U.S. patent application number 09/863721 was filed with the patent office on 2001-10-25 for organo-lewis acids of enhanced utility, uses thereof, and products based thereon.
Invention is credited to Chen, You-Xian, Marks, Tobin J..
Application Number | 20010034424 09/863721 |
Document ID | / |
Family ID | 46256497 |
Filed Date | 2001-10-25 |
United States Patent
Application |
20010034424 |
Kind Code |
A1 |
Marks, Tobin J. ; et
al. |
October 25, 2001 |
Organo-lewis acids of enhanced utility, uses thereof, and products
based thereon
Abstract
The organo-Lewis acids are novel triarylboranes which are are
highly fluorinated. Triarylboranes of one such type contain at
least one ring substituent other than fluorine. These organoboranes
have a Lewis acid strength essentially equal to or greater than
that of the corresponding organoborane in which the substituent is
replaced by fluorine, or have greater solubility in organic
solvents. Another type of new organoboranes have 1-3 perfluorinated
fused ring groups and 2-0 perfluorophenyl groups. When used as a
cocatalyst in the formation of novel catalytic complexes with d- or
f-block metal compounds having at least one leaving group such as a
methyl group, these triorganoboranes, because of their ligand
abstracting properties, produce corresponding anions which are
capable of only weakly, if at all, coordinating to the metal
center, and thus do not interfere in various polymerization
processes such as are described.
Inventors: |
Marks, Tobin J.; (Evanston,
IL) ; Chen, You-Xian; (Midland, MI) |
Correspondence
Address: |
SIEBERTH & PATY, L.L.C.
2924 BRAKLEY DRIVE, SUITE A-1
BATON ROUGE
LA
70816
US
|
Family ID: |
46256497 |
Appl. No.: |
09/863721 |
Filed: |
May 23, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09863721 |
May 23, 2001 |
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09329765 |
Jun 10, 1999 |
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09329765 |
Jun 10, 1999 |
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09220741 |
Dec 23, 1998 |
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6087460 |
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09220741 |
Dec 23, 1998 |
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08800548 |
Feb 18, 1997 |
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5856256 |
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60011920 |
Feb 20, 1996 |
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Current U.S.
Class: |
526/126 ;
502/152; 502/155; 526/134; 526/170; 526/317.1; 526/319; 526/346;
568/1 |
Current CPC
Class: |
B01J 2531/46 20130101;
B01J 31/1608 20130101; C07F 17/00 20130101; B01J 31/146 20130101;
C08F 10/00 20130101; Y10S 526/943 20130101; B01J 2531/49 20130101;
B01J 31/2295 20130101; C08F 10/00 20130101; C08F 4/61908 20130101;
C08F 4/52 20130101; B01J 2531/48 20130101; C08F 4/61908 20130101;
C08F 4/6592 20130101; C08G 65/20 20130101; B01J 2531/39 20130101;
C08F 10/00 20130101; C08G 65/12 20130101 |
Class at
Publication: |
526/126 ;
526/134; 526/170; 526/317.1; 526/319; 526/346; 502/152; 502/155;
568/1 |
International
Class: |
C08F 004/44 |
Goverment Interests
[0002] This invention was made with Government support under
Contract No. DE-FG02-86ER13511 awarded by the Department of Energy.
The Government has certain rights in this invention.
Claims
What is claimed is:
1. An organoborane represented by the formula:
BR'.sub.nR".sub.3-nwherein R' is a fluoroaryl group having at least
one additional substituent other than fluorine, wherein each R" is,
independently, (i) a fluoroaryl group having at least one
additional substituent other than fluorine, or (ii) a fluorinated
aryl group devoid of additional substitution, and n is 1 or 2.
2. An organoborane of claim 1 wherein n is 1, and both R" groups
are the same as each other.
3. An organoborane of claim 2 wherein both R" groups are fluoroaryl
groups having at least one additional substituent other than
fluorine.
4. An organoborane of claim 3 wherein R' and both R" groups are all
the same as each other.
5. An organoborane of claim 1 wherein n is 2, and wherein the two
R' groups are the same as each other.
6. An organoborane of claim 1 wherein n is 1, and wherein the two
R" groups are the same as each other and differ from R'.
7. An organoborane of claim 1 having the formula: 9wherein R is a
substituent other than a fluorine atom, and x is from 1 to 3.
8. An organoborane of claim 1 having the formula: 10wherein each R
is, independently, a substituent other than a fluorine atom, and x
is from 1 to 3.
9. An organoborane of claim 1 wherein said organoborane is a Lewis
acid of a strength essentially equivalent to or greater than that
of the corresponding organoborane in which each substituent other
than fluorine is replaced by a fluorine atom.
10. An organoborane of claim 1 wherein said organoborane has a
greater solubility in n-hexane at 20.degree. C. than that of the
corresponding organoborane in which each substituent other than
fluorine is replaced by a fluorine atom.
11. An organoborane represented by the formula:
B(R.sup.1).sub.n(R.sup.2).- sub.3-nwherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic or is partially aromatic
and partially cycloaliphatic, and wherein each R.sup.2 is a
pentafluorophenyl group, and wherein n is 1 to 3.
12. An organoborane of claim 11 wherein said compound is:
tris(nonafluoroanthracenyl)borane,
bis(nonafluoroanthracenyl)(pentafluoro- phenyl)borane, or
(nonafluoroanthracenyl)bis(pentafluorophenyl)borane.
13. An organoborane of claim 11 wherein said compound is:
tris(undecafluorotetrahydronaphthyl)borane,
bis(undecafluorotetrahydronap- hthyl)(pentafluorophenyl)borane, or
undecafluorotetrahydronaphthylbis(pent- afluorophenyl)borane.
14. An organoborane of claim 11 wherein said compound is:
tris(nonafluorofluorenyl)borane,
bis(nonafluorofluorenyl)(pentafluorophen- yl)borane, or
nonafluorofluorenylbis(pentafluorophenyl)borane.
15. A composition comprising a solution of an organoborane of any
of claims 1-14 in a nonpolar solvent.
16. A composition comprising an organoborane supported on a
catalyst support material, said organoborane being a
triorganoborane selected from those of set forth in A), or in B) or
in C) as follows: A) an organoborane represented by the formula:
BR'.sub.nR".sub.3-nwherein R' is a fluoroaryl group having at least
one additional substituent other than fluorine, wherein each R" is,
independently, (i) a fluoroaryl group having at least one
additional substituent other than fluorine, or (ii) a fluorinated
aryl group devoid of additional substitution, and n is 1 or 2; B)
an organoborane represented by the formula: BR'R".sub.2wherein R'
is a fluorinated biphenyl group having no more than two hydrogen
atoms thereon, and R" is (i) a fluorinated biphenyl group having no
more than two hydrogen atoms thereon, (ii) a fluorinated polycyclic
fused ring group having no more than two hydrogen atoms thereon, or
(iii) a phenyl group having no more than two hydrogen atoms
thereon; C) an organoborane represented by the formula:
B(R.sup.1).sub.n(R.sup.2).sub.3-nwherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic or is partially aromatic
and partially cycloaliphatic, wherein each R.sup.2 is a
pentafluorophenyl group, and wherein n is 1 to 3.
17. A composition of claim 16 wherein said triorganoborane is an
organoborane selected from A).
18. A composition of claim 16 wherein said triorganoborane is a
perfluorinated organoborane selected from B).
19. A composition of claim 18 wherein said triorganoborane is
nonafluorobiphenylbis(pentafluorophenyl)borane.
20. A composition of claim 18 wherein said triorganoborane is
tris(perfluorobiphenyl)borane.
21. A composition of claim 16 wherein said triorganoborane is an
organoborane selected from C).
22. A composition of any of claims 16-21 wherein the catalyst
support material consists essentially of an inorganic oxide.
23. A composition of any of claims 16-21 wherein the catalyst
support material consists essentially of porous silica.
24. A complex which comprises a cation formed from a d-block or
f-block metal compound by loss of a leaving group and an anion
formed by transfer of the leaving group to an organoborane of the
formula: BR'.sub.nR".sub.3-nwherein R' is a fluoroaryl group having
at least one additional substituent other than fluorine, wherein
each R" is, independently, (i) a fluoroaryl group having at least
one additional substituent other than fluorine, or (ii) a
fluorinated aryl group devoid of additional substitution, and n is
1 or 2.
25. A complex of claim 24 wherein the metal of said metal compound
is a metal from Groups 4 to 8 of the Periodic Table.
26. A complex of claim 24 wherein the metal of said metal compound
is thorium, titanium, zirconium, or hafnium.
27. A complex of claim 24 wherein said metal compound is a
metallocene represented by the formula:
Q.sub.aCp.sub.bML.sub.cX.sub.dwhere Cp independently in each
occurrence is a cyclopentadienyl-moiety-containing group which has
in the range of 5 to about 24 carbon atoms; Q is a bridging group
or ansa group that links two Cp groups together; M is a d- or
f-block metal atom; each L is, independently, a leaving group that
is bonded to the d-or f-block metal atom and is capable of being
abstracted by the triorganoborane used in forming the catalytic
complex; X is a group other than a leaving group that is bonded to
the d- or f-block metal atom and that does not detrimentally affect
propagation of a polymer chain during polymerization; a is 0 or 1;
b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the
sum of c and d is at least 2.
28. A complex of claim 27 wherein M is a Group 4 metal atom,
wherein a is 0, wherein b is 1, and the sum of c and d is 3.
29. A complex of claim 27 wherein M is a Group 4 metal atom,
wherein b is 2 and the sum of c and d is 2.
30. A complex of claim 24 wherein said metal compound is a
metallocene represented by the formula: 11wherein M is a metal of
Group 3 (other than scandium), Groups 4-10, or the lanthanide
series; L is a group containing a cyclic, delocalized, anionic,
pi-system through which the group is bound to M, and which group is
also bound to Z; Z is a moiety comprising boron, or a member of
Group 14 of the Periodic Table, and optionally sulfur or oxygen,
this moiety having up to about 20 non-hydrogen atoms; Y is an
anionic or nonanionic ligand group bonded to Z and M comprising
nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20
non-hydrogen atoms; R is a leaving group; X is a non-leaving group
that does not detrimentally affect propagation of a polymer chain
during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n
plus m being 1 to 4 depending upon the valence of M.
31. A complex of claim 30 wherein M is a titanium, zirconium or
hafnium atom, L is a cyclopentadienyl group or a substituted
cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a
hydrocarbylamido group, R is methyl, n is 2, and m is 0.
32. A complex of claim 30 wherein M is a titanium or zirconium
atom, L is a tetramethylcyclopentadienyl group, Z is a
dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n
is 2, and m is 0.
33. A complex of claim 24 wherein said organoborane is a Lewis acid
of a strength essentially equivalent to or greater than that of the
corresponding organoborane in which each substituent other than
fluorine is replaced by a fluorine atom.
34. A complex of claim 24 wherein said organoborane has a greater
solubility in n-hexane at 20.degree. C. than that of the
corresponding organoborane in which each substituent other than
fluorine is replaced by a fluorine atom.
35. A complex of claim 24 wherein said organoborane has the
formula: 12wherein R is a substituent other than a fluorine atom,
and x is from 1 to 3.
36. A complex of claim 24 wherein said organoborane has the
formula: 13wherein each R is, independently, a substituent other
than a fluorine atom, and x is from 1 to 3.
37. A complex of claim 24 wherein at least one said additional
univalent substituent of said organoborane is an electron
withdrawing substituent.
38. A complex of claim 24 wherein at least one said additional
univalent substituent of said organoborane is a
solubility-enhancing substituent.
39. A complex which comprises a cation formed from a d-block or
f-block metal compound by loss of a leaving group and an anion
formed by transfer of the leaving group to an organoborane of the
formula: B(R.sup.1).sub.n(R.sup.2).sub.3-nwherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic or is partially aromatic
and partially cycloaliphatic, wherein each R.sup.2 is a
pentafluorophenyl group, and wherein n is 1 to 3.
40. A complex of claim 39 wherein the metal of said metal compound
is a metal from Groups 4 to 8 of the Periodic Table.
41. A complex of claim 39 wherein the metal of said metal compound
is thorium, titanium, zirconium, or hafnium.
42. A complex of claim 39 wherein said metal compound is a
metallocene represented by the formula:
Q.sub.aCp.sub.bML.sub.cX.sub.dwhere Cp independently in each
occurrence is a cyclopentadienyl-moiety-containing group which has
in the range of 5 to about 24 carbon atoms; Q is abridging group or
ansa group that links two Cp groups together; M is a d- or f-block
metal atom; each L is, independently, a leaving group that is
bonded to the d-or f-block metal atom and is capable of being
abstracted by the triorganoborane used in forming the catalytic
complex; X is a group other than a leaving group that is bonded to
the d- or f-block metal atom and that does not detrimentally affect
propagation of a polymer chain during polymerization; a is 0 or 1;
b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the
sum of c and d is at least 2.
43. A complex of claim 42 wherein M is a Group 4 metal atom,
wherein a is 0, wherein b is 1, and the sum of c and d is 3.
44. A complex of claim 42 wherein M is a Group 4 metal atom,
wherein b is 2 and the sum of c and d is 2.
45. A complex of claim 39 wherein said metal compound is a
metallocene represented by the formula: 14wherein M is a metal of
Group 3 (other than scandium), Groups 4-10, or the lanthanide
series; L is a group containing a cyclic, delocalized, anionic,
pi-system through which the group is bound to M, and which group is
also bound to Z; Z is a moiety comprising boron, or a member of
Group 14 of the Periodic Table, and optionally sulfur or oxygen,
this moiety having up to about 20 non-hydrogen atoms; Y is an
anionic or nonanionic ligand group bonded to Z and M comprising
nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20
non-hydrogen atoms; R is a leaving group; X is a non-leaving group
that does not detrimentally affect propagation of a polymer chain
during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n
plus m being 1 to 4 depending upon the valence of M.
46. A complex of claim 45 wherein M is a titanium, zirconium or
hafinium atom, L is a cyclopentadienyl group or a substituted
cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a
hydrocarbylamido group, R is methyl, n is 2, and m is 0.
47. A complex of claim 45 wherein M is a titanium or zirconium
atom, L is a tetramethylcyclopentadienyl group, Z is a
dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n
is 2, and m is 0.
48. A complex of claim 39 wherein said organoborane is
tris(nonafluoroanthracenyl)borane,
bis(nonafluoroanthracenyl)(pentafluoro- phenyl)borane, or
(nonafluoroanthracenyl)bis(pentafluorophenyl)borane.
49. A complex of claim 39 wherein said organoborane is
tris(undecafluorotetrahydronaphthyl)borane,
bis(undecafluorotetrahydronap- hthyl)(pentafluorophenyl)borane, or
undecafluorotetrahydronaphthylbis(pent- afluorophenyl)borane.
50. A complex of claim 39 wherein said organoborane is
tris(nonafluorofluorenyl)borane,
bis(nonafluorofluorenyl)(pentafluorophen- yl)borane, or
nonafluorofluorenylbis(pentafluorophenyl)borane.
51. A process for preparing a catalytic complex or ion pair, which
process comprises contacting a d-block or f-block metal compound
having at least one leaving group with an organoborane of the
formula: BR'.sub.nR".sub.3-nwherein R' is a fluoroaryl group having
at least one additional substituent other than fluorine, each R"
is, independently, (i) a fluoroaryl group having at least one
additional substituent other than fluorine, or (ii) a fluorinated
hydrocarbyl group devoid of additional substitution, and n is 1 or
2 in a suitably anhydrous liquid medium and in a suitably inert
atmosphere or environment, such that a leaving group is abstracted
from the d-block or f-block metal compound and becomes unified with
the organoborane to produce the catalytic complex.
52. A process for preparing a catalytic complex or ion pair, which
process comprises contacting a d-block or f-block metal compound
having at least one leaving group with an organoborane of the
formula: B(R.sup.1).sub.n(R.sup.2).sub.3-nwherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic, or is partially aromatic
and partially cycloaliphatic, wherein each R.sup.2 is a
pentafluorophenyl group, and wherein n is 1 to 3.
53. A process of claim 51 or 52 wherein said metal compound is a
metallocene represented by the formula:
Q.sub.aCp.sub.bML.sub.cX.sub.dwhe- re Cp independently in each
occurrence is a cyclopentadienyl-moiety-contai- ning group which
has in the range of 5 to about 24 carbon atoms; Q is a bridging
group or ansa group that links two Cp groups together; M is a d- or
f-block metal atom; each L is, independently, a leaving group that
is bonded to the d-or f-block metal atom and is capable of being
abstracted by the triorganoborane used in forming the catalytic
complex; X is a group other than a leaving group that is bonded to
the d- or f-block metal atom and that does not detrimentally affect
propagation of a polymer chain during polymerization; a is 0 or 1;
b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the
sum of c and d is at least 2.
54. A process of claim 53 wherein M is a Group 4 metal atom,
wherein a is 0, wherein b is 1, and the sum of c and d is 3.
55. A process of claim 53 wherein M is a Group 4 metal atom,
wherein b is 2 and the sum of c and d is 2.
56. A process of claim 51 or 52 wherein said metal compound is a
metallocene represented by the formula: 15wherein M is a metal of
Group 3 (other than scandium), Groups 4-10, or the lanthanide
series; L is a group containing a cyclic, delocalized, anionic,
pi-system through which the group is bound to M, and which group is
also bound to Z; Z is a moiety comprising boron, or a member of
Group 14 of the Periodic Table, and optionally sulfur or oxygen,
this moiety having up to about 20 non-hydrogen atoms; Y is an
anionic or nonanionic ligand group bonded to Z and M comprising
nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20
non-hydrogen atoms; R is a leaving group; X is a non-leaving group
that does not detrimentally affect propagation of a polymer chain
during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n
plus m being 1 to 4 depending upon the valence of M.
57. A process of claim 56 wherein M is a titanium, zirconium or
hafnium atom, L is a cyclopentadienyl group or a substituted
cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a
hydrocarbylamido group, R is methyl, n is 2, and m is 0.
58. A process of claim 56 wherein M is a titanium or zirconium
atom, L is a tetramethylcyclopentadienyl group, Z is a
dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n
is 2, and m is 0.
59. A process for polymerizing a polymerizable olefinic monomer or
copolymerizing two or more copolymerizable olefinic monomers, which
process comprises contacting said monomer or monomers with a
polymerization catalyst complex which comprises a cation formed
from a d-block or f-block metal compound by abstraction therefrom
of a leaving group, and an anion formed by unification of the
leaving group with an organoborane of the formula:
BR'.sub.nR".sub.3-nwherein R' is a fluoroaryl group having at least
one additional substituent other than fluorine, wherein each R" is,
independently, (i) a fluoroaryl group having at least one
additional substituent other than fluorine, or (ii) a fluorinated
hydrocarbyl group devoid of additional substitution, and wherein n
is 1 or 2.
60. A process for polymerizing a polymerizable olefinic monomer or
copolymerizing two or more copolymerizable olefinic monomers, which
process comprises contacting said monomer or monomers with a
polymerization catalyst complex which comprises a cation formed
from a d-block or f-block metal compound by abstraction therefrom
of a leaving group, and an anion formed by unification of the
leaving group with an organoborane of the formula:
B(R.sup.1).sub.n(R.sup.2).sub.3-nwherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic, or is partially aromatic
and partially cycloaliphatic, and wherein each R.sup.2 is a
pentafluorophenyl group, and wherein n is 1 to 3.
