U.S. patent application number 09/899698 was filed with the patent office on 2002-01-24 for organo-lewis acid as cocatalyst for cationic homogeneous ziegler-natta olefin polymerizations.
Invention is credited to Chen, You-Xian, Marks, Tobin J..
Application Number | 20020010080 09/899698 |
Document ID | / |
Family ID | 27359530 |
Filed Date | 2002-01-24 |
United States Patent
Application |
20020010080 |
Kind Code |
A1 |
Marks, Tobin J. ; et
al. |
January 24, 2002 |
Organo-Lewis acid as cocatalyst for cationic homogeneous
Ziegler-Natta olefin polymerizations
Abstract
Organo-Lewis acids of the formula BR'R".sub.2 wherein B is
boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl,
fluorinated biphenyl, or fluorinated polycyclic fused ring group,
and cationic metallocene complexes formed therewith. Such complexes
are useful as polymerization catalysts.
Inventors: |
Marks, Tobin J.; (Evanston,
IL) ; Chen, You-Xian; (Midland, MI) |
Correspondence
Address: |
SIEBERTH & PATTY, L.L.C.
SUITE A-1
2924 BRAKLEY DRIVE
BATON ROUGE
LA
70816
US
|
Family ID: |
27359530 |
Appl. No.: |
09/899698 |
Filed: |
July 5, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09899698 |
Jul 5, 2001 |
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09329431 |
Jun 10, 1999 |
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Current U.S.
Class: |
502/117 ;
502/152; 502/158; 502/202; 526/127; 526/134; 526/170; 526/172;
526/348; 526/943; 556/12; 556/53; 556/7; 568/606; 568/617 |
Current CPC
Class: |
C08F 10/00 20130101;
C08G 65/12 20130101; C08F 10/00 20130101; C08F 4/61908 20130101;
C08F 4/52 20130101; C07F 17/00 20130101; Y10S 526/943 20130101;
C08F 10/00 20130101; C08F 4/61908 20130101; B01J 31/146 20130101;
B01J 2531/46 20130101; B01J 31/2295 20130101; C08F 4/6592 20130101;
B01J 2531/49 20130101; B01J 2531/48 20130101; C08G 65/20 20130101;
B01J 2531/39 20130101; B01J 31/1608 20130101 |
Class at
Publication: |
502/117 ;
526/127; 556/7; 556/12; 556/53; 502/152; 502/158; 502/202; 526/134;
526/170; 526/172; 526/943; 526/348; 568/606; 568/617 |
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
That which is claimed is:
1. An organo-Lewis acid of the formula BR'R".sub.2 wherein B is
boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl,
fluorinated biphenyl, or fluorinated polycyclic fused ring
group.
2. An organo-Lewis acid of claim 1 wherein said polycyclic fused
ring groups are naphthyl, anthracenyl, or fluorenyl.
3. An organo-Lewis acid of claim 1 wherein each R" is a fluorinated
biphenyl with (i) only one or two hydrogens thereon or (ii) no
hydrogens and all fluorines thereon.
4. An organo-Lewis acid of claim 1 wherein each R" is a fluorinated
biphenyl substituted with a phenyl group and wherein both said
biphenyls and the phenyl groups have (i) only one or two hydrogens
thereon or (ii) no hydrogens and all fluorines thereon.
5. Tris(perfluorobiphenyl)borane.
6. A solution of tris(perfluorobiphenyl)borane in a nonpolar
solvent.
7. A process of preparing an organo-Lewis acid including the step
of reacting a boron trihalide with perfluorobiphenyllithium at a
temperature from -78.degree. C. to room temperature.
8. A process of claim 7 wherein the boron trihalide is boron
trichloride.
9. A process of claim 7 wherein the boron trihalide is added to a
solution of the perfluorobiphenyllithium.
10. A process of claim 9 wherein the boron trihalide is boron
trichloride.
11. A process of claim 10 wherein the boron trichloride is added to
a solution of the perfluorobiphenyllithium which initially is at
about -78.degree. C.
