAO, or
mixed with Y in any order. When such supported catalysts are used
in slurry and gas phase ethylene polymerizations, novel polymer
compositions are provided insofar as such compositions are blends
of different polyolefin polymers. It is believed that when such
catalysts are attached to a solid support, such as silica,
polyolefin polymerizations using such supported catalysts provide a
polymer composition which possesses a broad compositional
distribution, This is believed to be due at least in part to both
the creation of unique reaction sites, and the sensitivity of these
catalysts to ethylene concentration. These unique reaction sites
are believed to result from the unique microenvironments created by
the location of the catalyst on the support. The resulting polymer
composition, which can be prepared solely from ethylene as an
olefin feedstock, is one which is actually a blend or plurality of
polymers having a variety of alkyl branched distributions with some
catalyst sites giving less branched high density polymer and other
sites giving more branched lower density polymer.
[0184] When the polymerizations are conducted in the liquid phase,
said liquid phase may include solvent or neat monomer. The molar
ratio of neutral Lewis acid to transition metal complex can be from
1 to 10000, preferably 10 to 1000. The pressure at which the
ethylene polymerizations and copolymerizations take place can be
from 1 atmosphere to 1000 atmospheres, preferably 1 to 100
atmospheres.
[0185] 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.
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.
[0186] Temperature and olefin concentration have significant
effects on polymer structure, composition, and molecular weight.
Suitable polymerization temperatures are preferably from about
-100.degree. C. to about 200.degree. C., more preferably in the
20.degree. C. to 150.degree. C. range.
[0187] 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.
[0188] 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.
[0189] 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.
[0190] 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.
[0191] 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.
EXAMPLES
[0192] Ligand Synthesis 23
[0193] C1: R.sup.8=Me, R.sup.9=1-naphthyl
[0194] C2: R.sup.8=iPr, R.sup.9=1-naphthyl
[0195] C3: R.sup.8=Me, R.sup.9=phenyl
[0196] C4: R.sup.8=iPr, R.sup.9=phenyl
[0197] C5: R.sup.8=iPr, R.sup.9=2,6-dimethoxyphenyl
[0198] C20: R.sup.8=Me, R.sup.9=2-biphenyl
Example 1
[0199] Synthesis of C1. Equimolar amounts of 1,2,4-triazole and
N-(2,6-dimethylphenyl)-1-naphthimidoyl chloride (derived in the
conventional fashion [H. Ulrich, The Chemistry of Imidoyl Halides,
Plenum, N.Y., 1968] from the corresponding amide and phosphorus
pentachloride) were treated with an excess of triethylamine in
methylene chloride at room temperature. After 1 hour, the solution
was concentrated, taken up in ethyl acetate, filtered, and washed
sequentially with saturated sodium bicarbonate solution, 0.5M HCI
solution, and brine, then dried over magnesium sulfate, filtered,
and concentrated to a syrup. Purification by flash chromatography
(hexane/EtOAc=4:1) afforded the triazole/imine ligand C1 as a pale
yellow solid.
Example 2
[0200] Synthesis of C20. A solution of
N-(2,6-dimethyl-phenyl)-biphenyl-2-- carboximidoyl chloride (833
mg, 2.6 mmol), 1,2,4-triazole (400 mg, 5.8 mmol) and triethylamine
(0.5 mL, 3.6 mmol) in CH.sub.2Cl.sub.2 (5 mL) was allowed to stand
at room temperature for 3 days. The resulting solution was washed
with water (50 mL), dried over Na.sub.2SO.sub.4 and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
20% ethyl acetate (EtOAc)/Hexanes) to afford C1 (470 mg, 59%) as a
light yellow oil: R.sub.f0.44 (20% EtOAC/Hexanes); field desorption
mass spectrometry (FDMS): m/z 352.
Example 3
[0201] Synthesis of C2. A mixture of 1,2,4-triazole (1.2 mmol) and
N-(2,6-diisopropylphenyl)-1-naphthimidoyl chloride (0.5 mmol) was
treated with triethylamine (1 mmol) and methylene chloride (5 mL)
and stirred four hours at room temperature. The reaction was worked
up as described in example 1 to afford C2 as a pale yellow
solid.
Example 4
[0202] Synthesis of C3. A mixture of 1,2,4-triazole (2.9 mmol) and
N-(2,6-dimethylphenyl)-1-benzimidoyl chloride (1.5 mmol) was
treated with triethylamine (1.5 mmol) and methylene chloride (7 mL)
and stirred 14 hours at room temperature. The reaction was worked
up as described in example 1 to afford C3 as a pale yellow solid
(242 mg).
Example 5
[0203] Synthesis of C3. A solution of N-(2,6-dimethylphenyl)-1
-benzimidoyl chloride (362 mg, 1.48 mmol) in CH.sub.2Cl.sub.2 (7
ml) was treated with 1,2,4-triazole (212 mg, 3.07 mmol) and
triethylamine (0 209 ml, 1.49 mmol). The resulting solution was
stirred at room temperature overnight. The solvent was removed in
vacuo, and the resulting residue was suspended in EtOAc (15 ml) and
filtered. The filtrate was washed with 0.5 M HCl (10 ml) and brine
(10 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
70% (EtOAc: Hexanes) to afford C3 (248 mg, 61%): R.sub.f 0.80 (70%
EtOAc: Hexanes); .sup.1H NMR (300 MHz, CDCl.sub.3, TMS reference)
.delta.9.14 (1H, s), 8.08 (1H, s), 7.21-7.38 (5H, m), 6.87-6.98
(3H, M), 2.06 (6H, s); FDMS m/z 276 (M.sup.+).
Example 6
[0204] Synthesis of C4. A mixture of 1,2,4-triazole (1.5 mmol) and
N-(2,6-diisopropylphenyl)-1-benzimidoyl chloride (0.7 mmol) was
treated with triethylamine (1 mmol) and methylene chloride (6 mL)
and stirred overnight at room temperature. The reaction was worked
up as described in example 1 to afford C4 as a pale yellow solid
(85 mg) after purification by flash chromatography
(hexane/EtOAc=3:1).
Example 7
[0205] Synthesis of C4. 1,2,4-Triazole (480 mg, 6.9 mmol) was added
to a solution of N-(2,6-diisopropylphenyl)-1-benzimidoyl chloride
(1.0 g, 3.3 mmol) in CH.sub.2Cl.sub.2 (10 mL). The resulting
suspension was treated with triethylamine (2 mL, 14.3 mmol) and
allowed to stand at room temperature overnight. The solvent was
removed in vacuo and the residue partitioned between EtOAc and
H.sub.2O. The organic layer was concentrated In vacuo and the
residue was purified by flash chromatography (SiO.sub.2) to afford
C4.
Example 8
[0206] Synthesis of C5. 2,6-Diisopropylaniline (25 mmol) was added
to a chilled suspension of 2,6-dimethoxybenzoyl chloride (25 mmol)
in pyridine (20 mL). After stirring three hours, water (50 mL) was
added, resulting in a purple precipitate that was isolated by
filtration and subsequently recrystallized from ethanol to provide
the amide as a purple solid.
[0207] A solution of the amide (690 mg, 2 mmol) in acetonitrile (8
mL) was added to a mixture formed by the addition of triethylamine
(580 .mu.L) to a cooled suspension of 1,2,4-triazole (420 mg, 6
mmol) and POCl.sub.3 in acetonitrile (8 mL). After stirring 24
hours at room temperature, the reaction contents were filtered, and
the filtrate was evaporated to an oil. The oil was dissolved in
EtOAc, and washed successively with aqueous solutions of sodium
bicarbonate, HCl, and NaCl. The organic layer was dried over
magnesium sulfate, filtered, and concentrated to an oil.
Purification by flash chromatography (hexane/EtOAc=3:1) afforded
the desired imino-substituted heterocyclic C5. 24
[0208] C6: R.sup.8=Me, R.sup.9=1-naphthyl, R.sup.10=CH.sub.3
[0209] C7: R.sup.8=iPr, R.sup.9=1-naphthyl, R.sup.10=CH.sub.3
[0210] C8: R.sup.8=Me, R.sup.9=1-naphthyl R.sup.10=H
[0211] C8a. R.sup.8=iPr, R9=phenyl, R.sup.10=H
Example 9
[0212] Synthesis of C6. A mixture of 3-methylpyrazole (0.8 mmol)
and N-(2,6-dimethylphenyl)-1-naphthimidoyl chloride (0.8 mmol) was
treated with triethylamine (1.5 mmol) and methylene chloride (5 mL)
and stirred 4 hours at room temperature. The reaction was worked up
as described in example 1 to afford the desired pyrazole/imine
C6.
Example 10
[0213] Synthesis of C7. A mixture of 3-methylpyrazole (1.0 mmol)
and N-(2,6-diisopropylphenyl)-1-naphthimidoyl chloride (0.7 mmol)
was treated with triethylamine (1.0 mmol) and methylene chloride (5
mL) and stirred 1 hour at room temperature. The reaction was worked
up as described in example 1 to afford the desired pyrazole/imine
C7.
Example 11
[0214] Synthesis of C8. A mixture of pyrazole (4.0 mmol) and
N-(2,6-dimethylphenyl)-1-naphthimidoyl chloride (1.5 mmol) was
treated with triethylamine (2.0 mmol) and methylene chloride (8 mL)
and stirred 16 hours at room temperature. The reaction was worked
up as described in example 1 to afford the desired pyrazole/imine
C8 as pale yellow crystals.