61. A process of claim 59 or 60 wherein said metal compound is a
metallocene represented by the formula:
Q.sub.aCp.sub.bML.sub.cXwhere Cp independently in each occurrence
is a cyclopentadienyl-moiety-containing group which has in the
range of 5 to about 24 carbon atoms; Q is abridging group or ansa
group that links two Cp groups together; M is a d- or f-block metal
atom; each L is, independently, a leaving group that is bonded to
the d-or f-block metal atom and is capable of being abstracted by
the triorganoborane used in forming the catalytic complex; X is a
group other than a leaving group that is bonded to the d- or
f-block metal atom and that does not detrimentally affect
propagation of a polymer chain during polymerization; a is 0 or 1;
b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the
sum of c and d is at least 2.
62. A process of claim 61 wherein M is a Group 4 metal atom,
wherein a is 0, wherein b is 1, and the sum of c and d is 3.
63. A process of claim 61 wherein M is a Group 4 metal atom,
wherein b is 2 and the sum of c and d is 2.
64. A process of claim 59 or 60 wherein said metal compound is a
metallocene represented by the formula: 16wherein M is a metal of
Group 3 (other than scandium), Groups 4-10, or the lanthanide
series; L is a group containing a cyclic, delocalized, anionic,
pi-system through which the group is bound to M, and which group is
also bound to Z; Z is a moiety comprising boron, or a member of
Group 14 of the Periodic Table, and optionally sulfur or oxygen,
this moiety having up to about 20 non-hydrogen atoms; Y is an
anionic or nonanionic ligand group bonded to Z and M comprising
nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20
non-hydrogen atoms; R is a leaving group; X is a non-leaving group
that does not detrimentally affect propagation of a polymer chain
during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n
plus m being 1 to 4 depending upon the valence of M.
65. A process of claim 64 wherein M is a titanium, zirconium or
hafnium atom, L is a cyclopentadienyl group or a substituted
cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a
hydrocarbylamido group, R is methyl, n is 2, and m is 0.
66. A process of claim 64 wherein M is a titanium or zirconium
atom, L is a tetramethylcyclopentadienyl group, Z is a
dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n
is 2, and m is 0.
67. A process of claim 59 or 60 wherein said monomer or monomers
comprise(s) a 1-olefin, a vinylaromatic monomer, or an ester of
acrylic or methacrylic acid.
Description
REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of prior copending
application Ser. No. 09/329,765, filed Jun. 10, 1999, which is a
continuation-in-part of application Ser. No. 09/220,741, filed Dec.
23, 1998, which is a division of application Ser. No. 08/800,548,
filed Feb. 18, 1997, now U.S. Pat. No. 5,856,256, issued Jan. 5,
1999, which in turn claims the benefit of U.S. provisional
application No. 60/011,920, filed Feb. 20, 1996. Reference is also
made to commonly-owned U.S. application Ser. No. 09/329,431, filed
Jun. 10, 1999.
BACKGROUND OF THE INVENTION
[0003] This invention relates, inter alia, to novel compositions of
matter useful, inter alia, as cocatalysts, to novel catalyst
compositions made using such cocatalysts, to methods for preparing
these catalysts, and to methods for polymerization utilizing the
catalysts.
[0004] The use of soluble Ziegler-Natta type catalysts in the
polymerization of olefins is well known in the prior art. In
general, such systems include a Group 4 metal compound and a metal
or metalloid alkyl cocatalyst, such as aluminum alkyl cocatalyst.
More broadly, it may be said to include a mixture of a Group 1, 2
or 13 metal alkyl and a transition metal complex from Group 4-5
metals, particularly titanium, zirconium, or hafnium with aluminum
alkyl cocatalysts.
[0005] First generation cocatalyst systems for homogeneous
metallocene Ziegler-Natta olefin polymerization, alkylaluminum
chlorides (AlR.sub.2Cl), exhibit low ethylene polymerization
activity levels and no propylene polymerization activity. Second
generation cocatalyst systems, utilizing methyl aluminoxane (MAO),
raise activities by several orders of magnitude. In practice
however, a large stoichiometric excess of MAO over catalyst ranging
from several hundred to ten thousand must be employed to have good
activities and stereoselectivities. Moreover, it has not been
possible to isolate characterizable metallocene active species
using MAO. The third generation of cocatalyst,
B(C.sub.6F.sub.5).sub.3, proves to be far more efficient while
utilizing a 1:1 catalyst-cocatalyst ratio. Although active catalyst
species generated with B(C.sub.6F.sub.5).sub.3 are isolable and
characterizable, the anion MeB(C.sub.6F.sub.5).sub.3.sup-
..crclbar., formed after Me.sup..crclbar. abstraction from
metallocene dimethyl complexes, is weakly coordinated to the
electron-deficient metal center, thus resulting in a drop of
certain catalytic activities. The recently developed
B(C.sub.6F.sub.5).sub.4.sup..crclbar. type of non-coordinating
anion exhibits some of the highest reported catalytic activities,
but such catalysts have proven difficult to obtain in the pure
state due to poor thermal stability and poor crystallizability,
which is crucial for long-lived catalysts and for understanding the
role of true catalytic species in the catalysis for the future
catalyst design. Synthetically, it also takes two more steps to
prepare such an anion than for the neutral organo-Lewis acid.
[0006] In our prior applications referred to hereinabove, and in
publications appearing in J. Am. Chem. Soc. 1996, 118, 12451-12452,
Organometallics 1998, 17, 3996-4003, and J. Am. Chem. Soc. 1998,
120, 6287-6305 new, sterically encumbered fluoroaryl boranes such
as tris(perfluorobiphenyl)borane (PBB), and the preparation and use
of such compounds as a catalyst for ring opening polymerization of
tetrahydrofuran (THF) and as a highly efficient cocatalyst for
metallocene-mediated olefin polymerization are described. For
example, PBB is a strong organo-Lewis acid which can be synthesized
in much higher yield than B(C.sub.6F.sub.5).sub.3. The anion
generated with PBB is non-coordinating instead of being weakly
coordinating as in the case of B(C.sub.6F.sub.5).sub.3. Thus, the
former exhibits higher catalytic activities and can activate
previously unresponsive metallocenes. The catalytically active
species generated with PBB are isolable, X-ray crystallographically
characterizable instead of the unstable, oily residues often
resulting in the case of B(C.sub.6F.sub.5).sub.4.sup..crcl- bar..
In addition, PBB exhibits even higher catalytic activities in most
cases.
[0007] This invention provides, inter alia, technology described in
the above-referred-to prior applications, and additionally,
improvements in the technology described in the above-referred-to
prior applications.
SUMMARY OF THE INVENTION
[0008] Accordingly, it is an object of the subject invention to
provide, prepare and utilize new types of organo-Lewis acids that
are useful in forming novel, highly-effective olefin polymerization
catalysts.
[0009] A further object of the subject invention is to provide a
catalyst which permits better control over molecular weight,
molecular distribution, stereoselectivity, and/or comonomer
incorporation.
[0010] Another object of the subject invention is to provide a
Ziegler-Natta type catalyst system which reduces the use of excess
cocatalyst and activates previously unresponsive metallocenes.
[0011] In accordance with one of its embodiments this invention
provides novel organoboranes which may be represented by the
formula
BR'.sub.nR".sub.3-n (I)
[0012] wherein R' is a fluoroaryl group having at least one
additional substituent other than fluorine, wherein each R" is,
independently, (i) a fluoroaryl group having at least one
additional substituent other than fluorine, or (ii) a fluorinated
aryl group devoid of additional substitution, and wherein n is 1 or
2. In these compounds both R" groups are preferably the same as
each other and, preferably, are fluoroaryl groups having at least
one additional substituent other than fluorine. Most preferably, n
is 3, and each R' of formula (I) is the same as the other two. The
substituent(s) other than fluorine present in the organoboranes of
formula (I) can be (i) one or more substituents which increase the
solubility of the compound in an organic solvent as compared to the
corresponding compound in which each such substituent other than
fluorine is replaced by a fluorine atom, (ii) one or more electron
withdrawing substituents other than fluorine, or (iii) a
combination of at least one substituent from (i) and at least one
substituent from (ii).
[0013] A second embodiment provides organoboranes which may be
referred to by the formula
BR'R".sub.2 (II)
[0014] where at least one of R' and R" is a fluorinated biphenyl or
fluorinated polycyclic fused ring group such as naphthyl,
anthracenyl or fluorenyl. Preferably two, and more preferably all
three, of R' and R" are fluorinated biphenyl or fluorinated
polycyclic fused ring groups such as naphthyl, anthracenyl or
fluorenyl. Two of the biphenyl groups may be substituted with a
phenyl group. That is, R' is a biphenyl group and each R" is a
phenyl group. The biphenyl groups and the phenyl groups plus any
polycyclic fused ring group or groups of the compounds of formula
(II) should be highly fluorinated, preferably with only one or two
hydrogen atoms on a group, and most preferably, as in PBB, with no
hydrogen atoms and all fluorine substituents. Thus in one subgroup
of these triorganoboranes R' of formula (II) is a fluorobiphenyl
group having 0 to 2 hydrogen atoms and 7 to 9 fluorine atoms on the
rings thereof, the sum of the foregoing integers being 9, and each
R" of formula (II) is a phenyl group having 0 to 2 hydrogen atoms
and 3 to 5 fluorine atoms on the ring, the sum of the foregoing
integers being 5. In this subgroup most preferably R' is
nonafluorobiphenyl and each R" group is a pentafluorophenyl group,
i.e., the compound is nonafluorobiphenyl-bis(pen-
tafluorophenyl)borane. In another subgroup of these
triorganoboranes R' of formula (II) is a fluorobiphenyl group
having 0 to 2 hydrogen atoms and 7 to 9 fluorine atoms on the rings
thereof, the sum of the foregoing integers being 9, and each R"
group of formula (II) is a fluorinated polycyclic fused ring group
such as naphthyl, anthracenyl or fluorenyl. Preferably the
polycyclic fused ring group is perfluorinated. However the fused
rings may have one or two hydrogen atoms on the ring with the other
available positions occupied by fluorine. A third subgroup of
organoboranes of this second embodiment are
tris(fluorobiphenyl)boranes wherein R' of formula (II) and each R"
of formula (II) is a fluorobiphenyl group having 0 to 2 hydrogen
atoms and 7 to 9 fluorine atoms on the rings thereof, the sum of
the foregoing integers being 9, especially where such
fluorobiphenyl groups are all the same as each other. The most
preferred compound of this third sub-group is
tris(perfluorobiphenyl)borane.
[0015] A third embodiment of this invention is comprised of
organoboranes of the formula:
B(R.sup.1).sub.n(R.sup.2).sub.3-n (III)
[0016] wherein each R.sup.1 is, independently, a perfluorinated
polycyclic fused ring group in which the ring system is totally
aromatic (e.g., as in naphthyl or anthracenyl), or is partially
aromatic and partially cycloaliphatic, (e.g., as in
tetrahydronaphthyl, acenaphthyl, indenyl, or fluorenyl), wherein
each R.sup.2 is a pentafluorophenyl group, and wherein n is 1 to 3.
Such compounds include, for example:
[0017] tris(nonafluoroanthracenyl)borane,
[0018] bis(nonafluoroanthracenyl)(pentafluorophenyl)borane,
[0019] nonafluoroanthracenylbis(pentafluorophenyl)borane,
[0020] tris(undecafluorotetrahydronaphthyl)borane,
[0021]
bis(undecafluorotetrahydronaphthyl)(pentafluorophenyl)borane,
[0022]
undecafluorotetrahydronaphthylbis(pentafluorophenyl)borane,
[0023] tris(nonafluorofluorenyl)borane,
[0024] bis(nonafluorofluorenyl)(pentafluorophenyl)borane, and
[0025] nonafluorofluorenylbis(pentafluorophenyl)borane.
[0026] Compounds of this embodiment in which less than half of the
fluorine atoms, and preferably up to about 3 fluorine atoms, are
replaced by a corresponding number of substituents other than
fluorine are included within the scope of the first embodiment
described above.
[0027] A fourth embodiment of this invention provides a novel
complex or ion pair formed from an organoborane of the first
embodiment. In particular, the novel complex or ion pair of this
fourth embodiment comprises a cation formed from a d-block or
f-block metal compound by abstraction therefrom of a leaving group
(e.g., a methyl group), and an anion formed by unification of the
leaving group with an organoborane of the formula
BR'.sub.nR".sub.3-n. In this formula, R' is a fluoroaryl group
having at least one additional substituent other than fluorine,
wherein each R" is, independently, (i) a fluoroaryl group having at
least one additional substituent other than fluorine, or (ii) a
fluorinated hydrocarbyl group devoid of additional substitution,
and n is 1 or 2.
[0028] A fifth embodiment of this invention provides a novel
complex or ion pair formed from an organoborane of the third
embodiment. Thus in accordance with this fifth embodiment the
complex or ion pair comprises a cation formed from a d-block or
f-block metal compound by abstraction therefrom of a leaving group
(e.g., a methyl group), and an anion formed by unification of the
leaving group with an organoborane of the formula
B(R.sup.1).sub.n(R.sup.2).sub.3-n. In this formula, each R' is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic (e.g., as in naphthyl or
anthracenyl), or is partially aromatic and partially
cycloaliphatic, (e.g., as in tetrahydronaphthyl, acenaphthyl,
indenyl, or fluorenyl), wherein each R.sup.2 is a pentafluorophenyl
group, and wherein n is 1 to 3.
[0029] In a sixth embodiment of this invention, a novel catalytic
complex or ion pair is produced by a process which comprises
contacting a d-block or f-block metal compound having at least one
leaving group (e.g., a methyl group) with an organoborane of the
formula BR'.sub.nR".sub.3-n. In this formula, R' is a fluoroaryl
group having at least one additional substituent other than
fluorine, each R" is, independently, (i) a fluoroaryl group having
at least one additional substituent other than fluorine, or (ii) a
fluorinated hydrocarbyl group devoid of additional substitution,
and n is 1 or 2. In this process, which typically is conducted in a
suitable anhydrous liquid solvent and in a suitably inert
atmosphere or environment, a leaving group is abstracted from the
d-block or f-block metal compound and becomes unified with the
organoborane to produce the catalytic complex.
[0030] A seventh embodiment is analogous to the process of the
sixth embodiment except that the organoborane has the formula
B(R.sup.1).sub.n(R.sup.2).sub.3-n wherein each R.sup.1 is,
independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic (e.g., as in naphthyl or
anthracenyl), or is partially aromatic and partially
cycloaliphatic, (e.g., as in tetrahydronaphthyl, acenaphthyl,
indenyl, or fluorenyl), wherein each R.sup.2 is a pentafluorophenyl
group, and wherein n is 1 to 3.
[0031] An eighth embodiment of this invention is a process for
polymerizing an olefinic monomer or copolymerizing two or more
olefinic monomers, which process comprises contacting the monomer
or monomers, preferably a single vinyl monomer or two or more
copolymerizable vinyl monomers, with a polymerization catalyst
complex which comprises a cation formed from a d-block or f-block
metal compound by abstraction therefrom of a leaving group (e.g., a
methyl group), and an anion formed by unification of the leaving
group with an organoborane of the formula BR'.sub.nR".sub.3-n,
wherein R' is a fluoroaryl group having at least one additional
substituent other than fluorine, wherein each R" is, independently,
(i) a fluoroaryl group having at least one additional substituent
other than fluorine, or (ii) a fluorinated hydrocarbyl group devoid
of additional substitution, and wherein n is 1 or 2.
[0032] A ninth embodiment is analogous to the polymerization
process of the eighth embodiment except that the organoborane has
the formula B(R.sup.1).sub.n(R.sup.2).sub.3-n wherein each R.sup.1
is, independently, a perfluorinated polycyclic fused ring group in
which the ring system is totally aromatic (e.g., as in naphthyl or
anthracenyl), or is partially aromatic and partially
cycloaliphatic, (e.g., as in tetrahydronaphthyl, acenaphthyl,
indenyl, or fluorenyl), wherein each R.sup.2 is a pentafluorophenyl
group, and wherein n is 1 to 3.
[0033] These and other objects, embodiments, features and
advantages of this invention will be apparent from the ensuing
description, appended claims, and accompanying Drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 is a structural depiction of PBB.
[0035] FIG. 2 is a reaction pathway for the synthesis of PBB, which
pathway is equally applicable to the synthesis of (a) analogous
triorganoboranes of formula (I) above in which n is 3 and in which
the three R' groups are all the same as each other, (b)
triorganoboranes of formula (II) above in which the R' group and
the two R" groups are all the same as each other, and (c)
triorganoboranes of formula (III) above in which n is 3, and all
three R.sup.1 groups are the same as each other.
[0036] FIG. 3 shows the reaction pathway for one type of catalytic
complex formed from PBB;
[0037] FIG. 4 shows the reaction pathway for another type of
catalytic complex formed from PBB;
[0038] FIG. 5 shows the reaction pathway for still another type of
catalytic complex formed from PBB;
[0039] FIG. 6 shows the reaction pathway for yet another type of
catalytic complex formed from PBB;
[0040] FIG. 7 shows the reaction pathway for another type of
complex formed from PBB;
[0041] FIG. 8 shows a reaction pathway for a binuclear catalytic
complex formed from PBB; and
[0042] FIG. 9 shows another reaction pathway for a binuclear
catalytic complex formed from PBB.
[0043] Pathways analogous to those depicted in FIGS. 3-9 exist when
PBB is replaced by (a) an analogous triorganoborane of formula (I)
above in which n is 3 and in which the three R' groups are all the
same as each other, (b) a triorganoborane of formula (II) above in
which the R' group and the two R" groups are all the same as each
other, and (c) a triorganoborane of formula (III) above in which n
is 3, and all three R.sup.1 groups are the same as each other.
[0044] It is to be understood that the present invention is not to
be limited to any spatial configurations for complexes depicted
either in the Figures or in the specification or claims of this
document. Such depictions are not presented as limitations or
requirements as regards stereochemical considerations, but rather
are presented for purposes of illustration only.
FURTHER DETAILED DESCRIPTION OF THE INVENTION
[0045] Organoboranes of this Invention
[0046] The compounds of the first, second, and third embodiments of
this invention are strong organo-Lewis acids. When used as a
cocatalyst in the formation of our novel catalyst compositions,
these triorganoboranes, because of their ligand abstracting
properties, produce corresponding anions which are capable of only
weakly, if at all, coordinating to the metal center, and thus do
not interfere in the olefin polymerization processes.
[0047] As noted above, the novel, eminently useful organoboranes of
the first embodiment of this invention can be represented by
formula (I), i.e., BR'.sub.nR".sub.3-n. In this formula R' is a
fluoroaryl group having at least one additional substituent other
than fluorine (hereinafter sometimes called a "substituted
fluoroaryl group"), R" is, independently, (i) a substituted
fluoroaryl group, or (ii) a fluorinated aryl group devoid of
additional substitution (hereinafter sometimes called an
"unsubstituted fluoroaryl group"), and n is 1 or 2. It will, of
course, be understood that the term "substituent" in reference to
the ring system of the fluoroaryl group does not include a hydrogen
or deuterium atom--the substituent is something other than these.