12. A catalytic complex selected from the group consisting of: A) a
complex of the formula
[CpCp'MMe(.mu.-Me)MeMCpCp'].sup..sym.[MeBR'R".sub.-
2].sup..crclbar.B) a complex of the formula
[CpCp'MH(.mu.-H)HMCpCp'].sup..- sym.[MeBR'R".sub.2].sup..crclbar.C)
a complex of the formula
[CpMMe.sub.2].sup..sym.[MeBR'R".sub.2].sup..crclbar.D) a complex of
the formula
[C.sub.5H.sub.mR.sub.4-mXNRMMe].sup..sym.[MeBR'R".sub.2].sup..crc-
lbar.E) a complex of the formula
[CpCp'MMe].sup..sym.[MeBR'R".sub.2].sup..- crclbar.where: Cp and
Cp' each is C.sub.5H.sub.nR.sub.5-n where n is 0-5, or indenyl; R
is an alkyl or benzyl or aryl or silyl group, each having 20 or
less carbon atoms; M is Th, Zr, Hf, or Ti; Me is methyl; B is
boron; H is hydrogen; R' is fluorinated biphenyl; R" is a
fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic
fused ring group; m is 0-4; X is R'".sub.2Si, R'" being alkyl or
aryl, either one having 10 or less carbon atoms; and N is
nitrogen.
13. A catalytic complex of claim 12 of the formula
[CpCp'MMe(.mu.-Me)MeMCp-
Cp'].sup..sym.[MeBR'R".sub.2].sup..crclbar.where each of Cp and Cp'
is C.sub.5H.sub.nR.sub.5-n and n is 0-5; R is alkyl or benzyl or
aryl, each of 20 or less carbon atoms; M is Th, Zr, Hf, or Ti; Me
is methyl; B is boron; R' is fluorinated biphenyl; and R" is a
fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic
fused ring group.
14. A complex of claim 13 wherein each R" is fluorinated
biphenyl.
15. A complex of claim 13 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
16. A complex of claim 14 wherein each of Cp and Cp' is
.eta..sup.5-cyclopentadienyl, .eta..sup.5-dimethylcyclopentadienyl,
or .eta..sup.5-pentamethylcyclopentadienyl.
17. A complex of claim 15 of the formula
[(.eta..sup.5-C.sub.5H.sub.5).sub-
.2ZrMe(.mu.-Me)MeZr(.eta..sup.5-C.sub.5H.sub.5).sub.2].sup..sym.[MePBB].su-
p..crclbar..
18. A complex of claim 15 of the formula
[(.eta..sup.5-1,2-Me.sub.2C.sub.5-
H.sub.3).sub.2ZrMe(.mu.-Me)MeZr(.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.3).su-
b.2].sup..sym.[MePBB].sup..crclbar..
19. A complex of claim 15 of the formula
[(.eta..sup.5-Me.sub.5C.sub.5).su- b.2ZrMe(.mu.-Me)MeZr(72
.sup.5-Me.sub.5C.sub.5).sub.2].sup..sym.[MePBB].su-
p..crclbar..
20. A catalytic complex of claim 12 of the formula
[CpCp'MH(.mu.-H)HMCpCp'-
].sup..sym.[MeBR'R".sub.2].sup..crclbar.where each of Cp and Cp' is
C.sub.5H.sub.nR.sub.5-n and n is 0-5; R is alkyl or benzyl or aryl,
each of 20 or less carbon atoms; M is a Th, Zr, Hf, or Ti; H is a
hydrogen atom; B is boron; R' is fluorinated biphenyl; and R" is a
fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic
fused ring group.
21. A complex of claim 20 wherein each R" is fluorinated
biphenyl.
22. A complex of claim 20 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
23. A complex of claim 22 wherein each of Cp and Cp' is
.eta..sup.5-cyclopentadienyl or
.eta..sup.5-dimethylcyclopentadienyl.
24. A complex of claim 22 of the formula
[(.eta..sub.5-C.sub.5H.sub.5).sub-
.2ZrH(.mu.-H)HZr(.eta..sup.5-C.sub.5H.sub.5).sub.2].sup..sym.[MePBB].sup..-
crclbar..
25. A complex of claim 22 of the formula
[(.eta..sup.5-1,2-Me.sub.2C.sub.5-
H.sub.3).sub.2ZrH(.mu.-H)HZr(.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.3).sub.2-
].sup..sym.[MePBB].sup..crclbar..
26. A catalytic complex of claim 12 of the formula
[CpMMe.sub.2].sup..sym.- [MeBR'R".sub.2].sup..crclbar.where Cp is
C.sub.5H.sub.nR.sub.5-n and n is 0-5; R is alkyl, benzyl or aryl,
each of 20 or less carbon atoms; M is Th, Zr, Hf, or Ti; Me is
methyl; B is boron; R' is fluorinated biphenyl; and R" is a
fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic
fused ring group.
27. A complex of claim 26 wherein each R" is fluorinated
biphenyl.
28. A complex of claim 26 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
29. A complex of claim 27 wherein Cp is
.eta..sup.5-cyclopentadienyl, .eta..sup.5-dimethylcyclopentadienyl,
or .eta..sup.5-pentamethylcyclopent- adienyl.