Example 12
[0215] Synthesis of C8a. Pyrazole (460 mg, 7.0 mmol) was added to a
solution of N-(2,6-diisopropylphenyl)-1-benzimidoyl chloride (1.0
g, 3.3 mmol) in CH.sub.2Cl.sub.2 (8 mL). The resulting solution was
treated with triethylamine (2 mL 14.3 mmol) and allowed to stand at
room temperature overnight. The solution was partitioned between
H.sub.2O and EtOAc. The organic layer was washed with HCl (0.2 N),
H.sub.2O, and brine, dried over MgSO.sub.4, filtered and
concentrated in vacuo. The residue was dissolved in
CH.sub.2Cl.sub.2/hexane and treated with methanol (MeOH) to induce
crystallization. The crystals were isolated by vacuum filtartion to
afford C8a (300 mg, 27%) as off white crystals. 25
[0216] C9: R.sup.8=iPr; R.sup.9=1-naphthyl; R.sup.10,
R.sup.11=CH
[0217] C10: R.sup.8 iPr; R.sup.9=phenyl; R.sup.10, R.sup.11=C-Ph
and N (one C-Ph, one N)
Example 13
[0218] Synthesis of C9. A mixture of 1H-1,2,3-triazole (100 .mu.L)
and N-(2,6-diisopropylphenyl)-1-naphthimidoyl chloride (200 mg) was
treated with triethylamine (150 .mu.l) and methylene chloride (6
mL) and stirred 1 hour at room temperature. The reaction was worked
up as described in example 1 to afford the desired triazole/imine
C9.
Example 14
[0219] Synthesis of C10. A mixture of 5-phenyl-1H-tetrazole (160
mg, 1.1 mmol) and N-(2,6-diisopropylphenyl)-1-benzimidoyl chloride
(0 7 mmol) was treated with triethylamine (250 .mu.l) and methylene
chloride (6 mL) and stirred 16 hours at room temperature. The
reaction was worked up as described in example 1. Attempts to
further purify the desired product using silica gel chromatography
led to ligand decomposition, and thus the crude product of the
workup was used directly in the next step to form the nickel
complex D10. 26
[0220] C11: R.sup.8=iPr; R.sup.9=phenyl; R.sup.11=COOH; X=CH;
Y=N
[0221] C12: R.sup.8=iPr; R.sup.9=phenyl; R.sup.11=H; X=N; Y=N
[0222] C13: R.sup.8=iPr; R.sup.9=CF.sub.3; R.sup.11=H; X=CH;
Y=CH
[0223] C14: R.sup.8=iPr; R.sup.9=CF.sub.3; R.sup.11=NO.sub.2; X=CH;
Y=CH
Example 15
[0224] Synthesis of C11. A mixture of benzotriazole-5-carboxylic
acid (163 mg, 1.0 mmol) and N-(2,6-diisopropylphenyl)-1-benzimidoyl
chloride (0.7 mmol) was treated with triethylamine (260 .mu.l) and
methylene chloride (6 mL) and stirred overnight at room
temperature. The reaction was worked up as described in example 1
and purified by flash chromatography (hexane/ethyl acetate=3:1) to
afford the desired benzotriazole/imine C11, as well as a
contaminant byproduct (MS=689) which may be the diacylated product
resulting from acylation of both the desired ring nitrogen and the
carboxylic acid.
Example 16
[0225] Synthesis of C12 A mixture of
1H-1,2,3-triazolo(4,5.beta.)pyridine (1.0 mmol) and
N-(2,6-diisopropylphenyl)-1-benzimidoyl chloride (0.5 mmol) was
treated with triethylamine (1.0 mmol) and methylene chloride (7 mL)
and stirred 16 hours at room temperature. The reaction was worked
up as described in example 1 and used directly without further
purification.
Example 17
[0226] Synthesis of C13 A solution of indazole (202 mg, 1.71 mmol)
in tetrahydrofuran (THF) (5.0 mL) was cooled to 0.degree. C. in an
ice bath and treated with NaH (60% dispersion in mineral oil, 106
mg, 2.66 mmol). The resulting suspension was stirred at 0.degree.
C. for 25 min, then treated with
N-(2,6-diisopropylphenyl)-trifluoroacetimidoyl chloride (497 mg,
1.70 mmol) [which had been prepared according to the procedure of
K. Tamura, et al., J. Org. Chem. 1993, 58, 32-35, from
trifluoroacetic acid, 2,6-diisopropyl aniline, carbon
tetrachloride, triphenylphosphine and triethylamine] via syringe,
rinsing the syringe with THF (0.5 mL). The ice bath was removed,
and the suspension allowed to stir at rt for 1.5 h. The solvent was
removed in vacuo, and the residue was partitioned between saturated
NaHCO.sub.3 (5 mL) and CH.sub.2Cl.sub.2 (5 mL). The aqueous layer
was further extracted with CH.sub.2Cl.sub.2 (2.times.5 mL). The
combined organic extracts were dried over Na.sub.2SO.sub.4,
filtered and concentrated in vacuo. The resulting residue was flash
chromatographed (SiO.sub.2, 4% EtOAc: Hex) to afford C13 (548 mg,
86%): R.sub.f 0.27 (4% EtOAc: Hex); .sup.1H-NMR (300 MHz,
CDCl.sub.3) .delta.8.45 (d, 1 H, J=8.2 Hz), 8.29 (d, 1 H, J=0.6
Hz), 7.84 (dt, 1 H, J=8.0 Hz, J=1.1 Hz) 7.54 (ddd, 1H, J=8.4 Hz,
J=7.1 Hz, J 1.1 Hz), 7.40 (ddd, 1 H, J=8.0Hz, J=7.1 Hz, J=0.8 Hz),
7.06-7.20 (m, 3H), 2.85 (p, 2H, J=6.9 Hz), 1.20 (d, 6H, J=6.9 Hz),
1.15 (d, 6 H, J=6.6 Hz); IR (film) 2965, 1684, 1431, 1171, 1154,
926 cm.sup.-1; FDMS m/z 373 (M+, 100%).
[0227] C13 was contaminated with a small amount of unidentified
impurities: .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.7.72 (d, J=9.1
Hz), 2.72 (d, J=6.9 Hz).
Example 18
[0228] Synthesis of C14 A solution of 5-nitroindazole (286 mg, 1.75
mmol) in THF (5 mL) was cooled to 0.degree. C. in an ice bath and
treated with NaH (60% dispersion in mineral oil, 110 mg, 2.74
mmol). The resulting suspension was stirred at 0.degree. C. for 20
min, then treated with
N-(2,6-diisopropylphenyl)-trifluoroacetimidoyl chloride (509 mg,
1.74 mmol) via syringe, rinsing the syringe with THF (0.5 mL). The
ice bath was removed, and the suspension stirred at rt for 2 h. The
solvent was removed in vacuo, and the residue partitioned between
saturated NaHCO.sub.3 (5 mL) and CH.sub.2Cl.sub.2 (5 mL). The
aqueous layer was further extracted with CH.sub.2Cl.sub.2
(2.times.5 mL). The combined organic extracts were dried over
Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue
was flash chromatographed (3% EtOAc: Hex) to afford C14 (573 mg,
78%): R.sub.f 0.16 (3% EtOAc: Hex); .sup.1H NMR (300 MHz,
CDCl.sub.3) .delta.8.80 (dd, 1 H, J=2.2 Hz, J=0.5 Hz), 8.47 (s,
1H), 8.42 (dd, 1H, J=9.2 Hz, J=1.9 Hz), 8.12 (dd, 0.5 H, J=9.8 Hz,
J=1.9 Hz), 7.85 (d, 0.5 H, J=9.6 Hz), 7.18-7.22 (m, 3 H), 2.79 (p,
2 H, J=6.9 Hz), 1.20 (br d, 6 H, J=5.8 Hz), 1.16 (br d, 6 H, J=6.0
Hz); IR (Film) 2965, 1686, 1528, 1431, 1345, 1172, 1150, 922; FDMS
m/z 418 (M+, 100%).
[0229] C14 was contaminated with a small amount of unidentified
impurities: .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.8.52-8.64 (br
m), 2.69 (p, J=6.9 Hz), 0.85-1.10 (br s). 27
[0230] C15: R.sup.8=CH.sub.3, R.sup.10=CF.sub.3
[0231] C16: R.sup.8=CH.sub.3, R.sup.10=OCH.sub.3
[0232] C17: R.sup.8=CH.sub.3, R.sup.10=NO.sub.2
[0233] C18: R.sup.8=CH.sub.3, R.sup.10=t-C.sub.4H.sub.9
Example 19
[0234] Synthesis of C15. A solution of
N-(2,6-dimethylphenyl)-4-trifluorom- ethyl-1-benzimidoyl chloride
(566.5 mg, 1.8 mmol) in CH.sub.2Cl.sub.2 (8.6 ml) was treated with
1,2,4-triazole (264 mg, 3.8 mmol) and triethylamine (0.254 ml, 1.8
mmol). The resulting solution was stirred at room temperature
overnight. The solvent was removed in vacuo, and the resulting
residue was suspended in EtOAc (20 ml) and filtered. The residue
was washed with EtOAc (2.times.5 mL). The combined filtrate was
washed with sat'd NaHCO.sub.3 (15 mL), 0.5 M HCl (15 mL), and brine
(15 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
30% EtOAc: Hexanes) to afford C15 (295 mg, 48%): R.sub.f 0.51 (30%
EtOAc: Hexanes); .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.9.24 (s,
1H), 8.09 (s, 1H), 7.58 (d, 2H, J=8.5 Hz), 7.36 (d, 2H, J=8.2 Hz),
6.94-7.27 (m, 3H), 2.06 (s, 6H); FDMS m/z 344 (M.sup.+, 100%).
Example 20
[0235] Synthesis of C16. A solution of
N-(2,6-dimethylphenyl)-4-methoxy-1 -benzimidoyl chloride (509.5 mg,
1.9 mmol) in CH.sub.2Cl.sub.2 (8.8 ml) was treated with
1,2,4-triazole (270 mg, 3.9 mmol) and triethylamine (0.260 ml, 1.9
mmol). The resulting solution was stirred at room temperature
overnight. The solvent was removed in vacuo, and the resulting
residue was suspended in EtOAc (20 ml) and filtered. The residue
was washed with EtOAc (2.times.5 mL). The combined filtrate was
washed with sat'd NaHCO.sub.3 (15 mL), 0.5 M HCl (15 mL), and brine
(15 ml), died over Na.sub.2SO.sub.4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
50% EtOAc: Hexanes) to afford C16 (424 mg. 77%): R.sub.f 0.58 (50%
EtOAc: Hexanes); .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.9.11 (s,
1H), 8.08 (s, 1H), 7.16 (d, 2H, J=8.8 Hz), 6.79 (d, 2H, J=8.5 Hz),
3.78 (s, 3H), 2.05 (s, 6H); FDMS m/z 307 (M+1, 100%).