Each fluoroaryl group is highly fluorinated. Thus preferably, each
substituted fluoroaryl group has (a) more fluorine atoms than such
other ring substituents, (b) no more than three such other ring
substituents, and at most only one hydrogen atom on the ring. More
preferably, each substituted fluoroaryl group has (a) no more than
two such other substituents on the ring, (b) no hydrogen atom on
the ring, and (c) a fluorine atom in each of the other ring
positions available for substitution. Similarly, each unsubstituted
fluoroaryl group preferably contains no more than two hydrogen
atoms on the ring, and more preferably no more than one hydrogen
atom on the ring. Most preferably, an unsubstituted fluoroaryl
group is perfluorinated.
[0048] The substituents other than fluorine on the ring(s) of R'
can be, for example, one or more of the following:
[0049] hydrocarbyloxy, RO--;
[0050] hydrocarbylthio, RS--;
[0051] tri(hydrocarbyl)silyl, R.sub.3Si--;
[0052] dihydrocarbylamino, R.sub.2N--;
[0053] dihydrocarbylphosphino, R.sub.2P--;
[0054] hydrocarbyl, R--;
[0055] trihydrocarbylsiloxy, R.sub.3SiO--;
[0056] dihydrocarbyloxidoamino, R.sub.2N(O)--;
[0057] dihydrocarbyloxidophosphino, R.sub.2P(O)--;
[0058] poly(hydrocarbyloxy), R(OR').sub.nO--, where R' is divalent
hydrocarbyl, e.g., methylene (--CH.sub.2--), dimethylene
(--CH.sub.2CH.sub.2--), methyldimethylene
(--CH(CH.sub.3)CH.sub.2--), ethyl-dimethylene
(--CH(C.sub.2H.sub.5)CH.sub.2--), cyclohexylene
(--C.sub.6H.sub.10--), phenylene (--C.sub.6H.sub.4--), or the like,
and n is 1 to about 100, and preferably 1 to about 50;
[0059] poly(hydrocarbylsiloxy),
R.sub.3SiO(R.sub.2SiO).sub.nR.sub.2SiO--, where n is 0 to about
20); and
[0060] halide of atomic number greater than 9.
[0061] In the above formulas of the substituent groups, R,
independently, is cyclic or acyclic or a group having both cyclic
and acyclic portions, is saturated or contains aliphatic or
aromatic unsaturation or both, and typically has no more than about
24 carbon atoms, and preferably no more than about 12 carbon atoms.
In addition, the hydrocarbyl moiety of the above substituents can
itself be substituted, e.g., by one or more groups such as halide,
hydroxy, alkoxy, or analogous substituents. Thus the substituents
other than fluorine atoms on the ring(s) of the fluoroaryl groups
can be, for example, substituted hydrocarbyloxy, substituted
hydrocarbylthio, substituted trihydrocarbylsilyl where 1 to 3 of
the hydrocarbyls are substituted, substituted dihydrocarbylamino
where one or both hydrocarbyls are substituted, substituted
dihydrocarbylphosphino where one or both hydrocarbyls are
substituted, substituted hydrocarbyl other than fluoroaryl, or
substituted trihydrocarbylsiloxy where 1 to 3 of the hydrocarbyls
are substituted.
[0062] Preferably, the organoborane of formula (I) is (i) a Lewis
acid of a strength essentially equivalent to or, more preferably,
greater than that of the corresponding organoborane in which each
substituent other than fluorine is replaced by a fluorine atom or
(ii) a Lewis acid having greater solubility in organic solvents.
For the purposes of this invention, comparative Lewis acid strength
is assessed by reacting bis(cyclopentadienyl)thorium dimethyl with
the respective organoboranes and the extent of ion pair formation
is determined by NMR. Similarly, comparative solubility in organic
solvents is measured by determining the solubility of the
respective organoboranes in n-hexane at 20.degree. C.
[0063] Illustrative examples of some of the preferred organoboranes
of this invention are presented in the following formulas wherein x
is 1 to 3, and R is a substituent other than a fluorine atom,
typically an electron-withdrawing group or a solubility-enhancing
group. In formulas (IV) through (X), one or more of the fluorine
atoms, typically no more than three fluorine atoms on any given
fused ring structure depicted, may be replaced by such a
substituent. 1
[0064] The organoboranes of this invention can be prepared by
reaction between (i) an active metal derivative of the
polyfluoroaromatic or substituted polyfluoroaromatic compound
corresponding in structure to the structure(s) desired for R', and
if present, R", or R.sup.1, and if present, R.sup.2, and (ii) a
boron trihalide or an etherate complex thereof. Thus in preparing a
triorganoborane of formula (I) above in which R' and R" are all the
same substituted fluoroaryl groups, the reaction may be depicted by
the following equation:
3M-R'+BX.sub.3.fwdarw.B(R').sub.3+3 MX (Eq. 1)
[0065] where M is an alkali metal (e.g., Li or Na), Al, Sn, Zn, Hg,
or a halomagnesium group, R' is a fluoroaryl group having at least
one ring substituent other than fluorine, and X is a halogen atom.
When preparing a triorganoborane of formula (I) above wherein one
or each of two of the fluoroaryl groups is a substituted fluoroaryl
group and each of the two remaining fluoroaryl groups or the one
remaining fluoroaryl group differs therefrom (e.g., it is an
unsubstituted fluoroaryl group, or it is a different substituted
fluoroaryl group), the reaction depicted in Equation (2) can be
used:
n M-R'+B(R").sub.3-nX.sub.n.fwdarw.B(R').sub.n(R").sub.3-n+n MX
(Eq. 2)
[0066] where M, R', and X are as defined above in connection with
equation (1), R" is a fluoroaryl group that is different from R',
and n is 1 or 2. An analogous two-step procedure is employed when
the three fluoraryl groups are to differ from each other.
[0067] Reactions pursuant to Equations (1) and (2) above can also
be used for preparing triorganoboranes of formula (II) above by
using reactants in which R', and if present, R" are as defined in
connection with formula (II). For example, PBB (FIG. 1) has been
synthesized via Equation (1) in yields as high as 91% as compared
to the 30-50% yields experienced with B(C.sub.6F.sub.5).sub.3,
currently a very important Lewis acidic cocatalyst in industry. The
Lewis acidity of PBB has been shown to be much greater than that of
B(C.sub.6F.sub.5).sub.3 by comparative reactions of
Cp*.sub.2ThMe.sub.2 with B(C.sub.6F.sub.5).sub.3 and PBB
(Cp*=C.sub.5Me.sub.5). The former reagent does not effect
Me.sup..crclbar. abstraction, while the latter gives methyl
abstraction in forming, for example, the catalyst shown in FIG. 3.
Preferred compounds of formula (I), (II), or (III) above having a
Lewis acid strength essentially equivalent to, and preferably
greater than, that of PBB also possess this important property.
[0068] Similarly, reactions pursuant to Equations (1) and (2) above
can be used for preparing triorganoboranes of formula (III) above.
In this case R' in these equations is replaced by R.sup.1, and R"
is replaced by R.sup.2, where R.sup.1 and R.sup.2 are as defined
above in connection with formula (III).
[0069] The reactions of Equations (1) and (2) are typically
conducted in a suitable non-coordinating solvent such as a liquid
paraffinic or aromatic hydrocarbon or mixture thereof, and
typically at temperatures in the range of about -78.degree. C. to
about 25.degree. C. However, ether solvents can be used, either
alone or in combination with a hydrocarbon solvent. When an ether
solvent is employed, the product will typically be coordinated with
the ether, which is then removed, for example by sublimation. FIG.
2 and Example 1 hereinafter illustrate an overall synthesis for
PBB, involving, inter alia, Equation (1) above. As noted, such
synthesis can readily be adapted for synthesis of organoboranes of
formulas (I), (II), and (III) above in which all three fluoroaryl
groups are the same. Likewise, Example 2 hereinafter illustrates a
synthesis procedure of Equation (2) above that can be used for
producing triorganoboranes having two different fluoroaryl groups
in the molecule. By appropriate substitution of reactants in this
procedure, a variety of such triorganoboranes of this invention can
be prepared.
[0070] Catalytic Complexes of this Invention
[0071] The reaction of tris(2-perfluorobiphenyl)borane and of
bis(perfluorophenyl)(2-perfluorobiphenyl)borane with a variety of
zirconocene and other actinide or transition metal dimethyl
complexes proceeds rapidly and quantitatively at room temperature
in noncoordinating solvents to yield catalytic complexes. These
catalytic complexes may be used in the polymerization,
copolymerization, oligomerization and dimerization of
.alpha.-olefins. In addition, each of these catalytic complexes may
be used together with aluminum alkyls, aluminum aryls, (e.g.,
AlR.sub.3, R=Me, Et, Ph, naphthyl) or alumoxanes (which are also
known as aluminoxanes), such as methylalumoxane for increased
polymer yields. This invention now makes it possible, inter alia,
to synthesize a wide variety of other new catalytic complexes which
can be used in the same manner for producing homopolymers,
copolymers, oligomers and dimers of .alpha.-olefins. These new
catalytic complexes can also be used in conjunction with
hydrocarbyl aluminum compounds or alumoxanes in the efficient
polymerization of various monomers of suitable, if not enhanced,
properties.
[0072] Pursuant to this invention a d- or f- block metal compound
having at least one leaving group is reacted with a triorganoborane
of this invention whereby a leaving group is abstracted from the
metal compound to produce a cation, and the abstracted leaving
group is unified with the triorganoborane to form an anion.
[0073] Various d- and f- block metal compounds may be used in
forming the catalytically active compounds of this invention. The
d-block and f-block metals of this reactant are the transition,
lanthanide and actinide metals. See, for example, the Periodic
Table appearing on page 225 of Moeller, et al., Chemistry, Second
Edition, Academic Press, Copyright 1984. References herein to
Groups of the Periodic Table are made with reference to the
Periodic Table appearing on page 225 of Moeller et al. As regards
the metal constituent, preferred are compounds of Groups 4-8 of the
Periodic Table. More preferred are compounds of the metals of
Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) and thorium, and
most preferred are thorium and the Group 4 metals, titanium and
hafinium, and especially zirconium.
[0074] A vital feature of the d- or f-block metal compound used in
forming the catalytic complexes of this invention is that it must
contain at least one leaving group that is abstracted by and
unifies with the triorganoborane of this invention whereby an ion
pair is formed. Univalent leaving groups that meet these criteria
include hydride, hydrocarbyl free of hydrogen atoms in a
.beta.-position, and silylcarbinyl (R.sub.3SiCH.sub.2--) groups.
Examples include methyl, benzyl, and trimethylsilylcarbinyl. Of
these, the methyl group is the most preferred leaving group.
[0075] Metallocenes make up a preferred class of d- and f-block
metal compounds used in making the catalytic complexes of this
invention. These compounds are characterized by containing at least
one cyclopentadienyl moiety pi-bonded to the metal atom. For use in
this invention, the metallocene must also have bonded to the d- or
f-block metal atom at least one leaving group capable of being
abstracted by and unified with the triorganoborane used.
[0076] Metallocene structures in this specification are to be
interpreted broadly, and include structures containing 1, 2, 3 or 4
Cp or substituted Cp rings. Thus metallocenes suitable for use in
this invention can be represented by the formula XI:
Q.sub.aCp.sub.bML.sub.cX.sub.d (XI)
[0077] where Cp independently in each occurrence is a
cyclopentadienyl-moiety-containing group which typically has in the
range of 5 to about 24 carbon atoms; Q is a bridging group or ansa
group that links two Cp groups together; M is a d- or f-block metal
atom; each L is, independently, a leaving group that is bonded to
the d-or f-block metal atom and is capable of being abstracted by
the triorganoborane used in forming the catalytic complex; X is a
group other than a leaving group that is bonded to the d- or
f-block metal atom; a is 0 or 1; b is a whole integer from 1 to 3
(preferably 1 or 2); c is 1 to 3; d is 0 or 1; and the sum of c and
d is at least 2. The sum of b, c, and d is sufficient to form a
stable compound, and often is the formal oxidation state (or formal
valence) of the d- or f-block metal atom. When using as a
polymerization catalyst a complex of this invention made from a
metallocene of formula (XI), X, if present, must not detrimentally
affect propagation of the polymer chain during polymerization. In
such case, X is preferably a hydrogen atom or a group bonded to the
metal atom via a carbon atom, and most preferably, is a hydrogen
atom or an alkyl group.
[0078] Cp is, independently, a cyclopentadienyl, indenyl, 4, 5, 6,
7-tetrahydroindenyl, 1-azaindenyl, fluorenyl, or related group,
including a benzo-fused indenyl and an acenaphthindenyl group as
described in U.S. Pat. No. 5,455,366, or a hydrocarbyl-, halo-,
halohydrocarbyl-, hydrocarbylmetalloid-, and/or
halohydrocarbylmetalloid-substituted derivative of any of the
foregoing groups, as long as the group can .pi.-bond to the metal.
Cp typically contains up to 75 non-hydrogen atoms. Q, if present,
is typically a silylene (>SiR.sub.2), benzo
(C.sub.6H.sub.4<), substituted benzo, methylene (--CH.sub.2--),
substituted methylene, ethylene (--CH.sub.2CH.sub.2--), or
substituted ethylene bridge. M is preferably a metal atom of Groups
4-8, and most preferably is thorium or a Group 4 metal atom,
especially titanium, and most especially zirconium. L is the
leaving group, such as hydride, or benzyl, and which in most cases
is methyl. X, if present, is a non-leaving group, and thus can be a
halogen atom, a non-leaving hydrocarbyl group, hydrocarbyloxy,
(alkoxy, aryloxy, etc.), trihydrocarbylsiloxy, and similar
univalent groups that form stable metallocenes. The sum of b, c,
and d is a whole number, and is often from 3-5. When M is a Group 4
metal or an actinide metal, and b is 2, the sum of c and d is 2, c
being at least 1. When M is a Group 3 or lanthanide metal, and b is
2, c is 1 and d is zero. When M is a Group 5 metal, and b is 2, the
sum of c and d is 3, c being at least 2.
[0079] In one preferred group of metallocene reactants of formula
(XI), b is 2, i.e., there are two cyclopentadienyl-moiety
containing groups in the molecule, and these two groups can be the
same or they can be different from each other.
[0080] In another preferred group of metallocene reactants, b in
formula (XI) is 1, i.e., there is only one cyclopentadienyl-moiety
containing group in the molecule, and typically the sum of c and d
is 3.
[0081] Also suitable for preparing catalytic complexes of this
invention are compounds analogous to those of formula (XI) where
one or more of the Cp groups are replaced by cyclic unsaturated
charged groups isoelectronic with Cp, such as borabenzene or
substituted borabenzene, azaborole or substituted azaborole, and
various other isoelectronic Cp analogs. See for example
Krishnamurti, et al., U.S. Pat. Nos. 5,554,775 and 5,756,611.
[0082] Another sub-group of useful metallocenes which can be used
in the practice of this invention are metallocenes of the type
described in WO 98/32776 published Jul. 30, 1998. These
metallocenes are characterized in that one or more cyclopentadienyl
groups in the metallocene are substituted by one or more polyatomic
groups attached via a N, O, S, or P atom or by a carbon-to-carbon
double bond. Examples of such substituents on the cyclopentadienyl
ring include --OR, --SR, --NR.sub.2, --CH.dbd., --CR.dbd., and
--PR.sub.2, where R can be the same or different and is a
substituted or unsubstituted C.sub.1-C.sub.16 hydrocarbyl group, a
tri-C.sub.1-C.sub.8 hydrocarbylsilyl group, a
tri-C.sub.1-C.sub.8hydrocar- byloxysilyl group, a mixed
C.sub.1-C.sub.8 hydrocarbyl and C.sub.1-C.sub.8 hydrocarbyloxysilyl
group, a tri-C.sub.1-C.sub.8 hydrocarbylgermyl group, a
tri-C.sub.1-C.sub.8 hydrocarbyloxygermyl group, or a mixed
C.sub.1-C.sub.8 hydrocarbyl and C.sub.1-C.sub.8
hydrocarbyloxygermyl group.
[0083] Still another subgroup of preferred metallocenes is
comprised of the so-called constrained geometry metal complexes.
See for example U.S. Pat. No. 5,539,068 and references cited
therein at Column 1, lines 44-57. The constrained geometry
complexes suitable for use in preparing catalytic complexes of this
invention can be represented by the formula: 2
[0084] wherein M is a metal of Group 3 (other than scandium),
Groups 4-10, or the lanthanide series; L is a group containing a
cyclic, delocalized, anionic, pi-system through which the group is
bound to M, and which group is also bound to Z; Z is a moiety
comprising boron, or a member of Group 14 of the Periodic Table,
and optionally sulfur or oxygen, this moiety having up to about 20
non-hydrogen atoms; Y is an anionic or nonanionic ligand group
bonded to Z and M comprising nitrogen, phosphorus, oxygen, or
sulfur, and having up to about 20 non-hydrogen atoms; R is a
leaving group; X is a non-leaving group, n is 1 to 4, m is 0 to 3,
with the sum of n plus m being 1 to 4 depending upon the valence of
M. Of such compounds, preferred are those in which M is titanium or
zirconium, L is a cyclopentadienyl group or a substituted
cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a
hydrocarbylamido group, R is methyl, n is 2, and m is 0.
Particularly preferred compounds of this type are those in which M
is titanium or zirconium, L is a tetramethylcyclopentadienyl group,
Z is a dimethylsilyl group, Y is a tert-butylamido group, R is
methyl, n is 2, and m is 0. The same comments regarding X as made
in connection with formula (XI) above, also apply to the group
designated X in the above formula. Thus, as noted above, most
preferably X is a hydrogen atom or an alkyl group.
[0085] Illustrative examples of suitable d- or f-block metal
compounds that can be used as reactants in forming the catalytic
complexes of this invention can be found, for example, in U.S. Pat.
Nos. 5,391,789; 5,498,581; 5,786,495; and in WO 98/50392 A1,
published Nov. 12, 1998, provided of course that the compound
contains, or is modified to contain, at least one leaving
group.