30. A complex of claim 28 of the formula
[(.eta..sup.5-C.sub.5H.sub.5)TiMe-
.sub.2].sup..sym.[MePBB].sup..crclbar..
31. A complex of claim 28 of the formula
[(.eta..sup.5-C.sub.5H.sub.5)ZrMe-
.sub.2].sup..sym.[MePBB].sup..crclbar..
32. A complex of claim 28 of the formula
[(.eta..sup.5-C.sub.5H.sub.5)HfMe-
.sub.2].sup..sym.[MePBB].sup..crclbar..
33. A complex of claim 28 of the formula
[(.eta..sup.5-Me.sub.2C.sub.5H.su-
b.3)HfMe.sub.2].sup..sym.[MePBB].sup..crclbar..
34. A complex of claim 28 of the formula
[(.eta..sup.5-Me.sub.2C.sub.5H.su-
b.3)TiMe2].sup..sym.[MePBB].sup..crclbar..
35. A complex of claim 28 of the formula
[(.eta..sup.5-Me.sub.5C.sub.5)ZrM-
e.sub.2].sup..sym.[MePBB].sup..crclbar..
36. A complex of claim 28 of the formula
[(.eta..sup.5-Me.sub.5C.sub.5)HfM-
e.sub.2].sup..sym.[MePBB].sup..crclbar..
37. A catalytic complex of claim 12 of the formula
[C.sub.5H.sub.mR.sub.4--
mXNRMMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.where m is 0-4; R is
alkyl, benzyl or aryl, each of 20 or less carbon atoms; X is
R'".sub.2Si, R'" being alkyl or aryl, either one having 10 or less
carbon atoms; M is Th, Zr, Hf, or Ti; N is nitrogen; Me is methyl;
B is boron; R' is fluorinated biphenyl; and R" is a fluorinated
phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring
group.
38. A complex of claim 37 wherein each R" is fluorinated
biphenyl.
39. A complex of claim 37 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
40. A complex of claim 37 wherein M is Zr.
41. A complex of claim 37 wherein M is Ti.
42. A complex of claim 37 of the formula
[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.-
sub.4)ZrMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.
43. A complex of claim 37 of the formula
[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.-
sub.4)TiMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.
44. A catalytic complex of claim 12 of the formula
[CpCp'MMe].sup..sym.[Me- BR'R".sub.2].sup..crclbar.where each of Cp
and Cp' is C.sub.5H.sub.nR.sub.5-n and n is 0-5, or indenyl; R is
alkyl or benzyl or aryl, each of 20 or less carbon atoms; M is Th,
Zr, Hf, or Ti; Me is methyl; B is boron; R' is fluorinated
biphenyl; and R" is a fluorinated phenyl, fluorinated biphenyl, or
fluorinated polycyclic fused ring group.
45. A complex of claim 44 wherein each R" is fluorinated
biphenyl.
46. A complex of claim 44 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
47. A complex of claim 44 wherein each of Cp and Cp' is
.eta..sup.5-cyclopentadienyl or
.eta..sup.5-dimethylcyclopentadienyl or
.eta..sup.5-pentamethylcyclopentadienyl.
48. A complex of claim 44 of the formula
[(.eta..sup.5-C.sub.5H.sub.5).sub-
.2ZrMe].sup..sym.[MePBB].sup..crclbar..
49. A complex of claim 44 of the formula
[(.eta..sup.5-1,2-Me.sub.2C.sub.5-
H.sub.3).sub.2ZrMe].sup..sym.[MePBB].sup..crclbar..
50. A complex of claim 44 of the formula
[(.eta..sup.5-Me.sub.5C.sub.5).su-
b.2ZrMe].sup..sym.[MePBB].sup..crclbar..
51. A complex of claim 44 of the formula
[(.eta..sup.5-Me.sub.5C.sub.5).su-
b.2ThMe].sup..sym.[MePBB].sup..crclbar..
52. A method of preparing a polyolefin polymer, which method
comprises polymerizing the alpha olefin using as catalyst a
catalytic complex selected from the group consisting of: A) a
complex of the formula
[CpCp'MMe(.mu.-Me)MeMCpCp'].sup..sym.[MeBR'R".sub.2].sup..crclbar.B)
a complex of the formula
[CpCp'MH(.mu.-H)HMCpCp'].sup..sym.[MeBR'R".sub.2].- sup..crclbar.C)
a complex of the formula [CpMMe.sub.2].sup..sym.[MeBR'R".s-
ub.2].sup..crclbar.D) a complex of the formula
[C.sub.5H.sub.mR.sub.4-mXNR-
MMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.E) a complex of the
formula [CpCp'MMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.where: Cp
and Cp' each is C.sub.5H.sub.nR.sub.5-n where n is 0-5, or indenyl;
R is alkyl or benzyl or aryl or silyl, each of 20 or less carbon
atoms; M is Th, Zr, Hf, or Ti; Me is methyl; B is boron; H is
hydrogen; R' is fluorinated biphenyl; R" is a fluorinated phenyl,
fluorinated biphenyl, or fluorinated polycyclic fused ring group; m
is 0-4; X is R'".sub.2Si, R'" being alkyl or aryl, either one
having 10 or less carbon atoms; and N is nitrogen.