Example 21
[0236] Synthesis of C17. A solution of
N-(2,6-dimethylphenyl)-4-nitro-1-be- nzimidoyl chloride (546.3 mg,
1.9 mmol) in CH.sub.2Cl.sub.2 (9 ml) was treated with
1,2,4-triazole (271 mg, 3.9 mmol) and triethylamine (0.260 ml, 1.9
mmol). The resulting solution was stirred at room temperature
overnight The solvent was removed in vacuo, and the resulting
residue was suspended in EtOAc (20 ml) and filtered. The residue
was washed with EtOAc (2.times.10 mL). The combined filtrate was
washed with sat'd NaHCO.sub.3 (20 mL), 0.5 M HCl (20 mL), and brine
(20 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography (SiO.sub.2,
30% EtOAc: Hexanes) to afford C17: R.sub.f 0.36 (30% EtOAc:
Hexanes); .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.9.26 (s, 1H),
8.16 (d, 2H, J=8.8 Hz), 8.08 (s, 1H), 7.42 (d, 2H, J=8.8 Hz),
6.94-6.97 (m, 3H), 2.07 (s, 6H); FDMS m/z 321 (M.sup.+, 100%).
Example 22
[0237] Synthesis of C18. A solution of
N-(2,6-dimethylphenyl)-4-(t-butyl)-- 1 -benzimidoyl chloride (506
mg, 1.7 mmol) in CH.sub.2Cl.sub.2 (5 ml) was treated with
1,2,4-triazole (257 mg. 3 7 mmol) and triethylamine (0.260 ml, 1.9
mmol). The resulting solution was allowed to stand at room
temperature for 10 days. The solvent was removed in vacuo. The
residue was re-dissolved in a minimal amount of CH.sub.2Cl.sub.2
and treated with hexane (20 mL). The supernatent was collected by
vacuum filtartion and concentrated in vacuo. The residue was
purified by flash chromatography (SiO.sub.2, 15% EtOAc/hex) to
afford C18 (238 mg, 42%) as a yellow solid: R.sub.f 0.35 (15%
EtOAc/hex); FDMS: m/z 332 28
Example 23
[0238] Synthesis of C19. CH.sub.2Cl.sub.2 (5 mL) was added to a
mixture of
N.sup.1,N.sup.4-bis(2,6-dimethyl-phenyl)-terephthalodiimidoyl
dichloride (1.07 g, 2.45 mmol) and pyrazole (615 mg, 9.03 mmol).
The resulting suspension was treated with triethylamine (1 mL, 7.17
mmol), CH.sub.2Cl.sub.2 (5 mL), triethylamine (1 mL, 7.17 mmol) and
CH.sub.2Cl.sub.2 (5 mL). The resulting solution was stirred at room
temperature overnight. The solvent was removed in vacuo and the
residue suspended in CH.sub.2Cl.sub.2/EtOAc/Et.sub.2O. The organic
mixture was washed several times with H.sub.2O and brine, dried
over Mg.sub.2SO.sub.4 filtered and concentrated in vacuo. The
residue was purified by flash chromatography (SiO.sub.2, 19%
EtOAc/hex). After chromatography, the bis(imine/pyrazole) C19
crystallized from the eluent and was collected by vacuum filtration
and dried in vacuo to afford C19 (611 mg, 53%); FDMS: m/z 472.
29
[0239] D1: R.sup.8=Me, R.sup.9=1 -naphthyl
[0240] D2: R.sup.8=iPr, R.sup.9=1 -naphthyl
[0241] D3: R.sup.8=Me, R.sup.9=phenyl
[0242] D4: R.sup.8=iPr, R.sup.9=phenyl
[0243] D5: R.sup.8=iPr, R.sup.9=2,6-dimethoxyphenyl
[0244] D20: R.sup.8=Me, R.sup.9=2-biphenyl
Example 24
[0245] Synthesis of D1. A methylene chloride solution of the
triazole/imine C1 (46 mg, 0.14 mmol) and (DME)NiBr.sub.2 (37 mg,
0.12 mmol) were combined via stainless steel cannula. The mixture
was left to stir at 23.degree. C. for 16 hours. The solvent was
partially evaporated under reduced pressure and 10 mL of hexane was
added to fully precipitate the complex. The resulting yellow solid
was washed with hexane and then placed under high vacuum to remove
all solvent. 37 mg of pre-catalyst D1 isolated (60% yield).
Example 25
[0246] Synthesis of D20. Methylene Chloride (5 mL) was added to a
mixture of triazole/imine C20 (168.2 mg, 0.48 mmol) and
(diemethyoxyethane(DME))N- iBr.sub.2 (124.6 mg, 0.40 mmol). The
resulting suspension was stirred at room temperature under Ar for 5
min, then an additional portion of ligand (23.3 mg, 0.066 mmol) was
added. The resultant suspension was stirred at room temperature for
one hour. 2 mL of hexane was added and the resulting supernatent
removed via filter tip cannula. The precipitate was dried in vacuo
to provide D20 (41 mg) as a green powder.
Example 26
[0247] Synthesis of D2. A flame dried Schlenk flask was equipped
with a magnetic stir bar and capped with a rubber septum. To the
flask was added (DME)NiBr.sub.2 (59 mg 0.191 mmol) and 10 mL of
methylene chloride. In a separate flask the imine/triazole C2 (78
mg, 0.204mmol) was dissolved in 5 mL of methylene chloride and
transferred via stainless steel canula onto the (DME)NiBr.sub.2
suspension. The mixture was stirred at room temperature for 16
hours. After 16 hours, the methylene chloride was removed in vacuo
resulting in a yellow/green solid. The solid was washed with
2.times.10 mL of hexane. The solid was left to dry under reduced
pressure for several hours resulting in 42 mg of the imine/triazole
complex D2.
Example 27
[0248] Synthesis of D3. Methylene chloride (8 mL) was added to a
mixture of triazole/imine C3 (54 mg) and (DME)NiBr.sub.2 (57 mg).
The reaction was stirred at room temperature overnight. Solvent was
removed via filter cannula, and the pale yellow powder was washed
with hexane, then dried in vacuo.
Example 28
[0249] Synthesis of D3. Methylene Chloride (15 mL) was added to a
mixture of triazole/imine C3 (107.4 mg, 0.39 mmol) and
(DME)NiBr.sub.2 (100 mg, 0.33 mmol). The resultant suspension was
stirred at room temperature overnight to afford a green suspension.
The solvent was removed under a stream of Ar then in vacuo to
afford D3 as a green solid.
Example 29
[0250] Synthesis of D4. Methylene chloride (6 mL) was added to a
mixture of triazole/imine C4 (60 mg) and (DME)NiBr.sub.2 (45 mg).
The reaction was stirred at room temperature overnight The solvent
was partially evaporated under a stream of argon, and hexane was
added. The precipitated pale green complex was washed several times
with hexane, then dried in vacua
Example 30
[0251] Synthesis of D4. CH.sub.2Cl.sub.2 (10 mL) was added to a
mixture of C4 (114.9 mg 0.34 mmol) and (DME)NiBr.sub.2 (96 mg, 0.31
mmol) in a flame dried Schlenk flask under N.sub.2. The resulting
suspension was stirred at room temperature under N.sub.2 for 42 h,
then concentrated under a stream of N.sub.2 and in vacua to afford
D4 (160 mg, 97%) as a green powder.
Example 31
[0252] Synthesis of D5. Methylene chloride (9 mL) was added to a
mixture of ligand C5 (125 mg) and (DME)NiBr.sub.2 (83 mg). The
reaction was stirred at room temperature overnight. The solvent was
partially evaporated under a stream of argon, and hexane was added.
The precipitated pale green complex was washed several times with
hexane, then dried in vacuo. 30
[0253] D6: R.sup.8=Me, R.sup.9=1-naphthyl, R.sup.10=CH.sub.3
[0254] D7: R.sup.8=iPr, R.sup.9=1-naphthyl,
R.sup.10=CH.sub.3D7a
[0255] R.sup.8=iPr, R.sup.9=phenyl, R.sup.10=H
Example 32
[0256] Synthesis of D6. Methylene chloride (10 mL) was added to a
mixture of the pyrazole/imine ligand C6 (81 mg, 0.24 mmol) and
(DME)NiBr.sub.2 (60 mg, 0.19 mmol). The suspension immediately
turned a deep orange/brown color, and was allowed to stir 18 hours.
The solvent was evaporated under a stream of argon, and the
precipitated orange solid was washed several times with hexane and
hexane/methylene chloride before drying in vacuo. The pre-catalyst
D6 was isolated as an orange/brown powder.
Example 33
[0257] Synthesis of D7. A flame dried Schlenk flask was equipped
with a magnetic stir bar and capped with a rubber septum. To the
flask was added (DME)NiBr.sub.2 (71 mg, 0.23 mmol) and 10 mL of
methylene chloride In a separate flask the imine/heterocycle C7 (98
mg, 0.25 mmol) was dissolved in 5 mL of methylene chloride and
transferred via stainless steel canula onto the (DME)NiBr.sub.2
suspension. The mixture was stirred at room temperature for 16
hours. After 16 hours, the methylene chloride was removed in vacuo
resulting in a red/brown solid. The solid was washed with 2.times.5
mL of hexane. The solid was left to dry under reduced pressure for
several hours resulting in 97 mg of the imine/heterocycle complex
D7.