[0086] Examples of metallocenes to which this invention is
applicable include such compounds as:
[0087] bis(methylcyclopentadienyl)titanium dimethyl;
[0088] bis(methylcyclopentadienyl)zirconium dimethyl;
[0089] bis(n-butylcyclopentadienyl)zirconium dimethyl;
[0090] bis(dimethylcyclopentadienyl)zirconium dimethyl;
[0091] bis(diethylcyclopentadienyl)zirconium dimethyl;
[0092] bis(methyl-n-butylcyclopentadienyl)zirconium dimethyl;
[0093] bis(n-propylcyclopentadienyl)zirconium dimethyl;
[0094] bis(2-propylcyclopentadienyl)zirconium dimethyl;
[0095] bis(methylethylcyclopentadienyl)zirconium dimethyl;
[0096] bis(indenyl)zirconium dimethyl;
[0097] bis(methylindenyl)zirconium dimethyl;
[0098] dimethylsilylenebis(indenyl)zirconium dimethyl;
[0099] dimethylsilylenebis(2-methylindenyl)zirconium dimethyl;
[0100] dimethylsilylenebis(2-ethylindenyl)zirconium dimethyl;
[0101] dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dimethyl;
[0102] 1,2-ethylenebis(indenyl)zirconium dimethyl;
[0103] 1,2-ethylenebis(methylindenyl)zirconium dimethyl;
[0104] 2,2-propylidenebis(cyclopentadienyl)(fluorenyl)zirconium
dimethyl;
[0105] dimethylsilylenebis(6-phenylindenyl)zirconium dimethyl;
[0106] bis(methylindenyl)zirconium benzyl methyl;
[0107] ethylenebis[2-(tert-butyldimethylsiloxy)-1-indenyl]zirconium
dimethyl;
[0108] dimethylsilylenebis(indenyl)chlorozirconium methyl;
[0109] 5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene zirconium
dimethyl;
[0110] dimethylsilylenebis(2-methylindenyl)hafinium dimethyl;
[0111] dimethylsilylenebis(2-ethylindenyl)hafnium dimethyl;
[0112] dimethylsilylenebis(2-methyl-4-phenylindenyl)hafnium
dimethyl;
[0113] 2,2-propylidenebis(cyclopentadienyl)(fluorenyl)hafnium
dimethyl;
[0114] bis(9-fluorenyl)(methyl)(vinyl)silane zirconium
dimethyl,
[0115] bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium
dimethyl,
[0116] bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium
dimethyl,
[0117] bis(9-fluorenyl)(methyl)(hex-5-enyl)silane zirconium
dimethyl,
[0118] bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium
dimethyl,
[0119] (cyclopentadienyl)(1-allylindenyl)zirconium dimethyl,
[0120] bis(1-allylindenyl)zirconium dimethyl,
[0121] (9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)zirconium
dimethyl,
[0122]
(9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)zirconium
dimethyl,
[0123] bis(9-(prop-2-enyl)fluorenyl)zirconium dimethyl,
[0124] (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)zirconium
dimethyl,
[0125] bis(9-(cyclopent-2-enyl)(fluorenyl)zirconium dimethyl,
[0126] 5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene
zirconium dimethyl,
[0127]
1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)metha-
ne zirconium dimethyl,
[0128] 5-(fluorenyl)-5-(cyclopentadienyl)-1-hexene hafnium
dimethyl,
[0129] (9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium
dimethyl,
[0130]
1-(2,7-di(.alpha.-methylvinyl)(9-fluorenyl)-1-(cyclopentadienyl)-1,-
1-dimethylmethane zirconium dimethyl,
[0131]
1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadienyl)-1,1-m-
ethane zirconium dimethyl,
[0132] 5-(cyclopentadienyl)-5-(9-fluorenyl)-1-hexene titanium
dimethyl,
[0133] 5-(cyclopentadienyl)-5-(9-fluorenyl) 1-hexene titanium
dimethyl,
[0134] bis(9-fluorenyl)(methyl)(vinyl)silane titanium dimethyl,
[0135] bis(9-fluorenyl)(methyl)(prop-2-enyl)silane titanium
dimethyl,
[0136] bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium
dimethyl,
[0137] bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium
dimethyl,
[0138] bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium
dimethyl,
[0139] (cyclopentadienyl)(1-allylindenyl)titanium dimethyl,
[0140] bis(1-allylindenyl)titanium dimethyl,
[0141] (9-prop-2-enyl)fluorenyl)(cyclopentadienyl)hafinium
dimethyl,
[0142] (9-prop-2-enyl)fluorenyl)dentamethylcyclopentadienyl)hafnium
dimethyl,
[0143] bis(9-(prop-2-enyl)fluorenyl)hafnium dimethyl,
[0144] (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)hafnium
dimethyl,
[0145] bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dimethyl,
[0146] 5-(2-methylcyclopentadienyl)-5-(9-fluorenyl)-1-hexene
hafnium dimethyl,
[0147] 5-(fluorenyl)-5-(cyclopentadienyl)-1-octene hafnium
dimethyl,
[0148] (9-fluorenyl)(1-allylindenyl)dimethylsilane hafnium
dimethyl.
[0149] (tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silane
titanium dimethyl;
[0150] (cyclopentadienyl)(9-fluorenyl)diphenylmethane zirconium
dimethyl;
[0151] (cyclopentadienyl)(9-fluorenyl)diphenylmethane hafnium
dimethyl;
[0152] dimethylsilanylene-bis(indenyl)thorium dimethyl;
[0153] dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)zirconium
dimethyl;
[0154] dimethylsilanylene-bis(indenyl)uranium dimethyl;
[0155] dimethylsilanylene-bis(2-methyl-4-ethyl-1-indenyl)zirconium
dimethyl;
[0156] dimethylsilanylene-bis(2-methyl-4, 5, 6,
7-tetrahydro-1-indenyl)zir- conium dimethyl;
[0157]
(tert-butylamido)dimethyl(tetramethyl-.eta..sup.5-cyclopentadienyl)-
silane titanium dimethyl;
[0158]
(tert-butylamido)dimethyl(tetramethyl-.eta..sup.5-cyclopentadienyl)-
silane chromium dimethyl;
[0159]
(tert-butylamido)dimethyl(tetramethyl-.eta..sup.5-cyclopentadienyl)-
silane titanium dimethyl; and
[0160]
(phenylphosphido)dimethyl(tetramethyl-.eta..sup.5-cyclopentadienyl)-
silane titanium dimethyl.
[0161] In many cases the metallocenes such as referred to above
will exist as racemic mixtures, but pure enantiomeric forms or
mixtures enriched in a given enantiomeric form can be used.
[0162] A few illustrative examples of catalytically active
catalytic complexes of this invention include the following,
wherein G is a moiety corresponding to an organoborane of any of
formulas (IV) to (X), above.
[0163] [(C.sub.5H.sub.5).sub.2ZrCH.sub.3].sup..sym.
[CH.sub.3G].sup..crclbar.
[0164] [(C.sub.5H.sub.5).sub.2HfCH.sub.3].sup..sym.
[CH.sub.3G].sup..crclbar.
[0165] [(C.sub.5H.sub.5).sub.2ZrH].sup..sym. [HG].sup..crclbar.
[0166] [(C.sub.5H.sub.5).sub.2HfH].sup..sym. [HG].sup..crclbar.
[0167] {[C.sub.5(CH.sub.3).sub.5].sub.2ZrCH.sub.3}.sup..sym.
[CH.sub.3G].sup..crclbar.
[0168] {[C.sub.5(CH.sub.3).sub.5].sub.2HfCH.sub.3}.sup..sym.
[CH.sub.3G].sup..crclbar.
[0169]
[(C.sub.5H.sub.5).sub.2(CH.sub.3)Zr--CH.sub.3--Zr(CH.sub.3)(C.sub.5-
H.sub.5).sub.2].sup..sym. [CH.sub.3G].sup..crclbar.
[0170]
[(C.sub.5H.sub.5).sub.2(CH.sub.3)Hf--CH.sub.3--Hf(CH.sub.3)(C.sub.5-
H.sub.5).sub.2].sup..sym. [CH.sub.3G].sup..crclbar.
[0171] {[C.sub.5(CH.sub.3).sub.5]Ti(CH.sub.3).sub.2}.sup..sym.
[CH.sub.3G].sup..crclbar.
[0172] {[C.sub.5(CH.sub.3).sub.5]Hf(CH.sub.3).sub.2}.sup..sym.
[CH.sub.3G].sup..crclbar. 3
[0173] The equations presented below illustrate some of the
reactions used in forming the new catalytic complexes of this
invention. In these equations Cp represents a cyclopentadienyl
moiety-containing group. Other abbreviations used in various
portions of this document include the following:
[0174] Cp'=.eta..sup.5--C.sub.5H.sub.5
[0175] CP*=.eta..sup.5-Me.sub.5C.sub.5
[0176] Cp"=.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.3
[0177] CGC=(.eta..sup.5-Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu
[0178] Ind=.eta..sup.5--C.sub.9H.sub.7 (Indenyl)
[0179] Flu=.eta..sup.5--C.sub.13H.sub.9 (Fluorenyl)
[0180] It is also worth noting that in accordance with common
practice in the art, the designations ".mu.-Me", ".mu.-H", and
".mu.-F" signify that the indicated group or element constitutes a
bridge between two metal centers.
[0181] Reaction of a compound of formula (I) above with a bis-Cp
type of dimethyl metallocene such as a zirconocene can form a
dinuclear methyl-bridged metallocene cation, for example: 4
[0182] When this reaction is performed in the presence of hydrogen,
a dinuclear hydrogen bridged metallocene cation can be formed, for
example: 5
[0183] More particularly, reaction of an organoborane of formula
(I) above with a Group 4 dimethyl or trimethyl or a Th dimethyl at
temperatures in the range of about -78.degree. C. to about
25.degree. C. proceeds cleanly to yield cationic complexes such as
set forth below. 6
[0184] M=Th, Zr, Hf. Ti
[0185] 1. [Cp*.sub.2ThMe].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0186] 2. [Cp'.sub.2ZrCl].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0187] 3. [Cp'.sub.2ZrMe(.mu.-Me)MeZrCp.sub.2].sup..sym.
[MeBR'.sub.nR"3-n.sup..crclbar.
[0188] 4. [Cp".sub.2ZrMe(.mu.-Me)MeZrCp".sub.2].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0189] 5. [Cp*.sub.2ZrMe(.mu.-Me)MeZrCp*.sub.2].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0190] 6. {[(Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu]ZrMe}.sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0191] 7. {[(Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu]TiMe}.sup..sym. B
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0192] 8. [Cp*ZrMe.sub.2].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0193] 9. [Cp*HfMe.sub.2].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0194] 10.
{[rac-Me.sub.2Si(Ind).sub.2ZrMe].sub.2(.mu.-Me)}.sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0195] 11. {[Me.sub.2C(Flu)(Cp)ZrMe].sub.2(.mu.-Me)}.sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0196] Monomeric metallocene cations such as zirconocene cations
can be produced by reacting an organoborane of formula (I) with a
bis-Cp type of dimethyl metallocene at a suitably elevated
temperature. An example is the following reaction which may be
performed at about 60.degree. C.: 7
[0197] The same end product can be formed by another new reaction
of this invention in which the methyl-bridged dinuclear metallocene
is used as the starting material: 8
[0198] Another novel reaction of this invention results from the
discovery that certain methyl-bridged dinuclear metallocenes can be
thermally transformed to fluorine-bridged dinuclear
metallocenes:
{[Cp".sub.2ZrMe].sub.2(.mu.-Me)}.sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..cr-
clbar..fwdarw.{[Cp".sub.2ZrMe].sub.2(.mu.-F)].sup..sym.
[MeBR'.sub.nR".sub.3-n].sup..crclbar.
[0199] Other types of cationic metallocene catalyst systems can
also be created with the organoboranes of this invention such as
depicted in formulas (I), (II), and (III) above. For example,
metallocene cations of mono-Cp type such as depicted in FIGS. 4 and
5 can be formed by the reaction of mono-pentamethyl Cp trimethyl
Group 4 complexes with PBB. When PBB is replaced in these reactions
by an organoborane of formula (I) the product contains an anion
formed by the unification of a methyl leaving group with the
organoborane. These are very good syndiospecific styrene
polymerization catalysts.
[0200] Constrained geometry types of zirconocene and titanocene
cations such as those in FIG. 6 where M=Zr or Ti, are readily
produced by the reaction of the corresponding dimethyl metallocenes
with organoboranes of formulas (I), (II), and (III). The resultant
catalytic complexes are highly naked cations, and are, in general,
more active catalysts than those generated with
B(C.sub.6F.sub.5).sub.3.
[0201] The following Examples are presented for purposes of
illustration. They are not intended to limit, and should not be
construed as limiting, the scope of this invention to the
particulars set forth therein.
EXAMPLE 1
Synthesis of Tris(2-perfluorobiphenyl)borane (PBB)
[0202] a) n-Butyllithium (1.6M in hexanes, 25 mL, 40 mmol) was
added dropwise to bromopentafluorobenzene 18.0 g, 9.1 mL, 72.9
mmol) in 100 mL of diethyl ether over a cold-water bath. The
mixture was then stirred for a further 12 h at room temperature.
Removal of solvent followed by vacuum sublimation at 60-65.degree.
C./10.sup.-4 torr gave 12.0 g of 2-bromononafluorobiphenyl as a
white crystalline solid: yield 83.3%. The dangerous and explosive
nature of C.sub.6F.sub.5Li either solutions in this preparation can
be avoided by (a) the use of excess of C.sub.6F.sub.5Br, (b) slow
addition of n-butyllithium, (c) frequent change of the cold water
bath or use of a continuous flowing cold water bath. b) To the
above prepared 2-bromononafluorobiphenyl (5.0 g, 12.7 mmol) in a
mixed solvent of 70 mL of diethyl ether and 70 mL of pentane was
gradually added 8.0 mL of n-butyllithium (1.6M in hexanes, 12.8
mmol) at -78.degree. C. The mixture was stirred for an additional 2
h, and boron trichloride (4.0 mL, 1.0M in hexanes, 4.0 mmol) was
then quickly added by a syringe. The mixture was left at
-78.degree. C. for 1 h and the temperature was then allowed to
slowly rise to room temperature. A suspension resulted after
stirring an additional 12 h. It was filtered to give a yellow
solution, and the solvent of the filtrate was removed in vacuo. The
resulting pale yellow powder was sublimed at 140.degree.
C./10.sup.-4 torr or 125.degree. C./10.sup.-6 torr to produce a
light yellow crystalline solid as an ether-free crude product.
Recrystallization from pentane at -20.degree. C. gave 3.5 g of the
pure PBB as a white crystalline solid: yield 91.0%. Analytical and
spectroscopic data for PBB are as follows. .sup.19F NMR
(C.sub.6D.sub.6, 23.degree. C.): .delta.-120.08 (s, br, 3 F, F-3),
-132.09 (s, br, 3 F, F-6), -137.66 (s, br, 6 F, F-2'/F-6'), -143.31
(t, .sup.3J.sub.F-F=21.4 Hz, 3 F, F-4), -149.19 (t, .sup.3JF-F=21.7
Hz, 3 F. F-4'), -150.56 (t, .sup.3J.sub.F-F=14.7 Hz, 3 F, F-5),
160.72 (s, br, 6 F, F-3'/F-5'). .sup.13C NMR (C.sub.6D.sub.6,
23.degree. C.): .delta.150.92 (dd, J=.sub.C-F=251.1 Hz,
.sup.2J.sub.C-F=10.1 Hz, 3 C), 146.35 (dd, .sup.1J.sub.C-F=254.3
Hz, .sup.2J.sub.C-F=12.1 Hz, 3 C), 144.26 (dd,
.sup.1J.sub.C-F=258.1 Hz, .sup.2J.sub.C-F=10.5 Hz, 6 C). 143.50
(tt, .sup.1J.sub.C-F=265.4 Hz, .sup.2J.sub.CF12.0 Hz, 3 C), 141.98
(tt, .sup.1J.sub.C-F=261.4 Hz, =11.7 Hz, 3 C), 141.17 (tt,
.sup.1J.sub.C-F=254.3 Hz, .sup.2J.sub.C-F=10.5 Hz, 3 C), 137.70
(tt. .sup.1J.sub.C-F=257.3 Hz. .sup.2J.sub.C-F=11.6 Hz, 6 C),
124.51 (d, .sup.2J.sub.C-F=11.7Hz, 3 C), 113.60
(d,.sup.2J.sub.C-F=11.5 Hz. 3 C), 106.05 (s, br, 3 C). MS: parent
ion at m/e 956. Anal. Calcd for C.sub.36 BF.sub.27: C, 45.22: H,
0.00. Found: C, 45.44; H, 0.05.
EXAMPLE 2
Synthesis of Bis(pentafluorophenyl)(2-perfluorobiphenyl)borane
(BPB)
[0203] In a 100 mL flask, 2-perfluorobiphenyl bromide (3.16 g, 8.0
mmol) was dissolved in 20 mL of drypentane. To another 250 mL
flask, were added 30mL of pentane and 5.1 mL of n-butyllithium
(1.6M in hexanes, 9.0 mmol), and the solution was cooled down to
-50.degree. C. The solution of 2-perfluorobiphenyl bromide was
added dropwise via syringe to the n-butyllithium solution. A white
precipitate formed immediately. The resultant mixture was stirred
between -40.degree. C. and -30.degree. C. for 90 minutes after the
addition was completed, and then 20 mL of (C.sub.6F.sub.5).sub.2BCl
(3.16 g, 8.0 mmol in pentane) was added at -50.degree. C. The
reaction mixture was allowed to warm slowly to room temperature
overnight. After filtration and removal of all the volatiles, a
sticky oil was left. This oil was washed with cold pentane
(-78.degree. C.) three times to give a white solid product. Yield,
2.0 g (37%). The complex can be further purified by sublimation at
110.degree. C. (0.05 torr) for 3 h. Spectroscopic and analytical
data for (BPB) are as follows. .sup.19F NMR (benzene-d.sub.6,
282.33 MHz, 23.degree. C.) .delta.-127.48 (d, .sup.3J.sub.F-F=21.5
Hz, 4 F, o-F), -128.28 (m, 1 F, 3-F), -135.10 (m, 1 F, 6-F),
-139.89 (d, .sup.3J.sub.F-F=21.5 Hz, 2 F, 2', 6'-F), -140.90 (tt,
.sup.3J.sub.F-F=20.8 Hz, 2 F, p-F), -144.94 (td,
.sup.3J.sub.F-F=21.0 Hz, .sup.5J.sub.F-F=7.6 Hz, 1 F, 5-F), -150.07
(t, .sup.3J.sub.F-F=21.2 Hz, 1 F, 4'-F), -151.48 (td,
.sup.3J.sub.F-F=22.2 Hz, .sup.5J.sub.F-F=6.8 Hz, 1 F, 4-F), -160.25
(m, 4 F, m-F), -160.98 (m, 2 F, 3', 5'-F). Anal. Calcd for
C.sub.24BF.sub.19: C, 43.67; H, 0.00; N, 0.00. Found C, 43.65, H,
0.10, N, 0.00.
EXAMPLE 3
Synthesis of [CP.sub.2MMe].sup..sym. [MePBB].sup..crclbar. (M=Th;
Cp=C.sub.5Me.sub.5)
[0204] (C.sub.5Me.sub.5).sub.2ThMe.sub.2 (0.106 g, 0.199 mmol) and
PBB (0.191 g, 0.199 mmol), in a glove box, were charged into a
25-mL reaction flask with a filter plug, and the flask was attached
to a high vacuum line. Benzene (15 mL) was then vacuum-transferred
into this flask at -78.degree. C. The mixture was slowly allowed to
warm to room temperature and stirred for 6 h. The solvent was
removed, pentane (20 mL) was next vacuum-transferred into the
flask, and the mixture was filtered after stirring. The white solid
which collected was dried under vacuum to give 0.210 g of product:
yield 70.9%. Analytical and spectroscopic data are as follows.