53. The method of claim 52 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
54. The method of claim 52 wherein said alpha olefin is ethylene or
propylene.
55. The method of claim 52 wherein said catalytic complex is a
complex of the formula
[CpCp'MMe(.mu.-Me)MeMCpCp'].sup..sym.[MeBR'R".sub.2].sup..crc-
lbar.where each of Cp and Cp' is C.sub.5H.sub.nR.sub.5-n and n is
0-5; R is alkyl or benzyl or aryl, each of 20 or less carbon atoms;
M is Th, Zr, Hf, or Ti; Me is methyl; B is boron; R' is fluorinated
biphenyl; and R" is a fluorinated phenyl, fluorinated biphenyl, or
fluorinated polycyclic fused ring group.
56. The method of claim 55 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
57. The method of claim 55 wherein said alpha olefin is ethylene or
propylene.
58. The method of claim 55 wherein the catalytic complex used is:
a)
[(.eta..sup.5-C.sub.5H.sub.5).sub.2ZrMe(.mu.-Me)MeZr(.eta..sup.5-C.sub.5H-
.sub.5).sub.2].sup..sym.[MePBB].sup..sym.; b)
[(.eta..sup.5-1,2-Me.sub.2C.-
sub.5H.sub.3).sub.2ZrMe(.mu.-Me)MeZr(.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.-
3).sub.2].sup..sym.[MePBB].sup..crclbar.; or c)
[(.eta..sup.5-Me.sub.5C.su-
b.5).sub.2ZrMe(.mu.-Me)MeZr(.eta..sup.5-Me.sub.5C.sub.5).sub.2].sup..sym.[-
MePBB].sup..crclbar..
59. The method of claim 52 wherein said catalytic complex is a
complex of the formula
[CpCp'MH(.mu.-H)HMCpCp'].sup..sym.[MeBR'R".sub.2].sup..crclba-
r.where each of Cp and Cp' is C.sub.5H.sub.nR.sub.5-n and n is 0-5;
R is alkyl or benzyl or aryl, each of 20 or less carbon atoms; M is
a Th, Zr, Hf, or Ti; H is a hydrogen atom; B is boron; R' is
fluorinated biphenyl; and R" is a fluorinated phenyl, fluorinated
biphenyl, or fluorinated polycyclic fused ring group.
60. The method of claim 59 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
61. The method of claim 59 wherein said alpha olefin is ethylene or
propylene.
62. The method of claim 59 wherein the catalytic complex used is:
a)
[(.eta..sup.5-C.sub.5H.sub.5).sub.2ZrH(.mu.-H)HZr(.eta..sup.5-C.sub.5H.su-
b.5).sub.2].sup..sym.[MePBB].sup..crclbar. or b)
[(.eta..sup.5-1,2-Me.sub.-
2C.sub.5H.sub.3).sub.2ZrH(.mu.-H)HZr(.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.-
3).sub.2].sup..sym.[MePBB].sup..crclbar..
63. The method of claim 52 wherein said catalytic complex is a
complex of the formula
[CpMMe.sub.2].sup..sym.[MeBR'R".sub.2].sup..crclbar.where Cp is
C.sub.5H.sub.nR.sub.5-n and n is 0-5; R is alkyl, benzyl or aryl,
each of 20 or less carbon atoms; M is Th, Zr, Hf, or Ti; Me is
methyl; B is boron; R' is fluorinated biphenyl; and R" is a
fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic
fused ring group.
64. The method of claim 63 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
65. The method of claim 63 wherein said alpha olefin is styrene or
ethylene and 1-hexene.