Example 34
[0258] Synthesis of D7a. CH.sub.2Cl.sub.2 (14 mL) was added to a
mixture of C8a (110 mg. 0.33 mmol) and (DME)NiBr.sub.2 (91 mg, 3.0
mmol) in a flame dried Schlenk flask. The resulting solution was
stirred at room temperature for 1 hour, then treated with hexane
(10 mL) and concentrated under a stream of N.sub.2 until
crystallization began The supernatent was removed via filter paper
tipped cannula. The crystals were dried in vacuo to afford D7a (128
mg, 80%) as tan crystals.
[0259] Synthesis of 31
[0260] D9: R.sup.8=iPr; R.sup.9=1-naphthyl; R.sup.10,
R.sup.11=CH
[0261] D10: R.sup.8=iPr; R.sup.9=phenyl; R.sup.10, R.sup.11=C-Ph
and N (one C-Ph, one N)
Example 35
[0262] Synthesis of D9. Methylene chloride (5 mL) was added to a
mixture of the triazole/imine ligand C9 (42 mg) and (DME)NiBr.sub.2
(200 mg). The suspension was allowed to stir 18 hours, at which
time the solvent was evaporated under a stream of argon, and the
precipitated yellow-orange solid was washed several times with
hexane and hexane/methylene chloride before drying in vacuo.
Example 36
[0263] Synthesis of D10. Methylene chloride (7 mL) was added to a
mixture of the tetrazole/imine ligand C10 (82 mg) and
(DME)NiBr.sub.2 (40 mg). The suspension was allowed to stir 18
hours, at which time the solvent was evaporated under a stream of
argon, and the precipitate pale green solid was washed several
times with hexane and hexane/methylene chloride before drying in
vacuo. 32
[0264] D11: R.sup.8=iPr; R.sup.9=phenyl; R.sup.11COOH, X=CH;
Y=N
[0265] D12: R.sup.8=iPr; R.sup.9=phenyl; R.sup.11=H; X=N; Y=N
[0266] D13: R.sup.8=iPr; R.sup.9=CF.sub.3; R.sup.11=H; X=CH;
Y=CH
[0267] D14: R.sup.8=iPr; R.sup.9=CF.sub.3; R.sup.11=NO.sub.2; X=CH;
Y=CH
Example 37
[0268] Synthesis of D11 Methylene chloride (5 mL) was added to a
mixture of excess benzotriazole/imine ligand C11 and
(DME)NiBr.sub.2. The reaction was allowed to stir 18 hours, at
which time the solvent was evaporated under a stream of argon, and
the precipitated beige solid was washed several times with hexane
and hexane/methylene chloride before drying in vacuo.
Example 38
[0269] Synthesis of D12. Methylene chloride was added to a mixture
of the benzotriazole/imine ligand C12 (82 mg) and a deficiency of
(DME)NiBr.sub.2. A green precipitate appeared almost immediately.
The solvent was evaporated under a stream of argon, and the
precipitated pale green solid was washed several times with hexane
and hexane/methylene chloride before drying in vacuo.
Example 39
[0270] Synthesis of D13 A mixture of imine/indazole adduct C13 (112
mg, 0.299 mmol) and (DME)NiBr.sub.2 (73 mg, 0.238 mmol) was
dissolved in CH.sub.2Cl.sub.2 (10 mL). The resulting solution was
stirred at rt overnight. The suspension was concentrated under a
stream of Ar, and the resulting precipitate was washed several
times with hexanes. The precipitate was dried in vacuo to afford
dibromo complex D13.
Example 40
[0271] Synthesis of D14 A mixture of imine/indazole adduct C14 (100
mg, 0.238 mmol) and (DME)NiBr.sub.2 (63 mg, 0.206 mmol) was
dissolved in CH.sub.2Cl.sub.2 (10 mL), and stirred at rt overnight.
The orange/yellow suspension was concentrated under a stream of Ar,
and washed with hexanes (10 mL). The residue was dried in vacuo to
afford D14 as an orange solid. 33
[0272] D15: R.sup.8=CH.sub.3, R.sup.10=CF.sub.3
[0273] D16: R.sup.8=CH.sub.3, R.sup.10=OCH.sub.3
[0274] D17: R.sup.8=CH.sub.3, R.sup.10=NO.sub.2
[0275] D18: R.sup.8=CH.sub.3, R.sup.10=t-C.sub.4H.sub.9
Example 41
[0276] Synthesis of D15. Methylene Chloride (15 mL) was added to a
mixture of triazole/imine C15 (108.1 mg, 0.31 mmol) and
(DME)NiBr.sub.2 (72 mg, 0.24 mmol). The resultant suspension was
stirred at room temperature for 2 hr to afford a green suspension
The solvent was removed under a stream of Ar then in vacuo to
afford D15 as a green solid.
Example 42
[0277] Synthesis of D16. Methylene Chloride (15 mL) was added to a
mixture of triazole/imine C16 (104.5 mg, 0.34 mmol) and
(DME)NiBr.sub.2 (84 mg, 0.27 mmol). The resultant suspension was
stirred at room temperature for 2.5 hr to afford a green
suspension. The solvent was removed under a stream of Ar then in
vacuo to afford D16 as a green solid.
Example 43
[0278] Synthesis of D17. A solution of imine/triazole C17 (100 mg,
0.311 mmol) dissolved in CH.sub.2Cl.sub.2 (15 mL) was added to
(DME)NiBr.sub.2 (76 mg, 0.249 mmol) in a flame dried Schlenk flask
under Ar. The resulting suspension was stirred at rt under Ar
overnight. The solvent was removed under a stream of Ar, then in
vacuo to afford D17 as a yellow/green solid.
Example 44
[0279] Synthesis of D18. Methylene Chloride (10 mL) was added to a
mixture of triazole/imine C18 (104 mg, 0.31 mmol) and
(DME)NiBr.sub.2 (74 mg, 0.25 mmol). The resultant suspension was
stirred at room temperature overnight. The solvent was removed
under a stream of N.sub.2. The residue was washed with hexane (5
mL) then dried in vacuo to afford D18 (89 mg) as a green solid.
34
Example 45
[0280] Synthesis of D19. CH.sub.2Cl.sub.2 (10 mL) was added to a
mixture of C19 (122 mg, 0.258 mmol) and (DME)NiBr.sub.2 (120 mg,
0.392 mmol) in a flame dried Schlenk flask. The resulting
suspension was stirred at room temperature overnight, then treated
with hexane (10 mL). The solvent was removed via a filter paper
tipped canula. The residue was washed with CH.sub.2Cl.sub.2 (10 mL)
and dried in vacuo to afford D19 (167 mg, 94%) as a green
solid.
[0281] Synthesis of Supported Catalysts
Example 46
[0282] Synthesis of the Supported Nickel Complex D19. A flame dried
Schlenk flask was charged with the imine/pyrazole complex D19 (45.5
mg, 50.0 .mu.mol) and MAO treated silica (1 g, purchased from Witco
TA 02794/HL/04) in an Ar filled dry box. The flask was immersed in
an ice water bath under Ar, then CH.sub.2Cl.sub.2 (25 mL) was
added. The resulting suspension was stirred at 0.degree. C. for 20
min then the solvent was removed in vacuo at 0.degree. C. to afford
supported D19 as an orange solid.
Example 47
[0283] Synthesis of the supported Nickel Complex D18. A flame dried
Schlenk flask was charged with the imine/triazole complex D18 (13.3
mg, 24.1 .mu.mol) and MAO treated silica (2.14 g, purchased from
Witco TA 02794/HL/04) in an Ar filled dry box. The flask was
removed from the box, and immersed in an ice water bath under Ar,
then CH.sub.2Cl.sub.2 (25 mL) was added. The resulting suspension
was stirred at 0.degree. C. for 25 min then the solvent was removed
in vacuo at 0.degree. C. to afford supported D18.
[0284] POLYMERIZATIONS
Example 48
[0285] The triazole/imine complex D1 (2.0 mg) was suspended in 50
mL of dry toluene. The reaction mixture was equilibrated at room
temperature under an ethylene atmosphere, then treated with MAO
(2.0 mL of a 10% by weight solution in toluene) and stirred under 1
atm ethylene. A white polyethylene precipitate was observed within
minutes. After five minutes, the reaction was quenched by the
sequential addition of acetone, methanol, and 6M HCl. The
precipitate was isolated by filtration, washed, and dried in vacuo
to yield 700 mg of polyethylene (85,000 To/h). DSC: T.sub.m=123.
GPC: M.sub.w=23,000.
Example 49
[0286] A stock solution of the triazole/imine complex D20 was
prepared by suspending complex D20 (4.0 mg, ) in toluene (4.0 mL)
and CH.sub.2Cl.sub.2 (4.0 mL). 50 mL of toluene was stirred
vigorously in an ice bath under 1 atm ethylene in a flame dried
Schlenk flask for 20 min. A 10% by weight solution of MAO in
toluene (4 mL) was added to the polymerization flask, followed by 2
mL of the nickel complex stock solution. The resulting solution was
stirred vigorously under 1 atm ethylene at 0.degree. C. for 40 min.
The reaction was quenched by sequential addition of MeOH, HCl (6N)
and acetone. The polyethylene was isolated by vacuum filtration and
dried in an 80.degree. C. vacuum oven overnight to afford 1.2 g of
polyethylene; GPC: M.sub.n=2,340, M.sub.w=19,800.
Example 50
[0287] The triazole/imine complex D3 (2.7 mg) was suspended in 20
mL of dry toluene. The reaction mixture was equilibrated at
0.degree. C. under an ethylene atmosphere, then treated with MAO
(2.0 mL of a 10% by weight solution in toluene) and stirred under 1
atm ethylene. After 15 minutes, the reaction was quenched by the
sequential addition of acetone, methanol, and 6M HCl. The
precipitate was isolated by filtration, washed, and dried in vacuo
to yield 747 mg of polyethylene. (19,600 To/h, M.sub.n=6900,
M.sub.w=52,200 (GPC); 2 branches/1000 carbons by .sup.1H NMR).