.sup.1H NMR (C.sub.6D.sub.6, 23.degree. C.): .delta.1.61 (s, 30 H,
C.sub.5Me.sub.5), 0.62 (s, 3 H, Th-CH.sub.3), -095 (s, br, 3 H,
B--CH.sub.3). .sup.19F NMR(C.sub.6D.sub.6, 23.degree. C.):
.delta.-124.57 (s, br,3F), -138.10 (s, br,3 F), -139.28 (d,
.sup.3J.sub.F-F=21.4 Hz, 3 F), -139.74 (d, .sup.3J.sub.F-F=21.2 Hz,
3 F), -155.08 (t, .sup.3J.sub.F-F 21.4 Hz, 3 F), -157.32 (t,
.sup.3J.sub.F-F=22.0 Hz, 3 F), -162.20 (t, .sup.3J.sub.F-F=22.0 Hz,
3 F), -163.13 (t, .sup.3J.sub.F-F=22.0 Hz, 3 F), -163.90 (t,
.sup.3J.sub.F-F=21.4Hz, 3 F). .sup.13C NMR (C.sub.6D.sub.6, 23
.degree. C.): .delta.129.54 (C.sub.5Me.sub.5),79.28 (Th-Me), 10.44
(C.sub.5Me.sub.5), 10.25 (B-Me). Anal. Calcd for
C.sub.58H.sub.36BF.sub.27 Th: C, 46.79; H, 2.44; N, 0.00. Found: C,
46.68; H, 2.24; N. 0.00.
EXAMPLE 4
Synthesis of [Cp.sub.2MCl].sup..sym. [MePBB].sup..crclbar. (M=Zr;
Cp=C.sub.5H.sub.5)
[0205] The procedure of Example 3 above was repeated using
(C.sub.5H.sub.5).sub.2Zr(Cl)Me instead of
(C.sub.5Me.sub.5).sub.2ThMe.sub- .2. This resulted in production of
[(C.sub.5H.sub.5).sub.2ZrCl].sup..sym. [MePBB].sup..crclbar. in 80%
yield. Analytical and spectroscopic data for
[(C.sub.5H.sub.5).sub.2ZrCl].sup..sym. [MePBB].sup..crclbar. are as
follows. .sup.1H NMR (C.sub.7D.sub.8,23.degree. C.): .delta.5.95
(s, 10H, Cp), -0.94 (s, br, 3 H, B--CH.sub.3) .sup.19F NMR
(C.sub.6D.sub.6,23.degr- ee. C.): .delta.-123.41 (s, br, 3 F),
-139.24 (d, .sup.3J.sub.F-F=24.0Hz, 3 F), -139.58 (d,
3J.sub.F-F=21.4Hz,3 F), -139.87 (d, .sup.3J.sub.F-F=23.1 Hz, 3 F),
-155.88 (t, .sup.3J.sub.F-F=21.4 Hz, 3 F), -159.22 (t,
.sup.3J.sub.F-F=22.6 Hz, 3 F), -162.96 (t, .sup.3J.sub.F-F=21.7 Hz,
3 F), -163.63 (t, .sup.3J.sub.F-F=22.6 Hz, 3 F), -164.12 (t,
.sup.3J.sub.F-F=25.4 Hz, 3 F).
EXAMPLE 5
Synthesis of [Cp.sub.2M(Me)(.mu.-Me)(Me)MCp.sub.2].sup..sym.
[MePBB].sup..crclbar. (M=Zr; Cp=C.sub.5H.sub.5,
C.sub.5H.sub.3Me.sub.2, or C.sub.5Me.sub.5)
[0206] Cp.sub.2ZrMe.sub.2 (0.398 mmol) and PBB (0.199 mmol) were
loaded into a 25 mL-flask, which was then attached to the vacuum
line. Pentane (20 mL) was then vacuum-transferred into this flask
at -78.degree. C. The mixture was slowly warmed to room temperature
and stirred for an additional 2 h (Cp=C.sub.5H.sub.5), 15 h
(Cp=C.sub.5H.sub.3Me.sub.2) or 48 h (Cp=C.sub.5Me.sub.5). The
resulting suspension was filtered, and the colored solids (light
pink for C.sub.5H.sub.5, light yellow for C.sub.5H.sub.3Me.sub.2
and yellow for C.sub.5Me.sub.5) were washed with a small amount of
pentane and dried under vacuum: yields 90.3% (C.sub.5H.sub.5),
86.3% (C.sub.5H.sub.3Me.sub.2) and 34.7% (C.sub.5Me.sub.5).
Analytical and spectroscopic data for the C.sub.5H.sub.5 complex
are as follows. .sup.1H NMR(C.sub.6D.sub.6, 23.degree. C.):
.delta.5.65 (s,20H, C.sub.5H.sub.5), -0.04 (s, 6 H, Zr--CH.sub.3),
-0.84 (s, br, 3 H, B--CH.sub.3), -1.15 (s, 3 H, Zr--CH.sub.3--Zr).
.sup.19F NMR (C.sub.6D.sub.6, 23.degree. C.): .delta.124.20 (d,
.sup.3J.sub.F-F=16.6 Hz, 3 F), -138.98 (d, .sup.3J.sub.F-F=20.3 Hz,
3 F), -139.20 (d, .sup.3J.sub.F-F=22.0 Hz, 3 F), -140.29 (d,
.sup.3J.sub.F-F=24.5 Hz, 3 F), -155.15 (t, .sup.3J.sub.F-F=20.9 Hz,
3 F), -160.06 (t, .sup.3J.sub.F-F=22.3 Hz, 3 F), -162.79 (t,
.sup.3J.sub.F-F=22.0 Hz, 3 F), -163.11 (t, .sup.3J.sub.F-F=21.5 Hz,
3 F), -163.97 (t, .sup.3J.sub.F-F=19.0 H, 3 F). .sup.13C NMR
(C.sub.6D.sub.6, 23.degree. C.): .delta.113.24 (C.sub.5H.sub.5),
38.88 (Zr--CH.sub.3), 21.53 (B--CH.sub.3), 15.80
(Zr--CH.sub.3--Zr). Anal. Calcd for
C.sub.60H.sub.32BF.sub.27Zr.sub.2: C, 49.39; H, 2.21; N, 0.00.
Found: C, 48.97; H, 1.92; N 0.00.
[0207] Analytical and spectroscopic data for the
C.sub.5H.sub.3Me.sub.2 complex are as follows. .sup.1H NMR
(C.sub.7D.sub.8, 23.degree. C.): .delta.5.51 (t,
.sup.3J.sub.H-H=2.8 Hz, 4 H, C.sub.5H.sub.3 Me.sub.2), 5.47 (t,
.sup.3J.sub.H-H=3.2 Hz, 4 H, C.sub.5H.sub.3Me.sub.2), 5.18 (t,
.sup.3J.sub.H-H=2.8 Hz, 4 H, C.sub.5H.sub.3Me.sub.2).1.73 (s, 12 H,
C.sub.5H.sub.3Me.sub.2), 1.51 (s, 12 H, C.sub.5H.sub.3MMe.sub.2),
-0.26 (s, 6 H, Zr--CH.sub.3), -0.92 (s, br, 3 H, B--CH.sub.3),
-1.50 (s, 3 H, Zr--CH.sub.3--Zr). .sup.19F NMR (C.sub.6D.sub.6,
23.degree. C.): .delta.123.37 (d, .sup.3J.sub.F-F=15.3 Hz, 3 F),
-139.20 (d,.sup.3J.sub.F-F=24.0 Hz, 3 F), -139.62 (d,
.sup.3J.sub.F-F=24.3 Hz, 3 F), -139.89 (d, .sup.3J.sub.F-F=24.0 Hz,
3 F), -155.81 (t,.sup.3J.sub.F-F=2.14 Hz, 3 F), -159.36 (t,
.sup.3J.sub.F-F=22.3 Hz, 3 F), -163.22 (t, .sup.3J.sub.F-F=21.4 Hz,
3 F), -16.55 (t, .sup.3J.sub.F-F=22.0 Hz, 3 F), -164.20 (t,
.sup.3J.sub.F-F=22.6 Hz, 3 F). .sup.13C NMR (C.sub.6D.sub.6,
23.degree. C.): .delta. 114.20 (d, .sup.1J.sub.CH=17.1 Hz,
C.sub.5H.sub.3Me.sub.2),113.62 (s, C.sub.5H.sub.3Me.sub.2), 112.80
(s, C.sub.5H.sub.3Me.sub.2), 111.29 (d, .sup.3J.sub.CH=165.7 Hz,
C.sub.5H.sub.3Me.sub.2), 106,57 (d, .sup.1J.sub.CH=173.3 Hz.
C.sub.5H.sub.3Me.sub.2), 41.63 (q, .sup.1J.sub.CH=118.4 Hz,
Zr--CH.sub.3), 31.26 (q, .sup.1J.sub.CH=116.5 Hz, B--CH.sub.3),
22.21 (q, .sup.1J.sub.CH=134.3 Hz, Zr--CH.sub.3--Zr), 12.94 (q,
.sup.1J.sub.CH=128.0 Hz, C.sub.5H.sub.2Me.sub.2), 12.71 (q,
.sup.1J.sub.CH=127.6 Hz. C.sub.5H.sub.2Me.sub.2). Anal. Calcd for
C.sub.68H.sub.48BF.sub.27Z.sub.2: C, 51,98; H, 3.08; N, 0.00.
Found: C, 51.61; H, 3.00; N, 0.00.
[0208] Analytical and spectroscopic data for the C.sub.5Me.sub.5
complex are as follows. .sup.1H NMR (C.sub.6D.sub.6, 23.degree.
C.): .delta.1.57 (s, 60 H, C.sub.5Me.sub.5) -0.84 (s, br, 3 H,
B--CH.sub.3). The bridging and terminal methyl groups are discrete
at low temperature. .sup.1H NMR (C.sub.7D.sub.8, -13.degree. C.):
.delta.-0.19 (s, br, 6 H. Zr--CH.sub.3), -0.92 (s, br, 3 H,
B--CH.sub.3), -2.42 (s, br, 3 H, Zr--CH.sub.3--Zr). .sup.19F NMR
(C.sub.6D.sub.6, 23.degree. C.): .delta.-123.11 (d, s, br, 3 F),
-139.27 (d, .sup.3J.sub.F-F=20.3 Hz, 3 F), -139.67 (t,
.sup.3J.sub.F-F=25.1 Hz, 6F), -155.73 (t, .sup.3J.sub.F-F=20.9 Hz,3
F), -160.91 (s, br, 3 F), -163.25 (t, .sup.3J.sub.F-F=21.7 Hz, 3F),
-163.56(t,.sup.3J.sub.F-F=22.0 Hz, 3 F), -164.13 (t,
.sup.3J.sub.F-F=21.4 Hz, 3 F). Anal. Calcd for
C.sub.80H.sub.72BF.sub.27Zr.sub.2: C, 55.23; H, 4.17; N, 0.00.
Found: C, 54.81; H, 3.98; N, 0.00.
EXAMPLE 6
Synthesis of [Cp.sub.2M(H)(.mu.-H)(H)ZrCp.sub.2].sup..sym.
[MePBB].sup..crclbar.; (M=Zr; Cp=C.sub.5H.sub.5 or
C.sub.5H.sub.3Me.sub.2)
[0209] The procedure here is similar to that of Example 5, except
that the reaction was carried out under 1 atm of H.sub.2 for 15 h:
yields 81.6% (Cp=C.sub.5H.sub.5, grey solid) and 75.6%
(Cp=C.sub.5H.sub.3Me.sub.2, orange solid). Analytical and
spectroscopic data for Cp=C.sub.5H.sub.5 are as follows. .sup.1H
NMR (C.sub.6D.sub.6, 58.degree. C.): .delta.6.67 (s, br, 2 H,
Zr--H), 5.64 (s, 20 H, C.sub.5H.sub.5), -0.81 (s, br, 3 H,
B--CH.sub.3), -1.38 (s, br, 1 H, Zr--H--Zr). The chemical shifts
and splitting patterns of .sup.19F NMR are same as those of Example
5 (Cp=C.sub.5H.sub.5). Anal. Calcd. for
C.sub.57H.sub.26BF.sub.27Zr.sub.2: C, 48.31; H, 1.85; N, 0.00.
Found: C, 47.90; H, 1.92; N, 0.00.
[0210] Analytical and spectroscopic data for
Cp=C.sub.5H.sub.3Me.sub.2 are as follows. .sup.1H NMR
(C.sub.7D.sub.8, 23.degree. C.): .delta.5.81 (m, 4 H,
C.sub.5H.sub.3Me.sub.2), 5.50 (m, 4 H, C.sub.5H.sub.3Me.sub.2), 523
(m, 4 H, C.sub.5H.sub.3Me.sub.2). 1.65 (m, 24 H,
C.sub.5H.sub.3Me.sub.2), 0.25 (s, br, 2 H, Zr--H), -0.94 (s, br, 3
H, B--CH.sub.3), -1.52 (s, br, I H, Zr--H--Zr). The chemical shifts
and splitting patterns of .sup.19F NMR are same as those of Example
5 (Cp=C.sub.5H.sub.3Me.sub.2). Anal. Calcd for
C.sub.65H.sub.42BF.sub.27Zr.sub.2: C, 51.05; H, 2.77; N, 0.00.
Found C, 51.07; H. -2.63; N. 0.00.
EXAMPLE 7
Synthesis of [Cp.sub.2MMe].sup..sym. [MePBB].sup..crclbar. (M=Zr;
Cp=C.sub.5H.sub.5, C.sub.5H.sub.3Me.sub.2, or C.sub.5Me.sub.5)
[0211] (a) Cp=C.sub.5H.sub.5. In a J-Young NMR tube, a small amount
of a mixture of (C.sub.5H.sub.5).sub.2ZrMe.sub.2 and PBB (1:1.2
molar ratio) was dissolved in C.sub.6D.sub.6). The NMR tube was
then put in an NMR probe and heated at 60.degree. C. After 0.5 h,
.sup.1H NMR revealed the above monomeric species formed. The same
structure was obtained by the reaction of the C.sub.5H.sub.5
product of Example 5 with an excess of PBB at 60.degree. C. for 0.5
h. In a polymerization test, these species were also generated in
situ by mixing (C.sub.5H.sub.5).sub.2ZrMe.sub.2 and PBB at
60.degree. C. for 0.5 h. .sup.1H NMR (C.sub.6D.sub.6, 60.degree.
C.) for: .delta.5.70 (s, 10 H, C.sub.5H.sub.5), 0.14 (s, 3 H,
Zr--CH.sub.3), -0.85 (s, br, 3 H, B--CH.sub.3). .sup.19F NMR is
similar to that of the corresponding dinuclear species of Example 5
(Cp=C.sub.5H.sub.5).
[0212] (b) Cp=C.sub.5H.sub.3Me.sub.2). The same procedure of
Example 5(a) was used to prepare this species. In the
polymerization test, the following was observed: .sup.1H NMR
(C.sub.7D.sub.8, 60.degree. C.) for 8: .delta.5.68 (t, 3 J H-H=2.8
Hz, 4 H, C.sub.5H.sub.3M.sub.2), 5.36 (t, .sup.3J.sub.H-H=3.1 Hz, 4
H, C.sub.5H.sub.3Me.sub.2), 5.23 (t, .sup.3JH-H=2.8 Hz, 4 H,
C.sub.5H.sub.3Me.sub.2).1.76 (s, 6 H, C.sub.5H.sub.3Me.sub.2), 1.56
(s, 6 H, C.sub.5H.sub.3Me.sub.2), 0.17 (s, 3 H, Zr--CH.sub.3),
-0.93 (s, br, 3 H, B--CH.sub.3). .sup.19F NMR of this species is
similar to that of the corresponding dinuclear species of Example 5
(Cp=C.sub.5Me.sub.5). .sup.13C NMR (C.sub.7D.sub.8, 60.degree. C.):
.delta.17.74 (C.sub.5H.sub.3Me.sub.2), 112.14
(C.sub.5H.sub.3Me.sub.2), 108.01 (C.sub.5H.sub.3Me.sub.2), 42.11
(Zr--CH.sub.3), 34.43 (B--CH.sub.3), 12.63
(C.sub.5H.sub.2Me.sub.2), 12.45 (C.sub.5H.sub.2Me.sub.2).
[0213] (c) Cp=C.sub.5Me.sub.5. The same procedure of Example 5(a)
was used to prepare this species. In the polymerization test, the
following was observed: .sup.1H NMR (C.sub.6D.sub.6, 60.degree.
C.): .delta.1.61 (s, 30 H, C.sub.5Me.sub.5), 0.13 (s, 3 H,
Zr--CH.sub.3), -0.86 (s, br, 3 H, B--CH.sub.3). .sup.19F NMR is
similar to that of the corresponding dinuclear species of Example
5, Cp=C.sub.5Me.sub.5.
EXAMPLE 8
Synthesis of [CpM(Me).sub.2].sup..sym. [MePBB].sup..crclbar. (M=Ti;
Cp=C.sub.5Me.sub.5)
[0214] The catalyst product of FIG. 5 was generated in an NMR tube
reaction by mixing C.sub.5Me.sub.5TiMe.sub.3 and PBB at 1:1 molar
ratio in C.sub.6D.sub.6 for 2 h. .sup.1H NMR (C.sub.6D.sub.6,
23.degree. C.): .delta.9.03 (s, br, 2 H. CH.sub.2), 1.69 (s, 6 H,
C.sub.5Me.sub.4), 1.65 (s, 6 H, C.sub.5Me.sub.4), 0.15 (s, 3 H,
Ti--CH.sub.3), -0.82 (s, br, 3 H, B--CH.sub.3).
EXAMPLE 9
Synthesis of
{[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]MMe}.sup..sym.
[MePBB].sup..crclbar. M=Zr or Ti)
[0215] (a) M=Zr. [Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]ZrMe.sub.2
(0.199 mmol) and PBB (0.199 mmol) were treated in the same way as
in the synthesis of Example 3 except that here the reaction time
was 2 hours. This procedure yielded 73.1% of
{[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]- ZrMe}.sup..sym.
[MePBB].sup..sym.(yellow solid). Analytical and spectroscopic data
are as follows. .sup.1H NMR (C.sub.7D.sub.8, 23.degree. C.):
.delta.1.73 (s, 3 H, C.sub.5Me.sub.4), 1.69 (s, 3 H,
(C.sub.5Me.sub.4), 1.63 (s, 3 H, C.sub.5Me.sub.4), 1.43 (s, 3 H,
C.sub.5Me.sub.4), 0.85 (s, 9 H, N-tBu), 0.28 (s, 3 H, SiMe.sub.2),
0.21 (s, 3 H, SiMe.sub.2), -0.48 (s, 3 H, Zr--CH.sub.3), -0.95 (s,
br,3 H, B--CH.sub.3). .sup.19F NMR (C.sub.7D.sub.8, 23 .degree.
C.): .delta.-124.20 (s, br,3 F), -139.14 (d, .sup.3J.sub.F-F=23.7
Hz, 3 F), -139.35 (d, .sup.3J.sub.F-F=22.0 Hz, 3 F), -139.93 (d,
.sup.3J.sub.F-F=21.2 Hz, 3 F), -155.79 (t, .sup.3J.sub.F-F=21.2 Hz,
3 F), -159.67 (t, .sup.3J.sub.F-F=22.3 Hz, 3 F), -163.28 (t,
.sup.3J.sub.F-F=21.7 Hz, 3 F), -163.87 (t, .sup.3J.sub.F-F=22.6 Hz,
3 F), -164.13 (t, .sup.3J.sub.F-F=22.6 Hz, 3 F). .sup.13C NMR
(C.sub.7D.sub.8, 23.degree. C.): .delta. 130.22 (C.sub.5Me.sub.4),
128.18 (C.sub.5Me.sub.4), 127.22 (C.sub.5Me.sub.4), 126.47
(C.sub.5Me.sub.4), 124.37 (C.sub.5Me.sub.4), 58.47 (N-CMe.sub.3),
34.37 (Zr--CH.sub.3), 34.10 (N-CMe3), 15.89 (C.sub.5Me.sub.4),
13.46 (C.sub.5Me.sub.4), 11.77 (C.sub.5Me.sub.4), 10.99
(C.sub.5Me.sub.4), 7.92 (SiMe.sub.2), 5.65 (SiMe.sub.2). Anal.
Calcd for C.sub.53H.sub.33BF.sub.27NSiZr: C, 47.97; H, 2.51; N,
1.06, Found: C, 47.79; H, 2.58; N, 0.86.
[0216] (b) M=Ti. The procedure of 9(a) was repeated using
[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]TiMe.sub.2 but with a
reaction time of 4 hours instead of 2 hours. This procedure yielded
47.0% of {[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]TiMe}.sup..sym.
[MePBB].sup..sym. (orange solid). The spectroscopic data are
similar to those of 9(a) above.
EXAMPLE 10
Synthesis of [CpM(Me).sub.2].sup..sym. [MePBB].sup..sym. (M=Zr or
Hf; Cp=C.sub.5Me.sub.5)
[0217] C.sub.5Me.sub.5MMe.sub.3 (0.199 mmol) and PBB (0.191 g,
0.199 mmol) were treated in the same manner as in Example 3 to
produce 0.174 g of [C.sub.5Me.sub.5Zr(Me).sub.2].sup..sym.
[MePBB].sup..sym. and 0.144 g of
[C.sub.5Me.sub.5Hf(Me).sub.2].sup..sym. [MePBB].sup..sym. as yellow
solids in yields of 69.1% and 43.6%, respectively. An NMR reaction
showed that a quantitative yield of these complexes was achieved if
isolation of the product is not required. Analytical and
spectroscopic data for [C.sub.5Me.sub.5Zr(Me).sub.2].sup..sym.
[MePBB].sup..sym. are as follows. .sup.1H NMR (C.sub.7D.sub.8,
23.degree. C.): .delta. 7.14 (s, 3 H, 1/2 C.sub.6H.sub.6), 1.40 (s,
15 H, (C.sub.5Me.sub.5), -0.60 (s, 6 H, Zr--CH.sub.3), -0.95 (s,
br, 3 H, B-CH.sub.3). .sup.19F NMR (C.sub.7D.sub.8, 23.degree. C.):
.delta.-124.21 (d, .sup.3J.sub.F-F=21.5 Hz, 3 F), -139.06 (t,
.sup.3J.sub.F-F=24.5 Hz, 6 F), -140.10 (d, .sup.3J.sub.F-F=23.7 Hz,
3 F), -155.42 (t, .sup.3J.sub.F-F=20.9 Hz, 3 F), -159.66 (s, br, 3
F), -163.14 (t, .sup.3J.sub.F-F=21.5 Hz, 3 F), -163.54 (t,
.sup.3J.sub.F-F=24.5 Hz, 3 F), -163.93 (t, .sup.3J.sub.F-F=21.7 Hz,
3 F). .sup.13C NMR (C.sub.7D.sub.8, 23.degree. C.): .delta. 128.29
(d, .sup.1J.sub.C-H=158.2 Hz, C.sub.6H.sub.6), 123.13 (s,
C.sub.5Me.sub.5), 45.07 (q, .sup.1J.sub.C-H=119.8 Hz,
Zr--CH.sub.3), 11.31 (q, .sup.1J.sub.C-H=127.38 Hz,
C.sub.5Me.sub.5). Anal. Calcd. for
C.sub.49H.sub.24BF.sub.27Zr.1/2C.sub.6H.sub.6:C, 49.30; H, 2.15.
Found: C, 49.18; H, 2.07. Analytical and spectroscopic data for
[C.sub.5Me.sub.5Hf(Me).sub.2].sup..sym. [MePBB].sup..sym. areas
follows. .sup.1H NMR (C.sub.7D.sub.8,23.degree. C.): .delta. 7.14
(s, 1.5 H, 1/4 C.sub.6H.sub.6), 1.46 (s, 15 H, C.sub.5Me.sub.5),
-0.84 (s, 6 H, Hf-CH.sub.3), -0.95 (s, br, 3 H, B-CH.sub.3).
.sup.19F NMR (C.sub.6D.sub.6, 23.degree. C.): .delta.-124.14 (d,
.sup.3J.sub.F-F=21.4 Hz, 3 F), -139.29 (t, .sup.3J.sub.F-F=22.6 Hz,
6 F), -140.12 (d, .sup.3J.sub.F-F=24.5 Hz, 3 F), -155.52 (t,
.sup.3J.sub.F-F=21.4 Hz, 3 F), -159.69 (t, .sup.3J.sub.F-F=22.6 Hz,
3 F), -162.91 (t, .sup.3J.sub.F-F=21.4 Hz, 3 F), -163.49 (t,
.sup.3J.sub.F-F=23.1 Hz, 3 F), -164.00 (t, .sup.3J.sub.F-F=22.3 Hz,
3 F). .sup.13C NMR (C.sub.66, 23.degree. C.); .delta.124.89
(C.sub.5Me.sub.5), 49.59 (Hf-Me), 11.07 (C.sub.5Me.sub.5), 10.85
(B-Me). Anal. Calcd for C.sub.49H.sub.24BF.sub.2- 7Hf
1/4C.sub.6H.sub.6: C, 45.5; H, 1.93. Found: C, 45.16; H, 2.08.
EXAMPLE 11
In Situ Generation of
{[rac-Me.sub.2Si(Ind).sub.2MMe].sub.2(.mu.-Me)}.sup.- .sym.
[MePBB].sup..sym. (M=Zr)
[0218] rac-Me.sub.2Si(Ind).sub.2ZrMe.sub.2 (8.2 mg, 0.020 mmol) and
PBB (9.6 mg, 0.010 mmol) were loaded into a J-Young NMR tube and
benzene-d.sub.6 was condensed in. The mixture was allowed to react
at room temperature for 1 h before the NMR spectrum was recorded. A
pair of diastereomers was formed in a2:1 ratio. .sup.1H NMR
(C.sub.6D.sub.6,23.degree. C.) for diastereomer A: .delta.7.30-6.78
(m, 16 H, C.sub.6H.sub.4), 5.68 (D, J.sub.H-H=2.5 Hz, 4 H,
C.sub.5H.sub.2), 5.31 (d, J.sub.H-H=2.5 Hz, 4 H, C.sub.5H.sub.2),
0.68 (s, 6 H, SiMe.sub.2), 0.47 (s, 6 H, SiMe.sub.2), -0.83 (s, br,
3 H, B--CH.sub.3), -0.92 (s, 6 H, Zr-CH.sub.3), -2.87 (s,3 H,
Zr--CH.sub.3--Zr). Diastereomer B: .delta.7.30-6.78 (m, 16 H,
C.sub.6H.sub.4), 6.59 (d, J.sub.H-H=2.5 Hz, 4 H, C.sub.5H.sub.2),
5.93 (d, J.sub.H-H=2.5 Hz, 4 H, C.sub.5H.sub.2), 0.67 (s, 6 H,
SiMe.sub.2), 0.44 (s, 6 H, SiMe.sub.2), -0.83 (s, br, 3 H,
B--CH.sub.3), 0.96 (s, 6 H, Zr--CH.sub.3), -3.07 (s, 3 H,
Zr--CH.sub.3--Zr). .sup.19F NMR (C.sub.6D.sub.6, 23.degree. C.:
.delta.-123.00 (d, .sup.3J.sub.F-F=17.5 Hz, 3 F), -139.28 (m, 6 F),
-140.09 (d,.sup.3J.sub.F-F=21.5 Hz, 3 F), -156.02 (t,
.sup.3J.sub.F-F=20.9 Hz, 3 F), -159.90 (t, J.sub.F-F=22.3 Hz, 3F),
-163.26 (t, J.sub.F-F=22.3 Hz, 3F), -163.67 (t,
.sup.3J.sub.F-F=22.5 Hz, 3 F), -164.20 (t,.sup.3J.sub.F-F=22.6 Hz,
3 F).
EXAMPLE 12
Synthesis of {[Me.sub.2C(Flu)(Cp)MMe].sub.2(.mu.-Me)}.sup..sym.
[MePBB].sup..sym. (M=Zr)
[0219] In a glovebox, Me.sub.2C(Flu)(Cp)ZrMe.sub.2 (39.2 mg, 0.100
mmol) and PBB (47.8 mg, 0.050 mmol) were loaded into a 25-mL
reaction flask having filter frit and the flask was reattached to
the high vacuum line. Benzene (20 mL) was then vacuum-transferred
into the flask at -78.degree. C. The mixture was slowly allowed to
warm to room temperature and stirred for an additional 2 hours. The
solvent was removed in vacuo, and pentane (20 mL) was condensed
into the flask. The resulting suspension was filtered, and the
collected solid was washed with 5 mL of pentane and dried under
vacuum to afford 73.9 mg of the title complex, yield 80.5%. Two
diastereomers are formed in a 1.8 (isomer A): 1 (isomer B) ratio.
.sup.1H NMR (C.sub.7D.sub.8, 23.degree. C.) for diastereomer A:
.delta.7.52 (t, J.sub.H-H=7.2 Hz 4 H, C.sub.6H.sub.4), 7.30 (t,
J.sub.H-H=7.2 Hz, 4H, C.sub.6H.sub.4), 7.10 (t, J.sub.H-H=7.2 Hz, 4
H, C.sub.6H.sub.4), 7.09-6.86 (m, 6H, C.sub.6H.sub.4), 6.23 (d,
J.sub.H-H=2.4 Hz, 2H, C.sub.5H.sub.4), 5.49 (d, J.sub.H-H=2.4 Hz, 2
H, C.sub.5H.sub.4), 5.17 (d, J.sub.H-H=2.4 Hz, 2 H,
C.sub.5H.sub.4),4.88 (d, J.sub.H-H=2.4 Hz, 2 H, C.sub.5H.sub.4),
1.76 (s, 6 H, CMe.sub.2), 1.62 (s, 6 H, CMe.sub.2), -0.91 (s, br, 3
H, B-CH.sub.3), -1.21 (s, 6 H, Zr--CH.sub.3), -3.38 (s, 3 H,
Zr--CH.sub.3--Zr). Isomer B: .delta.7.71 (d, J.sub.H-H=8.4 Hz, 4 H,
C.sub.6H.sub.4),7.61 (d, J.sub.H-H=8.4 Hz, 4 H, C.sub.6H.sub.4),
7.23 (t, J.sub.H-H=7.2 Hz, 4 H, C.sub.6H.sub.4), 7.09-6.86 (m, 6 H,
C.sub.6H.sub.4), 6.17 (d, J.sub.H-H=2.4 Hz, 2 H, C.sub.5H.sub.4),
5.51 (d, J.sub.H-H=2.4 Hz, 2 H, C.sub.5H.sub.4),5.08 (d,
J.sub.H-H=2.4 Hz, 2 H, C.sub.5H.sub.4), 4.78 (d, J.sub.H-H=2.4 Hz,
2 H, C.sub.5H.sub.4), 1.78 (s, 6 H, CMe.sub.2), 1.62 (s, 6 H,
CMe.sub.2), -0.91 (s, br, 3 H, B--CH.sub.3), -1.27
(s,6H,Zr--CH.sub.3), -3.29 (s, 3 H,Zr--CH.sub.3-Zr). .sup.19F
NMR(C.sub.7D.sub.8, 23.degree. C.): .delta.-123.56 (s, br, 3 F),
-138.86 (d, .sup.3J.sub.F-F=23.9 Hz, 3 F), -139.45 (d,
.sup.3J.sub.F-F=21.4 Hz,3 F), -139.74 (d, .sup.3J.sub.F-F=21.5 Hz,
3 F), -156.79 (t, .sup.3J.sub.F-F=20.9 Hz, 3 F), -159.94 (t,
.sup.3J.sub.F-F=22.6 Hz, 3 F), -163.20 (t, .sup.3J.sub.F-F=20.9 Hz,
3 F), -163.75 (t, .sup.3J.sub.F-F=22.5 Hz, 3 F), -164.14 (t,
.sup.3J.sub.F-F=22.6 Hz, 3 F). Anal. Calcd for
C.sub.82H.sub.48BF.sub.27Zr.sub.2: C, 56.62; H, 2.78. Found: C,
55.80; H, 2.10.
EXAMPLE 13
Conversion of [Cp.sub.2M(Me)(.mu.-Me)(Me)MCp.sub.2].sup..sym.
[MePBB].sup..crclbar. to
[Cp.sub.2M(Me)(.mu.-F)(Me)MCp.sub.2].sup..sym.
[MePBB].sup..crclbar. (M=Zr; C.sub.5H.sub.3Me.sub.2)
[0220] Upon standing at 25.degree. C. for four days or at
80.degree. C. for 1 hour, a solution of
[(C.sub.5H.sub.3Me.sub.2).sub.2Zr(Me)(.mu.-Me)(-
Me)Zr(C.sub.5H.sub.3Me.sub.2).sub.2].sup..sym.
[MePBB].sup..crclbar. in C.sub.7D.sub.8 decomposed to yield
[(C.sub.5H.sub.3Me.sub.2).sub.2Zr(Me)(-
.mu.-F)(Me)Zr(C.sub.5H.sub.3Me.sub.2).sub.2].sup..sym.
[MePBB].sup..crclbar., which was characterized both
spectroscopically and analytically from a scale-up synthesis in
toluene. .sup.1H NMR (C.sub.7D.sub.8, 23.degree. C.): .delta. 5.68
(t, .sup.3J.sub.H-H=2.8 Hz, 4 H, C.sub.5H.sub.3Me.sub.2),5.36
(t,.sup.3J.sub.H-H=3.1 Hz, 4 H, C.sub.5H.sub.3Me.sub.2), 5.23 (t,
.sup.3J.sub.H-H=2.8 Hz, 4 H, C.sub.5H.sub.3Me.sub.2), 1.71 (s, 12
H, C.sub.5H.sub.3Me.sub.2), 1.43 (s, 12 H, C.sub.5H.sub.3Me.sub.2),
0.12 (d, .sup.3J.sub.H-F=2.1 Hz, 6 H, Zr--CH.sub.3), -0.92 (s, br,
3 H, B-CH.sub.3). .sup.19F NMR spectrum is the same as that of
[(C.sub.5H.sub.3Me.sub.2).sub.2Zr(Me)(.mu.-Me)(Me)Zr(-
C.sub.5H.sub.3Me.sub.2).sub.2].sup..sym. [MePBB].sup..crclbar.
except there is an extra peak at -91.27 ppm (s) for the bridging F
signal. .sup.13C NMR (C.sub.7D.sub.8, 23.degree. C.): .delta.
117.74 (C.sub.5H.sub.3Me.sub.2),114.33
(C.sub.5H.sub.3Me.sub.2),112.14 (C.sub.5H.sub.3Me.sub.2),111.45
(C.sub.5H.sub.3Me.sub.2), 108.01 (C.sub.5H.sub.3Me.sub.2), 42.11
(Zr-CH.sub.3),34.43 (B--CH.sub.3), 12.63 (C.sub.5H.sub.3Me.sub.2),
12.45 (C.sub.5H.sub.3Me.sub.2). Anal. Calcd for
C.sub.67H.sub.45BF.sub.28Zr.sub.2: C, 51.09; H, 2.88. Found: C,
50.71; H, 2.61.
EXAMPLE 14
Synthesis of Cp.sub.2MMe.sup..sym.
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.- 9)Me].sup..crclbar. (M=Zr;
Cp=C.sub.5H.sub.5)
[0221] (C.sub.5H.sub.5).sub.2ZrMe.sub.2 (50 mg, 0.21 mmol) and
(C.sub.6F.sub.5).sub.2B(Cl.sub.2F.sub.9) (146 mg, 0.22 mmol) were
loaded into a 25-mL reaction flask in a glove box. On the high
vacuum line, C.sub.6H.sub.6 (15 mL) was condensed in at -78.degree.
C. The solution was then stirred at room temperature for 1 h, and
all the volatiles were removed under high vacuum to give a yellow
solid. Pentane was condensed in to wash the solid twice, and the
yellow solid was dried under vacuum (10.sup.-5 torr) for 4 h at
room temperature. Yield, 110 mg (61%). The spectroscopic data for
(C.sub.5H.sub.5).sub.2ZrMe.sup..sym.
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar. are as
follows. .sup.1H NMR (benzene-d.sub.6, 299.91 MHz, 23.degree. C.)
.delta.5.47 (s, 10 H, C.sub.5H.sub.5), 0.32 (s,3H, ZrCH.sub.3),
0.24 (br,3 H, BCH.sub.3). .sup.13C NMR (benzene-d.sub.6, 74.42 MHz,
23.degree. C.) .delta. 114.04 (C.sub.5H.sub.5),40.92 (ZrCH.sub.3),
.sup.19F NMR(benzene-d.sub.6, 282.33 MHz,23.degree. C.)
.delta.-128.75 (s, 1 F, 3-F), -132 (very broad, 4 F, o-F), -136.80
(s, 1 F, 6-F), -138.94 (s, 2 F, 2', 6'-F), -153.48 (t,
.sup.3J.sub.F-F=21.1 Hz, 1 F, 4'-F), -156.46 (t,
.sup.3J.sub.F-F=22.2 Hz, 1 F, 4-F), -158.41 (multi, 3 F, p-F, 5-F),
-162.91 (s, 2 F, 3', 5'-F), -164.00 (br, 4 F, m-F), Anal. Calcd.
for C.sub.36Hl.sub.6BF.sub.19Zr; C, 47.44; H, 1.76. Found: C,
47.09, H, 1.67.
EXAMPLE 15
Synthesis of rac-Me.sub.2Si(Cp).sub.2MMe.sup..sym.
[(C.sub.6F.sub.5).sub.2- B(C.sub.12F.sub.9)Me].sup..crclbar. (M=Zr;
Cp=C.sub.9H.sub.7)
[0222] rac-Me.sub.2Si(Ind).sub.2ZrMe.sub.2 (50 mg,0.13 mmol) and
(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9) (87 mg,0.13 mmol) were
loaded into a 25-mL reaction flask in a glove box. On the high
vacuum line, C.sub.6H.sub.6(10 mL) was condensed in at -78.degree.
C. The solution was then stirred at room temperature for 1 h, and
all of the volatiles were removed under high vacuum to give a
yellow solid. Pentane was condensed in to wash the solid twice, and
the yellow solid was dried under vacuum (10.sup.-5 torr) for 4 h at
room temperature. Yield, 82 mg (60%). The spectroscopic data for
rac-Me.sub.2Si(Ind).sub.2ZrMe.sup..sym.