Example 51
[0288] The triazole/imine complex D3 (4.5 mg, 9.05 .mu.mol) was
suspended in dry toluene (50 mL) in a flame dried 500 mL round
bottom flask fitted with a gas adapter. The suspension was cooled
to 0.degree. C. in an ice bath and placed under an ethylene
atmosphere (1 atm). A 10% by weight solution of MAO in toluene (2
mL) was added to the polymerization flask. The resulting solution
was stirred vigorously under 1 atm ethylene at 0.degree. C. for 20
min, then quenched by sequential addition of acetone, MeOH, and HCl
(6 N). The resulting polymer was collected by vacuum filtration and
dried in vacuo to afford 2.88 g of polyethylene (34,000 TO/hr,
M.sub.n=7390, M.sub.w=55,200 (GPC); 2 branches/1000 C's (.sup.1H
NMR)).
Example 52
[0289] The triazole/imine complex D3 (3.8 mg, 7.6 .mu.mol) was
suspended in dry toluene (100 mL) in a flame dried 500 mL round
bottom flask fitted with a gas adapter. The suspension was immersed
in a room temperature water bath and placed under an ethylene
atmosphere (1 atm). A 10% by weight solution of MAO in toluene (2
mL) was added to the polymerization flask. The resulting solution
was stirred vigorously under 1 atm ethylene at rt for 10 min, then
quenched by sequential addition of acetone, MeOH, and HCl (6 N).
The resulting polymer was collected by vacuum filtration and dried
in vacuo to afford 1.24 g of polyethylene (70,200 TO/hr,
M.sub.n=2410, M.sub.w=18,900 (GPC); 13 branches/1000 C's (.sup.1H
NMR)).
Example 53
[0290] The triazole/imine complex D4 (3.4 mg, 6.4 .mu.mol) was
suspended in toluene (50 mL) and cooled to 0-4.degree. C. in an ice
water bath under an atmosphere of ethylene. The suspension was
stirred vigorously under 1 atm ethylene for 10 min, then treated
with a 10% by weight solution of MAO in toluene (4 mL). The
resulting suspension was stirred vigorously under an atmosphere of
ethylene at 0-4.degree. C. for 10 min, then quenched by sequential
addition of MeOH, acetone, and 6N HCl. The precipitated polymer was
isolated by vacuum filtration and dried in an 80.degree. C. vacuum
oven overnight to afford 1.9 g of polyethylene (66,000 TO/h).
.sup.1H NMR: (M.sub.n=3014, 13.4 branches/1000 carbons).
Example 54
[0291] The pyrazole/imine complex D6 (14.6 mg) was suspended in 18
mL of dry toluene. The reaction mixture was cooled to 0.degree. C.
and placed under an ethylene atmosphere. A 10% by weight solution
of MAO in toluene (1.8 mL) was added to the polymerization flask.
The ice bath was removed and the mixture was left to stir for
thirty minutes with substantial evolution of heat. Acetone, 6M HCl,
and H.sub.2O were added to quench the polymerization and
precipitate the polyethylene. The polymer was isolated by
filtration, washed, and dried in vacuo. The procedure was repeated
without removing the ice bath, with similar polymer
characteristics. In both cases, .sup.1H NMR analysis was consistent
with branched polyethylene (M.sub.n<5.000).
Example 55
[0292] The pyrazole/imine complex D7a (5.2 mg, 9.4 .mu.mol) was
dissolved in toluene (50 mL) under an atmosphere of ethylene. The
resulting solution was stirred vigorously under 1 atm of ethylene,
then treated with a 10% by weight solution of MAO in toluene (4 mL)
and stirred vigorously under 1 atm of ethylene at room temperature
for 80 min. The reaction was quenched by sequential addition of
MeOH, 6N HCl, and acetone. The organic layer was separated, washed
with H.sub.2O, and concentrated in vacuo The resulting viscous oil
was treated with MeOH and concentrated in vacuo to afford 4.0 g of
polyethylene (11,400 TO/h). .sup.1H NMR: (M.sub.n=1162; 74.6
branches/1000 carbons).
Example 56
[0293] The triazole/imine complex D9 (4.0 mg) was suspended in 18
mL of dry toluene. The reaction mixture was cooled to 0.degree. C.
and placed under an ethylene atmosphere. A 10% by weight solution
of MAO in toluene (1.8 mL) was added to the polymerization flask.
The mixture was left to stir for 45 minutes at 0.degree. C.
Acetone, 6M HCl, and H.sub.2O were added to quench the
polymerization. No precipitated polyethylene was observed.
Separation and subsequent evaporation of the aqueous layer yielded
a small amount of solid. The reaction was repeated at room
temperature, and a small amount of amorphous material was
recovered.
Example 57
[0294] A 250 mL flame dried Schlenk flask was charged with
bis(1,5-cyclooctadiene)nickel(0) (14.0 mg, 0.051 mmol), HBAr.sub.4
(Ar=3,5-bis(trifluoromethyl)phenyl) (39.4 mg, 0.046 mmol) and
imine/indazole adduct C13 (13.7 mg, 0.037 mmol). The flask was
evacuated and backfilled with ethylene, then charged with toluene
(30 mL) resulting in the formation of a dark green/blue solution.
The reaction exothermed to .about.45.degree. C., and was allowed to
stir under ethylene (1 atm) with no temperature control for 1.5 h,
after which it was quenched by the addition of acetone and MeOH.
The solvent was removed in vacuo to afford an oily waxy solid (2.83
g): GPC: M.sub.n=327; M.sub.w/M.sub.n=9; .sup.1H NMR: 92
branches/1000 carbon atoms.
Example 58
[0295] A 250 mL flame dried Schlenk flask was charged with
bis(1,5-cyclooctadiene)nickel(0) (8.5 mg, 0.031 mmol), HBAr.sub.4
(Ar=3,5-bis(trifluoromethyl)phenyl) (24.3 mg, 0.028 mmol) and
imine/indazole adduct C14 (11.0 mg, 0.026 mmol). The flask was
evacuated and backfilled with ethylene, then charged with toluene
(30 mL) resulting in the formation of an orange/brown solution. The
reaction was allowed to stir under ethylene (1 atm) at rt for
.about.1.33 h, after which it was quenched by the addition of
acetone and MEOH. The resulting polyethylene was collected by
vacuum filtration, and dried in vacuo to afford a white
polyethylene (117.2 mg): GPC: M.sub.n=5710; M.sub.w/M.sub.n=4.7;
.sup.1H NMR: 42 branches/1000 carbon atoms.
Example 59
[0296] A flame dried Schlenk flask was charged with complex D7 (6
mg, 0.0098 mmol) and 50 mL of toluene. The flask was then cooled to
0.degree. C. in an ice bath. MAO (1.5 mL of a 10 wt. % solution in
toluene) was then added to the suspension and the reaction left to
stir for 30 minutes. Acetone, methanol and 6M HCl were added to
quench the reaction and precipitate the resulting branched
polyethylene (.sup.1H NMR M.sub.n=2500).
Example 60
[0297] A flame dried Schlenk flask was charged with complex D1 (5
mg, 0.0092 mmol), norbornene (2 g) and 50 mL of toluene. The flask
was then placed in a water bath (23.degree. C.) to control reaction
temperatue. MAO (2 mL of a 10 wt. % solution in toluene) was then
added to the suspension and the reaction left to stir for 16 hours.
Acetone and methanol were added to quench the reaction and
precipitate the resulting polynorbornene. The polymer was collected
by filtration and washed with 6M HCl, water, and acetone. The
polymer was dried in a vacuum oven resulting in 700 mg of
polynorbornene. GPC: M.sub.n=14,500; M.sub.n=44,000.
Example 61
[0298] A flame dried Schlenk flask was charged with complex D4 (6
mg, 0.0091 mmol), 1 atmosphere ethylene and 50 mL of toluene. The
flask was then placed in a water bath (23.degree. C.) to control
reaction temperatue. MAO (2 mL of a 10 wt. % solution in toluene)
was then added to the suspension and the reaction left to stir for
20 minutes (polymer began to precipitate within minutes). Acetone,
methanol and 6M HCl were added to quench the reaction and
precipitate the resulting polyethylene. The polymer was dried in a
vacuum oven resulting in 400 mg of polyethylene. GPC: M.sub.n=2100;
M.sub.w=5600. .sup.1H NMR: 30 branches/1000 carbon atoms. DSC:
T.sub.m=104.degree. C.
Example 62
[0299] A flame dried Fisher-Porter bottle was charged with complex
D2 (5 mg, 0.0083 mmol) and 50 mL of toluene. The flask was placed
in a water bath (23.degree. C.) to control reaction temperatue. MAO
(2 mL of a 10 wt. % solution in toluene) was then added to the
suspension and the bottle rapidly pressurized to 45 psig and the
reaction left to stir for 20 minutes. Acetone, methanol and 6M HCl
were added to quench the reaction and precipitate the resulting
polyethylene. The polymer was dried in a vacuum oven resulting in
150 mg of polyethylene. GPC: M.sub.w=22,000. .sup.1H NMR: 7
branches/i 1000 carbon atoms. DSC. T.sub.m=127.degree. C.
Example 63
[0300] A flame dried Schlenk flask was charged with complex D4 (2
mg, 0.0036 mmol), 1 atmosphere ethylene and 50 mL of toluene. The
flask was then placed in an ice-water bath (0.degree. C.) to
control reaction temperatue. MAO (2 mL of a 10 wt. % solution in
toluene) was then added to the suspension and the reaction left to
stir for 10 minutes (polymer began to precipitate within minutes).
Acetone, methanol and 6M HCl were added to quench the reaction and
precipitate the resulting polyethylene. The polymer was dried in a
vacuum oven resulting in 560 mg of polyethylene (33,000 TO/h). GPC:
M.sub.n=5500; M.sub.w=27,000. .sup.1H NMR: 4 branches/1000 carbon
atoms. DSC: T.sub.m=130.degree. C.
Example 64
[0301] A flame dried Schlenk flask was charged with complex D4 (2
mg, 0.0036 mmol), 1 atmosphere ethylene and 50 mL of toluene. The
flask was then placed in a water bath (23.degree. C.) to control
reaction temperatue. MAO (2 mL of a 10 wt. % solution in toluene)
was then added to the suspension and the reaction left to stir for
10 minutes (polymer began to precipitate within minutes). Acetone,
methanol and 6M HCl were added to quench the reaction and
precipitate the resulting polyethylene. The polymer was dried in a
vacuum oven resulting in 490 mg of polyethylene (30,000 TO/h). GPC:
M.sub.n=1600; M.sub.w=6100. .sup.1H NMR: 20 branches/1000 carbon
atoms DSC: T.sub.m=110.degree. C.
Example 65
[0302] The triazole/imine complex D15 (2.1 mg, 3.7 .mu.mol) was
suspended in dry toluene (100 mL) in a flame dried 500 mL round
bottom flask fitted with a gas adapter. The suspension was cooled
to 0.degree. C. in an ice bath and placed under an ethylene
atmosphere (1 atm). A 10% by weight solution of MAO in toluene (2
mL) was added to the polymerization flask. The resulting solution
was stirred vigorously under 1 atm ethylene at 0.degree. C. for 20
min, then quenched by sequential addition of acetone, MeOH, and HCl
(6 N). The resulting polymer was collected by vacuum filtration and
dried in vacuo to afford 1.034 g of polyethylene (29,900 TO/hr,
M.sub.n=8,190, M.sub.w=50,300 (GPC); 2 branches/1000 C's (.sup.1H
NMR)).
Example 66
[0303] The triazole/imine complex D16 (1.6 mg, 3.03 .mu.mol) was
suspended in dry toluene (100 mL) in a flame dried 500 mL round
bottom flask fitted with a gas adapter. The suspension was cooled
to 0.degree. C. in an ice bath and placed under an ethylene
atmosphere (1 atm). A 10% by weight solution of MAO in toluene (1.5
mL) was added to the polymerization flask. The resulting solution
was stirred vigorously under 1 atm ethylene at 0.degree. C. for 20
min, then quenched by sequential addition of acetone, MeOH, and HCl
(6 N). The resulting polymer was collected by vacuum filtration and
dried in vacuo to afford 0.338 g of polyethylene (12,000 TO/hr,
M.sub.n=12,300, M.sub.w=53,300 (GPC); 2 branches/1000 C's (.sup.1H
NMR)).
Example 67
[0304] The triazole/imine complex D17 (2.6 mg, 4.8 .mu.mol) was
suspended in dry toluene (100 mL) in a flame dried 500 mL round
bottom flask fitted with a gas adapter. The suspension was cooled
to 0.degree. C. in an ice bath and placed under an ethylene
atmosphere (1 atm). A 10% by weight solution of MAO in toluene (2.0
mL) was added to the polymerization flask The resulting suspension
was stirred vigorously under 1 atm ethylene at 0.degree. C. for 16
min, then quenched by sequential addition of acetone, MeOH, and HCl
(6N). The resulting polymer was collected by vacuum filtration and
dried in vacuo to afford a small amount of polyethylene.
Example 68
[0305] The triazole/imine complex D18 (16.6 mg) was suspended in
CH.sub.2Cl.sub.2 (16.6 mL). Toluene (50 mL) was charged to a flame
dried Schlenk flask under 1 atm ethylene and cooled to 0-4.degree.
C. in an ice bath. The toluene was stirred vigorously for 20 min,
then treated with a 10% by weight solution of MAO in toluene (4 mL)
and stirring continued for 5 min. The complex D18 suspension (2 mL)
was added, and the reaction was stirred vigorously under 1 atm of
ethylene in an ice water bath for 10.5 min. The reaction was
quenched by the sequential addition of MeOH, HCl (6N) and acetone.
The polyethylene was isolated by vacuum filtration and dried in a
vacuum oven to afford 2.4 g (135,000 TO/h) of polyethylene.
.sup.1Hnmr: (M.sub.n=4087; 7.5 branches/1000 carbons).
Example 69
[0306] The triazole/imine complex D18 (4.6 mg, 8.3 .mu.mol) was
suspended in CH.sub.2Cl.sub.2 (10 mL). Toluene (50 mL) was charged
to a flame dried Schlenk flask under 1 atm of ethylene. The toluene
was stirred vigorously under 1 atm ethylene for 10 min, then
treated with a 10% by weight solution of MAO in toluene (4 mL). The
complex suspension (1 mL, 0.46 mg, 0.83 .mu.mol) was added and the
resulting solution was stirred vigorously under 1 atm ethylene at
room temperature for 45 min, then quenched by sequential addition
of MeOH, acetone and 6 N HCl. The precipitated polymer was
collected by vacuum filtration and dried in vacuo at 80.degree. C.
overnight to afford 1.68 g of polyethylene (95,600 TO/h).
.sup.1Hnmr: (M.sub.n=2032; 8.4 branches/1000 carbons).
Example 70
[0307] A 600 mL Parr.RTM. autoclave was first heated to
.about.100.degree. C. under dynamic vacuum to ensure the reactor
was dry. The triazole/imine complex D18 (4.6 mg, 8.3 .mu.mol) was
suspended in CH.sub.2Cl.sub.2 (10 mL). Toluene (150 mL) and a 10%
by weight solution of MAO in toluene (4 mL) were added sequentially
to the reactor. The reactor was pressurized to 300 psig with
ethylene, then vented to ambient pressure. The above prepared
complex suspension (1.0 mL, 0.83 .mu.mol) was added and the reactor
was quickly pressurized to 300 psig ethylene. After 45 min at
24.degree. C. under 300 psig ethylene, the reactor was vented and
the reaction quenched by the addition 1 5 of acetone. The resulting
suspension was slurried with MeOH and 6N HCl, and the polymer was
isolated by vacuum filtration, then dried in vacuo at 80.degree. C.
overnight to afford 1.42 g of polyethylene (86,462 TO/h).
.sup.1Hnmr: (M.sub.n=3426; 1.9 branches/1000 carbons).
Example 71
[0308] The pyrazole/imine complex D19 (2.2 mg, 2.4 .mu.mol) was
suspended in toluene (50 mL) under I atm of ethylene in a flame
dried Schlenk flask immersed in a room temperature water bath. The
mixture was allowed to equilibrate under 1 atm ethylene for 10 min,
then a 10% by weight solution of MAO in toluene (4 mL) was added.
The reaction was stirred vigorously under 1 atm ethylene at rt for
29 min, then quenched by sequential addition of MeOH, 6N HCl and
acetone. The polymer was collected by vacuum filtration and dried
in vacuo overnight at 80.degree. C. to afford 600 mg of
polyethylene (9,100 TO/h). .sup.1Hnmr: (M.sub.n=3107; 28.6
branches/1000 carbons).
Example 72
[0309] The imine/pyrazole complex D19 (5.2 mg, 5.7 .mu.mol) was
suspended in toluene (50 mL) under 1 atm ethylene in a 200 mL flame
dried Schlenk flask immersed in an ice water bath. The mixture was
stirred vigorously under 1 atm ethylene at 0.degree. C. for 20 min,
then treated with a 10% by weight solution of MAO in toluene (4
mL). The resulting suspension was stirred vigorously under 1 atm
ethylene while warming to .about.10.degree. C. for 75 min. The
reaction was quenched by the sequential addition of MeOH and 6N
HCl. The precipitated polymer was isolated by vacuum filtration and
dried in vacuo at 80.degree. C. overnight to afford 1.22 g of
polyethylene (1700 TO/h). .sup.1H NMR: (M.sub.n=12649; 9.8
branches/1000 carbons).
Example 73
[0310] A 600 mL Parr.RTM. autoclave was first heated to
.about.100.degree. C. under dynamic vacuum to ensure the reactor
was dry. The pyrazole/imine complex D19 (7.5 mg, 8.25 .mu.mol) was
charged to the autoclave in an Ar filled glove box. Toluene (150
mL) was charged to the reactor under a stream of Ar. The autoclave
was rapidly pressurized to 800 psig ethylene. The pressure was
relieved to ambient pressure, and the reaction mixture was treated
with a 10% by weight solution of MAO in toluene (4 mL). The reactor
was immediately pressurized to 300 psig ethylene, and stirred
vigorously at 30.degree. C. for 120 min. The pressure was relieved,
and the reaction quenched with MeOH. The contents of the reactor
were slurried with MeOH, acetone and 6 N HCl. The polymer was
collected by vacuum filtration and dried in vacuo at 80.degree. C.
to afford 21.85 g of polyethylene (23,600 TO/h). .sup.1H NMR:
(M.sub.n=14024; 4.1 branches/1000 carbons).
Example 74
[0311] A 600 mL Parr.RTM. autoclave was first heated to
.about.100.degree. C. under dynamic vacuum to ensure the reactor
was dry. The pyrazole/imine complex D19 (7.2 mg, 7.9 .mu.mol) was
charged to the autoclave in an Ar filled glove box. Toluene (150
mL) was charged to the reactor under a stream of Ar. The autoclave
was rapidly pressurized to 200 psig ethylene. The pressure was
relieved to ambient pressure, and the reaction mixture was treated
with a 10% by weight solution of MAO in toluene (4 mL). The reactor
was immediately pressurized to 300 psig ethylene and heated to
45.degree. C. over 2 min. The reaction was stirred vigorously at
45.degree. C. for 90 min. The pressure was relieved, and the
reaction quenched with acetone. The contents of the reactor were
slurried with MeOH, acetone and 6 N HCl. The polymer was collected
by vacuum filtration and dried in vacuo at 80.degree. C. to afford
47.4 g of polyethylene (70,500 TO/h). .sup.1H NMR: (M.sub.n=5066;
9.2 branches/1000 carbons).