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar. are as
follows. .sup.1H NMR (C.sub.6D.sub.6, 23.degree. C., 399.941 MHz):
.delta. 7.63 (d, .sup.3J.sub.H-H=8.5 Hz, 1 H, Ind), 7.26 (d,
.sup.3J.sub.H-H=8.5 Hz, 1 H, Ind). 7.06 (t, .sup.3J.sub.H-H=7.4 Hz,
1 H, Ind), 6.99 (d, .sup.3J.sub.H-H=8.4 Hz, 1 H, Ind), 6.62 - 6.72
(m, 2 H, Ind), 6.58 (d, .sup.3J.sub.H-H=3.0 Hz, 1 H, Ind), 6.54 (d,
.sup.3J.sub.H-H=7.8 Hz, 1 H, Ind), 6.26 (d, 1 H .sup.3J.sub.H-H=8.1
Hz, Ind), 6.21 (d, 1 H .sup.3J.sub.H-H=3.0 Hz, Ind), 5.65 (d, 1 H
.sup.3J.sub.H-H=3.3 Hz, Ind), 4.95 (d, 1 H .sup.3J.sub.H-H=3.3 Hz,
Ind), 0.36 (s, 3 H, Me.sub.2Si), 0.21 (s, 3 H, Me.sub.2Si), -0.32
(s, br, 3 H, B--CH.sub.3), -0.55 (s, 3 H, Zr--CH.sub.3). .sup.19F
NMR (benzene-d.sub.6, 282.33 MHz, 23.degree. C.) .delta.-127.53 (s,
1 F, 3-F), -131 (verybroad, 4 F, o-F), -137.15 (m, 1 F, 6-F),
-137.94 (m, 2 F, 2', 6'-F), -153.74 (t, .sup.3J.sub.F-F=21 Hz, 1 F,
4'-F), -156.65 (t, .sup.3J.sub.F-F=22 Hz, 1 F, 4-F), -158.56 (m, 2
F, p-F), -159.26 (t, .sup.3J.sub.F-F=21 Hz, 1 F, 5-F), -162.75 (br,
1 F, 3'/5'-F), -163.33 (br, 1 F, 3'/5'-F), -164.16 (br, 4 F, m-F).
Anal. Calcd. for C.sub.46H.sub.24BF.sub.19Zr: C, 53.14; H, 2.33.
Found: C, 52.82, H, 2.37.
EXAMPLE 16
Synthesis of
{[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]MMe}.sup..sym.
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar.
(M=Zr)
[0223] CGCZrMe.sub.2 (80 mg, 0.22 mmol)
(C.sub.6F.sub.5).sub.2B(C.sub.12F.- sub.9) (142 mg, 0.22 mmol) were
loaded into a 25 mL reaction flask in the glove box. On the high
vacuum line C.sub.6H.sub.6 (15 mL) was condensed in at -78.degree.
C. The solution was then stirred at room temperature for 1 h, and
all the volatiles were removed under high vacuum to give a yellow
solid. Pentane was condensed in to wash the solid twice, and the
yellow solid was dried under vacuum (10.sup.-5 torr) for 4 hours at
room temperature. Yield, 119 mg (53%). The spectroscopic data for
{[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]MMe}.sup..sym.
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar. are as
follows. .sup.1H NMR (benzene-d.sub.6, 299.91 MHz, 23.degree. C.)
.delta. 1.73 (s,3 H, CH.sub.3), 1.68 (s,3 H, CH.sub.3),1.59 (s,3 H,
CH.sub.3), 1.46 (s,3 H, CH.sub.3), 1.00 (s, 12 H,
CMe.sub.3/BCH.sub.3), 0.31 (s, 3 H, ZrCH.sub.3), 0.24 (s, 3 H,
SiCH.sub.3), 0.17 (s, 3 H, SiCH.sub.3), .sup.13C NMR
(benzene-d.sub.6, 74.42 MHz, 23.degree. C.) .delta. 57.74
(ZrCH.sub.3), 44.27 (CMe.sub.3), 33.05 (CMe.sub.3),15.04
(CH.sub.3),12.74 (CH.sub.3),11.37 (CH.sub.3),10.37 (CH.sub.3),5.54
(SiCH.sub.3),5.12 (SiCH.sub.3), .sup.19F NMR (benzene-d.sub.6,
282.33 MHz, 23.degree. C.) .delta.-129.31 (s, 1 F, 3-F), -131.67
(br, 4 F, o-F), -136.49 (s, 1 F, 6-F), -138.38 (s, 2 F, 2', 6'-F),
-153.48 (t,.sup.3J.sub.F-F=21.3 Hz, 1 F, 4'-F), -156.02 (t,
.sup.3J.sub.F-F=21.5 Hz, 1 F, 4-F), -158.42 (s, 3 F, p-F, 5-F),
-162.99 (s, 2 F, 3', 5'-F), -163.89 (br, 4 F, m-F). Anal. Calcd.
for C.sub.41H.sub.33BF.sub.19NSiZr: C, 47.77; H, 3.22. Found: C,
47.10, H, 3.01.
EXAMPLE 17
Synthesis of
{[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]MMe}.sup..sym.
[(C.sub.6F.sub.%).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar.
(M=Ti)
[0224] CGCTiMe.sub.2 (70 mg, 0.21 mmol) and
(C.sub.6F.sub.5).sub.2B(C.sub.- 12F.sub.9) (141 mg, 0.21 mmol) were
loaded into a 25 mL reaction flask in the glove box. On the high
vacuum line C.sub.6H.sub.6 (15 mL) was condensed in at -78.degree.
C. The solution was then stirred at room temperature for 1 hour,
and all the volatiles were removed under high vacuum to give a
yellow solid. Pentane was condensed in to was the solid twice, and
the yellow solid was dried under vacuum (10.sup.-5 torr) for 4
hours at room temperature. Yield, 101 mg (48%). The spectroscopic
data for {[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)]MMe}.sup..sym.
[(C.sub.6F.sub.%).sub.2B(C.sub.12F.sub.9)Me].sup..crclbar. are as
follows. .sup.1H NMR (benzene-d.sub.6, 299.91 MHz, 23.degree. C.)
.delta. 1.71 (s, 3 H, CH.sub.3),1.54 (s, 3 H, CH.sub.3),1.53 (s, 3
H, CH.sub.3), 1.41 (s, 3 H, CH.sub.3), 0.99 (s, 9 H, CMe.sub.3),
0.95 (s, 3 H, TiCH.sub.3), 0.66 (br, 3 H, BCH.sub.3), 0.29 (s, 3 H,
SiCH.sub.3), 0.16 (s, 3 H, SiCH.sub.3), .sup.19F NMR
(benzene-d.sub.6, 282.33 MHz, 23.degree. C.) .delta.-126.96 (s, 1
F, 3-F), -131.04 (br, 4 F, o-F), -136.85 (m, 1 F, 6-F), -138.10 (s,
2 F, 2', 6'-F), -153.60 (t,.sup.3J.sub.F-F=21 Hz, 1 F, 4'-F),
-156.26 (.sup.3J.sub.F-F=22 Hz, 1 F, 4-F), -158.44 -158.75 (m, 2 F,
p-F), -158.84 (t, .sup.3J.sub.F-F=22 Hz, 1 F, 5-F), -162.90 (s, 1
F, 3'/5'-F), -163.34 (s, 1 F, 3'/5'-F), -164.12 (br, 4 F, m-F).
Anal. Calcd. for C.sub.41H.sub.33BF.sub.19NSiTi: C, 49.87; H, 3.37.
Found: C, 49.89, H, 3.43.
[0225] Analogous catalytic complexes of this invention are formed
when Examples 3-17 are repeated using chemically equivalent amounts
of organoboranes of formula (I), or organoboranes of formula (II),
or of formula (III), in place of the organoboranes used in Examples
3-17.
[0226] Polymerization Reactions and Supported Cocatalysts of this
Invention
[0227] The catalytic complexes of this invention are effective for
use as catalysts for producing a variety of homopolymers and
copolymers. When employed as catalysts, the catalytic complexes of
this invention can be used in solution or deposited on a solid
support. When used in solution polymerization, the solvent can be,
where applicable, a large excess quantity of the liquid olefinic
monomer. Typically, however, an ancillary inert solvent, typically
a liquid paraffinic or aromatic hydrocarbon solvent is used, such
as heptane, isooctane, decane, toluene, xylene, ethylbenzene,
mesitylene, or mixtures of liquid paraffinic hydrocarbons and/or
liquid aromatic hydrocarbons. When the catalytic complexes of this
invention are supported on a carrier, the solid support or carrier
can be any suitable particulate solid, and particularly a porous
support such as talc, one or more zeolites, or one or more
inorganic oxides, or a resinous support material such as a
polyolefin. Preferably, the support material is an inorganic oxide
in finely divided form.
[0228] Suitable inorganic oxide support materials which are
desirably employed include metal oxides such as silica, alumina,
silica-alumina and mixtures thereof. Other inorganic oxides that
may be employed either alone or in combination with the silica,
alumina or silica-alumina are magnesia, titania, zirconia, and like
metal oxides. Such support materials can be treated with a suitable
reagent such as an alumoxane (e.g., methylalumoxane) or an
alkylaluminum compound (e.g., an aluminum trialkyl such as
triethylaluminum). Other suitable support materials are finely
divided polyolefins such as finely divided polyethylene.
[0229] In a preferred embodiment of this invention there is
provided a supported cocatalyst composition comprising an
organoborane of formula (I), formula (II), or formula (III) above
supported on a carrier such as described above, and especially on a
porous support such as talc, a zeolite, or one or inorganic oxides,
most preferably a porous silica. Such compositions are of advantage
in that such supported cocatalysts can be provided to various end
users for carrying out polymerization reactions using their own
respective preferred d- or f-block metal-containing catalyst. All
that is required is for the end user to contact the selected d- or
f-block metal-containing compound having at least one leaving group
with the supported organoborane composition of this invention in
the presence of a suitable solvent or diluent so that the catalytic
complex is formed on and/or in the pores of the support, thereby
forming a supported catalyst of this invention.
[0230] Another preferred embodiment of this invention is a
supported catalyst composition comprising a catalytic complex of
this invention formed from d- or f-block metal-containing compound
having at least one leaving group, and an organoborane of formula
(I), formula (II), or formula (III) above, supported on a carrier
such as described above, and especially on a porous support such as
talc, a zeolite, or one or more inorganic oxides, most preferably a
porous silica.
[0231] In preparing the supported organoborane cocatalysts of this
invention, the organoborane of this invention can be added to and
mixed with a slurry of the support in a suitable anhydrous inert
liquid diluent so that the cocatalyst is deposited on the support.
Agitation and heat can be utilized in performing this operation.
After the deposition has occurred, the treated support is isolated
and dried under an inert atmosphere to prepare a supported
cocatalyst of this invention. Such supported dried cocatalyst
should be kept under an inert atmosphere or in an anhydrous inert
diluent under an inert atmosphere until the use of the supported
cocatalyst in forming an active catalyst composition, a step which
typically will be conducted in situ immediately prior to initiation
of a polymerization reaction pursuant to this invention. Another
preferred way of forming the supported organoborane cocatalyst
compositions of this invention is to employ the incipient
impregnation technique described in U.S. Pat. Nos. 5,332,706 and
5,473,028. In utilizing this technique, a supported catalyst is
formed by contacting a porous silica having a known total pore
volume with a solution of an organoborane of formula (I), (II), or
(III) above, the volume of the solution being equal to or less than
such total pore volume so that the solution impregnates the silica
and is thus disposed within the body of the resultant dry
particles. In U.S. Pat. No. 5,602,067 this concept is expanded to
using an even larger volume of the solution, provided the volume of
the solution is less than required for forming a slurry of the
catalyst particles in the solution, and this procedure can be
adapted for use with the organoboranes of formulas (I), (II), and
(III) above in lieu of the aluminoxanes referred to in the
patent.
[0232] To prepare the supported catalyst compositions of this
invention, the procedures described in the immediately preceding
paragraph can be utilized with the exception that in addition to an
organoborane of formula (I), (II), or (III) above, a d- or f-block
metal compound having at least one leaving group is used so that
the metal compound and the organoborane interact with each other to
produce the active catalytic complex which is supported on and/or
in the pores of the support. Thus use can be made of any catalyst
slurry deposition procedure, or the incipient impregnation
procedures of U.S. Pat. Nos. 5,332,706 and 5,473,028, or the
procedure of U.S. Pat. No. 5,602,067 involving use of a volume of
treating solution in excess of the total pore volume but less than
the volume required for forming a slurry of the catalyst particles
in the solution of the catalyst.
[0233] [0095] Polymers can be produced pursuant to this invention
by homopolymerization of polymerizable olefins, typically 1-olefins
(also known as .alpha.-olefins) such as ethylene, propylene,
1-butene, styrene, or copolymerization of two or more
copolymerizable monomers, at least one of which is typically a
1-olefin. The other monomer(s) used in forming such copolymers can
be one or more different 1-olefins and/or a diolefin, and/or a
polymerizable acetylenic monomer. Olefins that can be polymerized
in the presence of the catalysts of this invention include
.alpha.-olefins having 2 to 20 carbon atoms such as ethylene,
propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and
1-octadecene. Normally, the hydrocarbon monomers used, such as
1-olefins, diolefins and/or acetylene monomers, will contain up to
about 10 carbon atoms per molecule. Preferred 1-olefin monomers for
use in the process include ethylene, propylene, 1-butene,
3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. It
is particularly preferred to use supported or unsupported catalysts
of this invention in the polymerization of ethylene, or propylene,
or ethylene and at least one C.sub.3-C.sub.8 1-olefin
copolymerizable with ethylene. Typical diolefin monomers which can
be used to form terpolymers with ethylene and propylene include
butadiene, hexadiene, norbomadiene, and similar copolymerizable
diene hydrocarbons. 1-Heptyne and 1-octyne are illustrative of
suitable acetylenic monomers which can be used. Often the monomer
or monomers being polymerized comprise(s) a 1-olefin, a
vinylaromatic monomer, or an ester of acrylic or methacrylic
acid.
[0234] The catalytic complexes of this invention can also be used
for producing homopolymers and copolymers of certain
functionally-substituted monomers or mixtures of monomers in which
at least one monomer is a functionally-substituted monomer. One
such group of functionally-substituted monomers which can be
homopolymerized or copolymerized pursuant to this invention is
comprised of monomers of the formula:
(R.sup.5)(R.sup.6)C.dbd.C(R.sup.7)--COOR.sup.8
[0235] wherein R.sup.5, R.sup.6, and R.sup.7, are, independently
hydrogen atoms or hydrocarbyl groups typically having up to about
20 carbon atoms, such as alkyl or aryl groups, and R.sup.8 is a
hydrocarbyl group such as an alkyl or aryl group having up to about
20 carbon atoms. When R.sup.5, R.sup.6, and/or R.sup.7 are
hydrocarbyl groups, each one present preferably is an alkyl group
containing from 1 to 4 carbon atoms. Most preferably R.sup.5 is a
methyl group, R.sup.6 is a hydrogen atom or methyl group, and
R.sup.7 is a hydrogen atom.
[0236] Polymerization of ethylene or copolymerization with ethylene
and an .alpha.-olefin having 3 to 10 carbon atoms may be performed
in either the gas or liquid phase (e.g. in a solvent, such as
toluene, or heptane). The polymerization can be conducted at
conventional temperatures (e.g., 0.degree. to 120.degree. C.) and
pressures (e.g., ambient to 50 kg/cm.sup.2) using conventional
procedures as to molecular weight regulations and the like.
[0237] The heterogeneous catalysts of this invention can be used in
polymerizations conducted as slurry processes or as gas phase
processes. By "slurry" is meant that the particulate catalyst is
used as a slurry or dispersion in a suitable liquid reaction medium
which may be composed of one or more ancillary solvents (e.g.,
liquid aromatic hydrocarbons, etc.) or an excess amount of liquid
monomer to be polymerized in bulk. Generally speaking, these
polymerizations are conducted at one or more temperatures in the
range of about 0 to about 160.degree. C., and under atmospheric,
subatmospheric, or superatmospheric conditions. Conventional
polymerization adjuvants, such as hydrogen, may be employed if
desired. Preferably polymerizations conducted in a liquid reaction
medium containing a slurry or dispersion of a catalyst of this
invention are conducted at temperatures in the range of about 40 to
about 110.degree. C. Typical liquid diluents for such processes
include hexane, toluene, and like materials. Typically, when
conducting gas phase polymerizations, superatmospheric pressures
are used, and the reactions are conducted at temperatures in the
range of about 50 to about 160.degree. C. These gas phase
polymerizations can be performed in a stirred or fluidized bed of
catalyst in a pressure vessel adapted to permit the separation of
product particles from unreacted gases. Thermostated ethylene,
comonomer, hydrogen and an inert diluent gas such as nitrogen can
be introduced or recirculated to maintain the particles at the
desired polymerization reaction temperature. An aluminum alkyl such
as triethylaluminum may be added as a scavenger of water, oxygen
and other impurities. In such cases the aluminum alkyl is
preferably employed as a solution in a suitable dry liquid
hydrocarbon solvent such as toluene or xylene. Concentrations of
such solutions in the range of about 5.times.10.sup.-5 molar are
conveniently used. But solutions of greater or lesser
concentrations can be used, if desired. Polymer product can be
withdrawn continuously or semi-continuously at a rate that
maintains a constant product inventory in the reactor.
[0238] Because of the high activity and productivity achievable by
use of catalysts of this invention, the catalyst levels used in
olefin polymerizations can be less than previously used in typical
olefin polymerizations conducted on an equivalent scale. In
general, the polymerizations and copolymerizations conducted
pursuant to this invention are carried out using a catalytically
effective amount of a novel catalyst composition of this invention,
which amount may be varied depending upon such factors such as the
type of polymerization being conducted, the polymerization
conditions being used, and the type of reaction equipment in which
the polymerization is being conducted. In many cases, the amount of
the catalyst of this invention used will be such as to provide in
the range of about 0.000001 to about 0.01 percent by weight of d-
or f-block metal based on the weight of the monomer(s) being
polymerized.
[0239] After polymerization and deactivation of the catalyst in a
conventional manner, the product polymer can be recovered from the
polymerization reactor by any suitable means. When conducting the
process with a slurry or dispersion of the catalyst in a liquid
medium the product typically is recovered by a physical separation
technique (e.g. decantation, etc.). The recovered polymer is
usually washed with one or more suitably volatile solvents to
remove residual polymerization solvent or other impurities, and
then dried, typically under reduced pressure with or without
addition of heat. When conducting the process as a gas phase
polymerization, the product after removal from the gas phase
reactor is typically freed of residual monomer by means of a
nitrogen purge, and often can be used without further catalyst
deactivation or catalyst removal.
[0240] When preparing polymers pursuant to this invention
conditions may be used for preparing unimodal or multimodal polymer
types. For example, mixtures of catalysts of this invention formed
from two or more different metallocenes having different
propagation and termination rate constants for ethylene
polymerizations can be used in preparing polymers having broad
molecular weight distributions of the multimodal type.
[0241] The following Examples of polymerizations conducted pursuant
to this invention are presented for purposes of illustration and
not limitation.