Example 75
[0312] A 600 mL Parr.RTM. autoclave was first heated to
.about.120.degree. C. under dynamic vacuum to ensure the reactor
was dry. A 1 mg/mL stock solution of imine/pyrazole complex D19 in
o-difluorobenzene was prepared. Toluene (150 mL) and a 10% by
weight solution of MAO in toluene (4 mL) were added sequentially to
the reactor. The reactor was pressurized to 150 psig ethylene, then
vented to ambient pressure The pressurization and venting was
repeated while the autoclave was heated to 51 .degree. C. The
reactor was pressurized to 150 psig ethylene, the above prepared
stock solution (2.0 mL, 2.2 .mu.mol) was injected and the reactor
heated to 60.degree. C. After 22 min at 60.degree. C. under 150
psig ethylene, the reactor was vented and the reaction quenched by
the addition of MeOH (2.times.2 mL). The resulting suspension was
slurried with MeOH, acetone and 6N HCl, and the polymer was
isolated by vacuum filtration, then dried in vacuo at 80.degree. C.
overnight to afford 11.9 g of polyethylene (257,000 TO/h). .sup.1H
NMR: (M.sub.n=1926; 19.5 branches/1000 carbons).
Example 76
[0313] A 600 mL Parr.RTM. autoclave was first heated to
.about.120.degree. C. under dynamic vacuum to ensure the reactor
was dry. A 1 mg/mL stock solution of imine/pyrazole complex D19 in
o-difluorobenzene was prepared. Toluene (1 50 mL) and a 10% by
weight solution of MAO in toluene (4 mL) were added sequentially to
the reactor. The reactor was pressurized to 300 psig ethylene, then
vented to ambient pressure while the autoclave was heated to
53.degree. C. The reactor was pressurized to 150 psig ethylene, the
above prepared stock solution (2.0 mL, 2.2 .mu.mol) was injected
and the reactor heated to 60.degree. C. and pressurized to 300 psig
ethylene. After 11 min at 60.degree. C. under 300 psig ethylene,
the reactor was vented and the reaction quenched by the addition of
MeOH (2.times.2 mL). The resulting suspension was slurried with
MeOH, acetone and 6N HCl, and the polymer was isolated by vacuum
filtration, then dried in vacuo at 80.degree. C. overnight to
afford 5.68 g of polyethylene (252,000 TO/h). .sup.1H NMR:
(M.sub.n=2024; 19.9branches/1000 carbons).
Example 77
[0314] A 600 mL Parr.RTM. autoclave was first heated to
.about.120.degree. C. under dynamic vacuum to ensure the reactor
was dry. A 1 mg/mL stock solution of imine/prazole complex D19 in
o-difluorobenzene was prepared. Toluene (150 mL) and a 10% by
weight solution of MAO in toluene (4 mL) were added sequentially to
the reactor. The reactor was pressurized to 150 psig ethylene, then
vented to ambient pressure. The reactor was pressurized to 150 psig
ethylene, the above prepared stock solution (2.0 mL, 2.2 .mu.mol)
was injected and the reactor heated to 60.degree. C. and
pressurized to 300 psig ethylene. After 33 min at 60.degree. C. and
300 psig ethylene, the reactor was vented and the reaction quenched
by the addition of MeOH (2.times.2 mL). The resulting suspension
was slurried with MeOH, acetone and 6N HCl, and the polymer was
isolated by vacuum filtration, then dried in vacuo at 80.degree. C.
overnight to afford 13.3 g of polyethylene (196,000 TO/h). .sup.1H
NMR (M.sub.n=2122; 17.9 branches/1000 carbons).
Example 78
[0315] A 600 mL Parr.RTM. autoclave was first heated to
.about.120.degree. C. under dynamic vacuum to ensure the reactor
was dry. A 0.5 mg/mL stock solution of imine/prazole complex D19 in
o-difluorobenzene was prepared. Toluene (230 mL) and a 10% by
weight solution of MAO in toluene (4 mL) were added sequentially to
the reactor. The reactor was pressurized to 300 psig ethylene, then
vented to ambient pressure. The reactor was pressurized to 150 psig
ethylene and heated to 57.degree. C., and the above prepared stock
solution (2.0 mL, 1.1 .mu.mol) was injected and the reactor heated
to 60.degree. C. and pressurized to 300 psig ethylene. After 66 min
at 60.degree. C. and 300 psig ethylene, the reactor was vented and
the reaction quenched by the addition of MeOH (2.times.2 mL). The
resulting suspension was slurried with MeOH acetone and 6N HCl, and
the polymer was isolated by vacuum filtration, then dried in vacuo
at 80.degree. C. overnight to afford 8.3 g of polyethylene (245.000
TO/h). .sup.1H NMR (M.sub.n=2652. 16.2 branches/1000 carbons)
Example 79
[0316] A 600 mL Parr.RTM. autoclave was first heated to
.about.120.degree. C. under dynamic vacuum to ensure the reactor
was dry. A 1.0 mg/mL stock solution of imine/prazole complex D19 in
o-difluorobenzene was prepared. Toluene (245 mL) was added, and the
reactor was heated to 80.degree. C. A 10% by weight solution of MAO
in toluene (4 mL) was added to the reactor under an Ar purge. The
reactor was pressurized to 300 psig ethylene, then vented to
ambient pressure. The reactor was pressurized to 150 psig ethylene
and the above prepared stock solution (2.0 mL, 2.2 .mu.mol) was
injected and the reactor pressurized to 300 psig ethylene. After 22
min at 80.degree. C. and 300 psig ethylene, the reactor was vented
and the reaction quenched by the addition of MeOH (2.times.2 mL).
The resulting suspension was slurried with 6N HCl, and the polymer
was isolated by vacuum filtration to afford 0.20 g of polyethylene.
The organic layer from the filtrate was concentrated in vacuo to
afford 0.50 g of polyethylene. .sup.1H NMR: (M.sub.n=3101; 23.7
branches/1000 carbons).
[0317] Supported Catalyst Polymerizations
Example 80
[0318] Polymerization of Ethylene Using the Supported Catalyst
Prepared in Example 46. A 600 mL Parr.RTM. autoclave was first
heated to about 100.degree. C. under dynamic vacuum to ensure the
reactor was dry. The reactor was then purged with argon. The 600 mL
Parr.RTM. autoclave was charged in the glove box with vacuum oven
dried NaCl (200 mg), the supported catalyst prepared in Example 46
(120 mg, 5.55 .mu.mol Ni) and an additional 103 mg NaCl The
autoclave was removed from the dry box, heated to 57.degree. C.
with stirring, then pressurized to 300 psig ethylene. After 1 hr at
57-60.degree. C. the pressure was relieved and the reaction
quenched in hot H.sub.2O then MeOH. The precipitated polymer was
isolated by vacuum filtration and dried in vacuo at 80.degree. C.
overnight to afford 0.82 g of polyethylene (5300 TO/h). .sup.1H
NMR: (M.sub.n=4902; 16.3 branches/1000 carbons).
Example 81
[0319] A 200 mL flame dried Schlenk flask was charged with the
supported catalyst prepared in example 47 (240 mg, 2.6 .mu.mol Ni)
in an Ar filled dry box. The flask was removed from the dry box and
immersed in an ice water bath under Ar. The flask was evacuated and
refilled with 1 atm of ethylene, then toluene (50 mL) was
immediately added. The resulting suspension was stirred vigorously
under 1 atm of ethylene at 0.degree. C. for 2 h 45 min. The
reaction was quenched by the sequential addition of MeOH and 6 N
HCl. The precipitated polymer was isolated by vacuum filtration and
dried in vacuo at 80.degree. C. to afford 1.046 g of polyethylene
(5,200 TO/h). .sup.1H NMR: (M.sub.n=12898; 3.7 branches/1000
carbons).
Example 82
[0320] A 200 mL flame dried Schlenk flask was charged with the
supported catalyst prepared in example 47 (199.5 mg, 2.2 .mu.mol
Ni) in an Ar filled dry box. The flask was removed from the dry box
and immersed in a room temperature water bath under Ar. The flask
was evacuated and refilled with 1 atm of ethylene, then toluene (50
mL) was immediately added. The resulting suspension was stirred
vigorously under 1 atm of ethylene at rt for 2 h 40 min. The
reaction was quenched by the sequential addition of MeOH and 6 N
HCl. The precipitated polymer was isolated by vacuum filtration and
dried in vacuo at 80.degree. C. to afford 1.018 g of polyethylene
(6.200 TO/h). .sup.1H NMR: (M.sub.n=10615, 5.5 branches/1000
carbons).
Example 83
[0321] Polymerization of Ethylene Using the Supported Catalyst
Prepared in Example 47. A 600 mL Parr.RTM. autoclave was first
heated to about 100.degree. C. under dynamic vacuum to ensure the
reactor was dry. The reactor was then purged with argon. The 600 mL
Parr.RTM. autoclave was charged in the glove box with vacuum oven
dried NaCl (300 mg) and the supported catalyst prepared in Example
47 (100 mg, 1.09 .mu.mol Ni). The autoclave was removed from the
dry box then pressurized to 800 psig ethylene. After stirring 40
min at 23.degree. C. and 800 psig ethylene, the pressure was
relieved and the reaction quenched in hot H.sub.2O. The
precipitated polymer was isolated by vacuum filtration and dried in
vacuo at 80.degree. C. overnight to afford 0.328 g of polyethylene
(16,120 TO/h). .sup.1H NMR: (M.sub.n=10189; 5.5 branches/1000
carbons).
Example 84
[0322] Polymerization of Ethylene Using the Supported Catalyst
Prepared in Example 47. A 600 mL Parr.RTM. autoclave was first
heated to about 100 .degree. C. under dynamic vacuum to ensure the
reactor was dry. The reactor was then purged with argon. The 600 mL
Parr.RTM. autoclave was charged in the glove box with vacuum oven
dried NaCl (300 mg) and the supported catalyst prepared in Example
47 (199 mg, 2.2 .mu.mol Ni). The autoclave was removed from the dry
box then pressurized to 800 psig ethylene. After stirring 22 min at
24.degree. C. and 800 psig ethylene, the pressure was relieved and
the reaction quenched in hot H.sub.2O. The precipitated polymer was
isolated by vacuum filtration and dried in vacuo at 80.degree. C.
overnight to afford 0 552 g of polyethylene (24,440 TO/h). .sup.1H
NMR (M.sub.n=4838; 6.1 branches/1000 carbons).