EXAMPLE 18
Ethylene Polymerization
[0242] Ethylene polymerizations were carried out at room
temperature in 250-mL flamed, round-bottom flasks attached to a
high-vacuum line. In a typical experiment, a solution of each of
the catalysts of Example 5 in 2 mL of toluene was quickly injected
using a gas-tight syringe equipped with a spraying needle into
respective rapidly-stirred flasks containing 100 mL of toluene
which was pre-saturated under 1 atm of rigorously purified
ethylene. The polymerization mixture was quenched with acidic MeOH
at which point polyethylene precipitated. The respective polymers
were collected by filtration, washed with MeOH and dried under high
vacuum to a constant weight. Additional polymerizations were
conducted using ethylene, ethylene and 1-hexene, styrene, and
ethylene and styrene, using various catalyst systems. Conditions
and results of these polymerizations are summarized in Tables
1-3.
1TABLE 1 Comparison of Ethylene Polymerization Activities Mediated
by Monomeric and Dinuclear Metallocene Cations Having Counteranions
MeB(C.sub.6F.sub.5).sub.3.sup..crclbar., MePBB.sup..crclbar., and
Polymer Properties.sup.a .mu.mol Reaction Polymer Entry Catalyst of
cat. time (s) yield (g) Activity.sup.b 10.sup.-3 M.sub.w
M.sub.w/M.sub.n 1
Cp'.sub.2ZrMe.sup..sym.MeB(C.sub.6F.sub.5).sub.3.sup..crclbar. 0.15
60 1.0 4.0 .times. 10.sup.6 124 2.03 2
[(Cp'.sub.2ZrMe).sub.2(.mu.-Me- )].sup..sym.[MePBB].sup..crclbar.
0.15 40 0.8 4.8 .times. 10.sup.6 559 3.06 3
Cp".sub.2ZrMe.sup..sym.MeB(C.sub.6F.sub.5).sub.3.sup..crclb- ar.
0.15 60 1.5 6.0 .times. 10.sup.6 321 1.42 4
[(Cp".sub.2ZrMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar.
0.15 40 1.3 7.8 .times. 10.sup.6 392 2.72 5
Cp*.sub.2ZrMe.sup..sym.MeB(C.s- ub.6F.sub.5).sub.3.sup..crclbar.
0.15 60 0.8 3.2 .times. 10.sup.6 136 2.54 6
[(Cp*.sub.2ZrMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar.
0.15 60 1.1 4.4 .times. 10.sup.6 370 2.28 .sup.aCarried our at
25.degree. C., 1.0 atm of ethylene, and 100 mL of toluene on a high
vacuum line. .sup.bIn units of grams of polymer/(mole of cat
.multidot. atm .multidot. h).
[0243]
2TABLE 2 Summary of Ethylene (E) Polymerization, Ethylene-1-Hexene
(E/H), and Ethylene-Styrene (E/S) Copolymerizations Catalyzed by
Constrained Geometry Catalysts.sup.a .mu.mol Reaction Polymer %
Comonomer Entry Catalyst Monomer of cat. time (min) yield (g)
Activity.sup.b incorporation 10.sup.-3 M.sub.w M.sub.w/M.sub.n 1
CGCZrMe.sup..sym.MeB(C.sub.6F.sub.5).sub- .3.sup..crclbar. E 15 20
0 0 2 [CGCZrMe].sup..sym.[MePBB].sup..c- rclbar. E 15 4 1.60 1.60
.times. 10.sup.6 7.69 2.78 3
CGCTiMe.sup..sym.MeB(C.sub.6F.sub.5).sub.3.sup..crclbar. E 15 10
0.20 8.00 .times. 10.sup.6 1058 9.54 4
[(CGCTiMe).sub.2Me].sup..sym.[- MePBB].sup..crclbar. E 15 4 0.80
5.60 .times. 10.sup.6 305 2.56 5
CGCZrMe.sup..sym.Meb(C.sub.6F.sub.5).sub.3.sup..crclbar. E/H 50 15
0 0 6 [CGCZrMe].sup..sym.[MePBB].sup..crclbar. E/H 50 15 6.97 5.58
.times. 10.sup.5 33.6 10.0 2.68 7 CGCTiMe.sup..sym.MeB(C.sub.6F.s-
ub.5).sub.3.sup..crclbar. E/H 25 10 0.05 1.20 .times. 10.sup.4 63.2
8 [(CGCTiMe).sub.2Me].sup..crclbar.[MePBB].sup..crclbar. E/H 25 10
1.95 4.68 .times. 10.sup.5 65.3 105 1.86 9
CGCTiMe.sup..sym.MeB(C.sub.6- F.sub.5).sub.3.sup..crclbar. E/S 25
15 0.45 7.20 .times. 10.sup.4 35.2 10
[(CGCTiMe).sub.2Me].sup..sym.[MePBB].sup..crclbar. E/S 25 15 0.80
1.28 .times. 10.sup.5 33.4 .sup.aEthylene (E) polymerizations were
carried out at 25.degree. C., 1 atm ethylene, and 100 mL of toluene
on a high-vacuum line; ethylene-1-hexene (E/H) and ethylene-styrene
(E/S) copolymerizations were carried out at 25.degree. C., 0.356M
of ethylene, 1.78 of 1-hexene and styrene, and 25 mL of toluene on
a high-vacuum line. .sup.bIn units of grams of polymer/(mole of cat
.multidot. atm .multidot. h).
[0244]
3TABLE 3 Summary of Styrene Polymerization, and Ethylene-1-Hexene
(E/H) Copolymerizations Catalyzed by Mono-Cp Metallocene
Catalysts.sup.a Reaction Polymer Entry Catalyst Monomer time (min)
yield (g) Activity 10.sup.-3 M.sub.w M.sub.wM.sub.n Remarks 1
Cp*TiMe.sub.3-PBB Styrene 15 0.40 1.80 .times. 10.sup.6 170 2.56
[mr] = 98% 2 [Cp*ZrMe.sub.2].sup..sym.[MePBB].sup..crclbar. Styrene
10 1.51 1.01 .times. 10.sup.7 atactic 3
[Cp*HfMe.sub.2].sup..sym.[MePBB].sup.- .crclbar. Styrene 15 1.21
5.51 .times. 10.sup.6 22.9 2.78 atactic 4
Cp*HfMe.sub.3--B(C.sub.6F.sub.5).sub.3 Styrene 15 0.70 3.20 .times.
10.sup.6 24.8 2.98 atactic 5 Cp*TiMe.sub.3--B(C.sub.6F.sub.5).sub.-
3 E/H 5.0 0.70 1.70 .times. 10.sup.5 848 23.7 % H = 39.5 6
Cp*TiMe.sub.3--PBB E/H 5.0 4.51 1.08 .times. 10.sup.6 151 4.32 % H
= 43.6 .sup.aStyrene polymerizations (entries 1-4) were carried out
at 25.degree. C., 2.0 mL (17.4 mmol) of styrene, 50 .mu.mol of
catalyst, and 5 mL of toluene on high-vacuum line. Titanium
catalysts were generated by in situ reaction of Cp'TiMe.sub.3 +
borane in 2 mL toluene. Activities in units of gram of bulk
polymer/(mole of cat.) .multidot. (mole of monomer) .multidot. h;
ethylene-1-hexene (E/H) copolymerizations (entries 5 and 6) were
carried out at 25.degree. C., #0.356M of ethylene, 1.78M of
1-hexene, 50 .mu.mol of catalyst, and 25 mL of toluene on a
high-vacuum line.
EXAMPLE 19
Propylene Polymerization
[0245] These reactions were carried out in a 100 mL quartz Worden
vessel equipped with a magnetic stirring bar, a pressure gauge and
a stainless steel O-ring assembly attached to a high vacuum line.
In a typical experiment, the reaction vessel is flamed and then
pumped under high vacuum for several hours, filled with inert gas
and brought into a glove box. A measured amount of catalyst is
added into the vessel. On the high vacuum line, a measured amount
of the solvent and propylene are condensed at -78.degree. C. The
reaction apparatus is sealed off and warmed to the desired
temperature. During the polymerization process, the reaction tube
is immersed in a large amount of tap water (20-25.degree. C.) or
ice water (0.degree. C.) to help dissipate the heat produced from
the polymerization and keep the temperature constant. The progress
of the polymerization reactions is monitored through observance of
the pressure change. After the reaction is finished (pressure drops
to zero psi), the resultant product is removed from the vessel,
washed with methanol and water and dried under vacuum. Conditions
and results of such polymerizations are summarized in Table 4.
4TABLE 4 Isospecific and Syndiospecific Propylene Polymerizations
Catalyzed by C.sub.2- and C.sub.5- Symmetric
Metallocene/B(C.sub.6F.sub.5).sub.3, PBB, and
Ph.sub.3C.sup..sym.B(C.sub.6F.sub.5).sub.4.sup..crclbar.Catalysts.sup.a
.mu.mol T.sub.p Reaction Polymer Entry Catalyst Reactants of cat.
(.degree. C.) time (min) yield (g) Activity.sup.b M.sub.w .times.
10.sup.3 M.sub.w/M.sub.n T.sub.m (.degree. C.) mmmm % 1
Me.sub.2Si(Ind).sub.2ZrMe.sub.2, B(C.sub.6F.sub.5).sub.3 10 24 2.5
0.73 1.8 .times. 10.sup.6 32.6 2.40 146 93 2
Me.sub.2Si(Ind).sub.2ZrMe.sub.2,
Ph.sub.3C.sup..sym.B(C.sub.6F.sub.5).sub- .4.sup..crclbar. 2.0 24
4.0 0.77 5.8 .times. 10.sup.6 123 1.94 147 93 3
Me.sub.2Si(Ind).sub.2ZrMe.sub.2,PBB 2.0 24 2.0 0.62 9.3 .times.
10.sup.6 99.2 1.91 146 93 4 Me.sub.2Si(Ind).sub.2ZrMe.sub.2,
B(C.sub.6F.sub.5).sub.3 10 60 1.75 0.63 2.2 .times. 10.sup.6 2.7
1.39 122 86 5 Me.sub.2Si(Ind).sub.2ZrMe.sub.2,
Ph.sub.3C.sup..sym.B(C.s- ub.6F.sub.5).sub.4.sup..crclbar. 2.0 60
1.5 0.93 19 .times. 10.sup.6 41.1 2.23 127 84 6
Me.sub.2Si(Ind).sub.2ZrMe.sub.2, PBB 2.0 60 1.0 0.53 16 .times.
10.sup.6 43.6 2.04 130 86 7 Me.sub.2C(Cp')(Flu)ZrMe.su- b.2,
B(C.sub.6F.sub.5).sub.3 20 24 40 3.15 2.4 .times. 105 .sup.
77.sup.c 8 Me.sub.2C(Cp')(Flu)ZrMe.sub.2, PBB 20 24 20 3.53 5.3
.times. 10.sup.5 .sup. 81.sup.c .sup.aAll polymerizations carried
out on high-vacuum line in 50 mL of toluene under 1 atm of
propylene pressure. .sup.bGram of polymer/[(mole of cationic
metallocene) .multidot. atm .multidot. h]. .sup.c% ITIT
EXAMPLE 20
Methyl Methacrylate Polymerization
[0246] A group of experiments were carried out to study the
effectiveness of isolable, well-characterized cationic dinuclear
complexes derived from PBB as compared to a catalyst system
produced from Cp.sub.2ZrMe.sub.2 and tris(perfluorophenyl)borane.
The conditions used and results obtained are summarized in Table
5.
5TABLE 5 Methyl Methacrylate Polymerization Mediated by Dinuclear
Cationic Complexes Derived From PBB.sup.1 Tacticity Entry
Catalyst.sup.b T.sub.p (.degree. C.) Time (h) Conversion (%) [mm]
[mr] [rr] 1 Cp'.sub.2ZrMe.sup..sym.MeB-
(C.sub.6F.sub.5).sub.3.sup..crclbar. 0 6.0 0 2
[(Cp'.sub.2ZrMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar. 0
6.0 100 3.3 34.3 62.4 3
[(Cp'.sub.2ZrMe).sub.2(.mu.-Me)].sup..sym.[MePBB]- .sup..crclbar.
25 2.5 100 3.8 36.0 60.2 4 [(Cp'.sub.2ZrMe).sub.2(-
.mu.-Me)].sup..sym.[MePBB].sup..crclbar. 25 2.3 100 2.9 29.8 67.3 5
[(Cp*.sub.2ThMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar. 25
8.5 46 2.4 30.0 67.6 6
{[rac-Me.sub.2Si(Ind).sub.2ZrMe].sub.2(.mu.-Me-
)}.sup..sym.[MePBB].sup..crclbar. 0 5.5 100 93.0 4.8 2.2 7
[(CGCTiMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar. 0 7.0 0 8
[(CGCZrMe).sub.2(.mu.-Me)].sup..sym.[MePBB].sup..crclbar. 25 3.0 0
9
{[Me.sub.2C(Cp')(Flu)ZrMe].sub.2(.mu.-Me)}.sup..sym.[MePBB].sup..crc-
lbar. 0 6.0 0 10 {[Me.sub.2C(Cp')(Flu)ZrMe].sub.2(.mu.-Me)}.sup..s-
ym.[MePBB].sup..crclbar. 25 6.0 0 .sup.1Conditions: 20 .mu.mol
catalyst; 2.0 mL MMA (18.7 mmol); MMA/cat., mol/mol = 935; 20 mL
toluene; solvent/[M.sub.0] = 10 vol/vol. .sup.bCatalysts (entries 5
and 8) generated by in situ reaction of 2Cp.sub.2MMe.sub.2 + PBB in
2 mL of toluene for 0.5 h.
EXAMPLE 21
Ethylene and Propylene Polymerizations
[0247] In order to compare the effectiveness of catalysts of this
invention formed from
bis(pentafluorophenyl)(2-perfluorobiphenyl)borane (BPB) with
effectiveness of other catalytic species, several polymerizations
were carried out using either ethylene or propylene. As above, on a
high vacuum line (10.sup.-5 torr), these polymerizations were
carried out in a 250-mL round-bottom three-neck flask equipped with
a large magnetic stirring bar and a thermocouple probe. A measured
quantity of dry toluene was vacuum-transferred into the flask,
saturated under 1 atmosphere of rigorously purified ethylene or
propylene (pressured controlled using a mercury bubbler) and
equilibrated at the desired reaction temperature using an external
bath. The catalytic active species was freshly generated (within 1
minute) using a solution having a 1:1 metallocene:cocatalyst ratio
in 1.5 mL of toluene. The solution of catalyst was then quickly
injected into the rapidly stirred flask using a gas-tight syringe
equipped with a spraying needle. The temperature of the toluene
solution in representative polymerization experiments was monitored
using a thermocouple (OMEGA Type K thermocouple with a Model HH21
microprocessor thermometer). The reaction exotherm temperature rise
was invariably less than 5.degree. C. during these polymerizations.
After a measured time interval (short to minimize mass transport
and exotherm effects), the polymerization mixture was quenched by
the addition of 15 mL of 2% acidified methanol. Another 30 mL of
methanol was then added and the polymer was collected by
filtration, washed with methanol, and dried on the high-vacuum line
overnight to a constant weight. Results of these polymerization
experiments are summarized in Table 6. Uncertainties in activities
reported in Table 6 are the average of 3 trials.
EXAMPLE 22
Polymerization of Tetrahydrofuran
[0248] A small amount of
{[(C.sub.5H.sub.3Me.sub.2).sub.2ZrMe](.mu.-Me)[Me-
Zr(C.sub.5H.sub.3Me.sub.2).sub.2]}.sup..sym. [MePBB].sup..crclbar.
was loaded into a J-Young NMR tube and THF-d.sub.8 was then
vacuum-transferred into the tube. The mixture was slowly warmed to
room temperature and left for several hours. The solid polymer
formed in the tube was shown to be poly(tetrahydrofuran) by .sup.1H
analysis.
6TABLE 6 Olefin Polymerization Data for Metallocenes Activated by
[(C.sub.6F.sub.5).sub.2B(C.sub.12F.sub.9)](BPB)- .sup.a Cond..sup.c
Polymer Temp Cat. mL, yield Activity.sup.d M.sub.w.sup.e Entry
Catalyst Monomer.sup.b (.degree. C.) .mu.mol min (g) .times.
10.sup.5 .times. 10.sup.3 M.sub.wM.sub.n Remarks 1
[Cp'.sub.2ZrMe].sup..sym.[MeBPB].- sup..crclbar. ethylene 23 15
100, 1.0 0.92 34 (6) 149 1.88 2.sup.f
Cp'.sub.2ZrMe.sup..sym.MeB(C.sub.6F.sub.5).sub.3.sup..crclbar.
ethylene 25 15 100, 1.0 1.00 40.0 124 2.03 3
[CGCTiMe].sup..sym.[MeBPB].sup..crclbar. ethylene 23 15 100, 10
0.72 2.4 (3) 1330 7.90 4.sup.g
CGCTiMe.sup..sym.MeB(C.sub.6F.sub.5).sub.3.s- up..crclbar. ethylene
25 15 100, 10 0.21 0.84 1058 9.54 5
[rac-Me.sub.2Si(Ind).sub.2ZrMe].sup..sym.[MeBPB].sup..crclbar.
propylene 24 10 50, 2.0 0.68 20 (2) 41 2.03 T.sub.m = 146.degree.
C.; % mmmm = 93 6.sup.h
rac-Me.sub.2Si(Ind).sub.2ZrMe.sup..sym.MeB(C.sub.6F.sub.5)-
.sub.3.sup..crclbar. propylene 24 10 50, 2.5 0.73 18 33 2.40
T.sub.m = 146.degree. C.; % mmmm = 93 .sup.aAll polymerizations
carried out on a high vacuum line (10.sup.-5 torr); uncertainties
in activities are the average of 3 runs. .sup.bEthylene (E) and
propylene (P) atm pressure. .sup.cConditions given as milliliters
of toluene, time in minutes. .sup.dGram of polymer/[(mole of
cationic metallocene) .multidot. atm .multidot. h]. .sup.dGPC
relative to polystyrene standards. .sup.eData from Table 1
(reproducibility between runs .apprxeq. 10-15%). .sup.fData from
Table 2 (reproducibility between runs .apprxeq. 10-15%). .sup.hData
from Table 4 (reproducibility between runs .apprxeq. 10-15%).
[0249] Compounds referred to by chemical name or formula anywhere
in this document, whether referred to in the singular or plural,
are identified as they exist prior to coming into contact with
another substance referred to by chemical name or chemical type
(e.g., another component, a solvent, or etc.). It matters not what
preliminary chemical changes, if any, take place in the resulting
mixture or solution, as such changes are the natural result of
bringing the specified substances together under the conditions
called for pursuant to this disclosure. Also, even though the
claims may refer to substances in the present tense (e.g.,
"comprises", "is", etc.), the reference is to the substance as it
exists at the time just before it is first contacted, blended or
mixed with one or more other substances in accordance with the
present disclosure.
[0250] Each and every patent or publication referred to in any
portion of this specification is incorporated in toto into this
disclosure by reference, as if fully set forth herein.
[0251] This invention is susceptible to considerable variation in
its practice. Therefore the foregoing description is not intended
to limit, and should not be construed as limiting, the invention to
the particular exemplifications presented hereinabove. Rather, what
is intended to be covered is as set forth in the ensuing claims and
the equivalents thereof permitted as a matter of law.
* * * * *