[0323] Ligand Synthesis
Example 85
[0324] This example illustrates the preparation of a compound IV
having the formula: 35
[0325] for use in a catalyst system according to the present
invention. 2-Thiazolecarboxylic acid (0.1 mol) is reacted with
1,1-carbonyldiimidazole (0.1 mol) and 2,6-diisopropylaniline (0.1
mol) to obtain the corresponding amide. This is reacted with
Lawesson's reagent to form the thioamide, which is treated with Mel
and base to give compound IV.
[0326] Synthesis of the Metal Complex
Example 86
[0327] This example illustrates the synthesis of a metal complex
having the formula V: 36
[0328] wherein: Ar 2,6-diisopropylphenyl.
[0329] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum is charged with 0.2 mmol of compound IV from
example 85 and 0.2 mmol (1,2-dimethoxyethane)nickel(II) dibromide
(Aldrich) under an inert atmosphere. Dry, deoxygenated
dichloromethane (5 mL) is added and the mixture is stirred under an
argon atmosphere, slowly preparing a crystalline precipitate. After
1 h, another 5 mL dichloromethane is added The mixture is stirred
another 21 h at 21.degree. C., then diluted with 10 mL dry,
deoxygenated hexane and stirred another 8 h. The supernatant is
removed via a filter paper-tipped cannula, and the residue dried in
vacuo at 1 mm Hg to afford complex V.
[0330] Olefin Polymerization
Example 87
[0331] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum is charged with 10 mg of compound
V. The flask is evacuated and refilled with ethylene, then charged
with 75 mL dry. deoxygenated toluene. The resultant suspension is
cooled to 0.degree. C. and allowed to equilibrate with 1 atm
ethylene for 15 min, then treated with 4.0 mL of a 10 wt % solution
of MAO in toluene (Aldrich) and stirred under 1 atm ethylene. After
60 minutes, the reaction is quenched by the addition of methanol,
acetone and 6 N aqueous HCl to produce a polyethylene
precipitate.
[0332] Ligand Synthesis
Example 88
[0333] This example illustrates the preparation of a compound VI
having the formula: 37
[0334] wherein:
[0335] Ar=2,6-diisopropylphenyl, for use in a catalyst system
according to the present invention.
[0336] Thiophosgene (0.1 mol) is reacted with 1,2,4-triazole (0.2
mol) and base to afford thiocarbonylditriazole. This is heated with
2,6-diisopropylaniline (0.1 mol) to obtain the mixed thiourea,
which is treated with Mel (methyl-iodine) and base to give compound
VI.
[0337] Synthesis of the Metal Complex
Example 89
[0338] This example illustrates the synthesis of a metal complex
having the formula VII: 38
[0339] wherein:
[0340] Ar=2,6-diisopropylphenyl.
[0341] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum is charged with 0.2 mmol of compound VI from
example 88 and 0.2 mmol (1,2-dimethoxyethane)nickel(III) dibromide
(Aldrich) under an inert atmosphere. Dry, deoxygenated
dichloromethane (5 mL) is added and the mixture is stirred under an
argon atmosphere, slowly preparing a crystalline precipitate. After
1 hour, another 5 mL dichloromethane is added. The mixture is
stirred another 21 hour at 21.degree. C., then diluted with 10 mL
dry, deoxygenated hexane and stirred another 8 hour. The
supernatant is removed via a filter paper-tipped cannula, and the
residue dried in vacuo at 1 mm Hg to afford compound VII.
[0342] Olefin Polymerization
Example 90
[0343] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum is charged with 10 mg of compound
VII from example 89. The flask is evacuated and refilled with
ethylene, then charged with 75 mL dry, deoxygenated toluene. The
resultant suspension is cooled to 0.degree. C. and allowed to
equilibrate with 1 atm ethylene for 15 min, then treated with 4.0
mL of a 10 wt % solution of MAO in toluene (Aldrich) and stirred
under 1 atm ethylene. After 60 minutes, the reaction is quenched by
the addition of methanol, acetone and 6 N aqueous HCl to produce a
polyethylene precipitate.
[0344] Ligand Synthesis 39
[0345] E1: R.sup.6=Me, R.sup.7S
[0346] E2: R.sup.6=H, R.sup.7=N(H)
Example 91
[0347] Synthesis of E1
[0348] A cooled solution of 2-acetylthiazole (4 mmol) and
2,6-diisopropylaniline (12 mmol) in toluene (15 mL) is treated with
TiCl.sub.4 (2.0 mL of 1.0 M solution in toluene), immediately
yielding an olive green precipitate. After allowing the reaction to
warm to room temperature, stirring is continued for 72 hours before
the reaction contents are filtered through alumina, rinsing with
ethyl acetate. The filtrate is washed sequentially with 0.6 M HCl,
saturated sodium bicarbonate, and brine, then dried over magnesium
sulfate, filtered, and concentrated to afford E1 as a yellow
solid
Example 92
[0349] Synthesis of E2
[0350] 2-Imidazolecarboxaldehyde (2.9 mmol) is added to a solution
of diisopropylaniline (2.9 mmol) in ethanol (10 mL). The reaction
is refluxed for 4 hours, then concentrated to a small volume, taken
up in ethyl acetate, and washed. Removal of solvent by rotary
evaporation gives an oil that crystallized over time, is isolated
by filtration, washed, and used without further purification.
[0351] Synthesis of the Metal Complex 40
[0352] F1: R.sup.6=Me, R.sup.7=S
[0353] F2: R.sup.6=H, R.sup.7=N(H)
Example 93
[0354] Synthesis of F1.
[0355] A molar excess of thiazole/imine E1, from Example 91, and
(DME)NiBr.sub.2 are combined as solids in an inert atmosphere glove
box, then removed from the glove box and treated with dry
CH.sub.2Cl.sub.2. The suspension immediately develops a deep
orange/brown color and is stirred overnight at room temperature.
The solvent is evaporated under a stream of argon, and the
precipitated solid is washed several times with hexane and
hexane/methylene chloride before being dried in vacuo to give the
pre-catalyst F1 as an orange/brown powder.
Example 94
[0356] Synthesis of F2.
[0357] Methylene chloride (10 mL) is added to a mixture of crude
imidazole/imine E2 (100 mg), from example 92, and (DME)NiBr.sub.2
(27 mg) The suspension gradually develops a bright green color,
then appears to darken somewhat. After stirring overnight, the
solvent is evaporated under a stream of argon, and the precipitated
solid is washed several times with hexane and hexane/methylene
chloride before being dried in vacuo to give the pre-catalyst F2 as
a yellow-green powder.
[0358] Olefin Polymerization
Example 95
[0359] The thiazole/imine complex F1 (12 mg), from Example 93, is
suspended in 20 mL of dry toluene. The reaction mixture is cooled
to 0.degree. C. and equilibrated under an ethylene atmosphere, then
treated with MAO (1.8 mL of a 10% by weight solution in toluene)
and stirred under 1 atm ethylene for 30 minutes. The reaction is
quenched by the sequential addition of acetone, methanol, and 6M
HCl. The precipitated polyethylene is isolated by filtration,
washed, and dried in vacuo.
Example 96
[0360] Polymerization of ethylene with catalyst system IV. 41
[0361] A 500 mL round bottom flask equipped with a magnetic stir
bar, and a side-arm adapter with a Kontes high vacuum valve and a
24/40 septum, is flame-dried under vacuum (0.3 mm Hg), then (in the
glovebox) charged with 10.0 mg of the ligand IV, 5.0 mg
Ni(1,5-cyclooctadiene).sub.2 (Aldrich) and 106 mg
B(C.sub.6F.sub.5).sub.3 (Strem). On the Schlenk line, the flask is
evacuated and refilled with ethylene, then charged with 100 mL dry,
deoxygenated toluene while being stirred at 21.degree. C. After 30
min., the reaction is quenched by the addition of MeOH and acetone.
The white flocculent polyethylene which separates is isolated by
vacuum filtration and dried in vacuo (0.4 mm Hg, 6 h) to yield
polyethylene.
[0362] Synthesis of Supported Catalyst
Example 97
[0363] Synthesis of the Supported Nickel Complex D3. A flame dried
Schlenk flask was charged with the imine/triazole complex D3 (15.5
mg, 31.2 ,.mu.mol) and MAO treated silica (0.509 g, purchased from
Witco TA 02794/HL/04) in an Ar filled dry box. The flask was
immersed in an ice water bath under Ar, then CH.sub.2Cl.sub.2 (15
mL) was added. The resulting suspension was stirred at 0.degree. C.
for 1 hour then the solvent was removed via filter paper-tipped
cannula and then in vacuo at 0.degree. C. to afford supported
D3.
[0364] Polymerization
Example 98
[0365] A 500 mL flame dried round bottom flask fitted with a gas
adapter was charged with the supported catalyst prepared in example
97 (152 mg 9.2 .mu.mol Ni) in an Ar filled dry box. The flask was
removed from the dry box and evacuated and refilled with 1 atm of
ethylene, then toluene (100 mL) was immediately added. The
resulting suspension was stirred vigorously under 1 atm of ethylene
at room temperature for 2 h 15 min. The reaction was quenched by
the sequential addition of acetone, MeOH and 6 N HCl. The
precipitated polymer was isolated by vacuum filtration, washed a
second time with HCl/MeOH, filtered and dried in vacuo at
80.degree. C. to afford 0.871 g of polyethylene (1,500 TO/h). GPC:
M.sub.n=4,570, M.sub.w=123,000; .sup.1H NMR: (M.sub.n=4,936; 7.6
branches/1000 carbons).
[0366] The invention has been described above in detail with
particular reference to preferred embodiments thereof, but it will
be understood that variations and modifications other than as
specifically described herein can be effected within the spirit and
scope of the invention. Moreover, all patents and literature
references or other references herein are hereby incorporated by
reference.
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