66. The method of claim 63 wherein the catalytic complex used is:
a)
[(.eta..sup.5-C.sub.5H.sub.5)TiMe.sub.2].sup..sym.[MePBB].sup..crclbar.;
b)
[(.eta..sup.5-C.sub.5H.sub.5)ZrMe.sub.2].sup..sym.[MePBB].sup..crclbar-
.; c)
[(.eta..sup.5-C.sub.5H.sub.5)HfMe.sub.2].sup..sym.[MePBB].sup..crclb-
ar.; d)
[(.eta..sup.5-Me.sub.2C.sub.5H.sub.3)HfMe.sub.2].sup..sym.[MePBB].-
sup..crclbar.; e)
[(.eta..sup.5-Me.sub.2C.sub.5H.sub.3)TiMe.sub.2].sup..sy-
m.[MePBB].sup..crclbar.; f)
[(.eta..sup.5-Me.sub.5C.sub.5)ZrMe.sub.2].sup.-
.sym.[MePBB].sup..crclbar.; or g)
[(.eta..sup.5-Me.sub.5C.sub.5)HfMe.sub.2-
].sup..sym.[MePBB].sup..crclbar..
67. The method of claim 52 wherein said catalytic complex is a
complex of the formula
[C.sub.5H.sub.mR.sub.4-mXNRMMe].sup..sym.[MeBR'R".sub.2].sup.-
.crclbar.where m is 0-4; R is alkyl, benzyl or aryl, each of 20 or
less carbon atoms; X is R'".sub.2Si, R'" being alkyl or aryl,
either one having 10 or less carbon atoms; M is Th, Zr, Hf, or Ti;
N is nitrogen; Me is methyl; B is boron; R' is fluorinated
biphenyl; and R" is a fluorinated phenyl, fluorinated biphenyl, or
fluorinated polycyclic fused ring group.
68. The method of claim 67 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
69. The method of claim 67 wherein M is Zr.
70. The method of claim 67 wherein M is Ti.
71. The method of claim 67 wherein said alpha olefin is ethylene or
ethylene and 1-hexene.
72. The method of claim 67 wherein the catalytic complex used is:
a)
[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)ZrMe].sup..sym.[MeBR'R".sub.2].sup-
..crclbar.; or b)
[Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)TiMe].sup..sym.[M-
eBR'R".sub.2].sup..crclbar..
73. The method of claim 52 wherein said catalytic complex is a
complex of the formula
[CpCp'MMe].sup..sym.[MeBR'R".sub.2].sup..crclbar.where each of Cp
and Cp' is C.sub.5H.sub.nR.sub.5-n and n is 0-5, or indenyl; R is
alkyl or benzyl or aryl, each of 20 or less carbon atoms; M is Th,
Zr, Hf, or Ti; Me is methyl; B is boron; R' is fluorinated
biphenyl; and R" is a fluorinated phenyl, fluorinated biphenyl, or
fluorinated polycyclic fused ring group.
74. The method of claim 73 wherein R' is nonafluorobiphenyl, and
wherein each R" is nonafluorobiphenyl.
75. The method of claim 73 wherein said alpha olefin is
propylene.
76. The method of claim 73 wherein the catalytic complex used is:
[(.eta..sup.5-C.sub.5H.sub.5).sub.2ZrMe].sup..sym.[MePBB].sup..crclbar..
77. A method of preparing polytetrahydrofuran, which method
comprises polymerizing tetrahydrofuran using as catalyst a
catalytic complex of the formula
[CpCp'MMe(.mu.-Me)MeMCpCp'].sup..sym.[MeBR'R".sub.2].sup..crclbar-
.where each of Cp and Cp' is C.sub.5H.sub.nR.sub.5-n and n is 0-5;
R is alkyl or benzyl or aryl, each of 20 or less carbon atoms; M is
Th, Zr, Hf, or Ti; Me is methyl; B is boron; R' is fluorinated
biphenyl; and R" is a fluorinated phenyl, fluorinated biphenyl, or
fluorinated polycyclic fused ring group.
78. The method of claim 77 wherein M is zirconium.
79. The method of claim 77 wherein the catalytic complex used is
[(C.sub.5H.sub.3Me.sub.2).sub.2(Me)Zr--Me--Zr(Me)(C.sub.5H.sub.3Me.sub.2)-
.sub.2].sup..sym.(MePBB).sup..crclbar..
Description
REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of prior copending
application Ser. No. 09/329,431, filed Jun. 10, 1999, which is a
continuation-in-part of application Ser. No.09/220,741, filed Dec.
23, 1998, now U.S. Pat. No. 6,087,460, issued Jul. 11, 2000, 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 priority of U.S. provisional application Ser.
No.60/011,920, filed Feb. 20, 1996.
BACKGROUND OF THE INVENTION
[0003] This invention relates to the compositions of matter useful
as catalysts, to a method for preparing these catalysts and to a
method 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 IV-B 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 I-III metal alkyl and a transition metal complex from Group
IVB-VB 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.
SUMMARY OF THE INVENTION
[0006] Accordingly, it is an object of the subject invention to
prepare and utilize a new class of olefin polymerization
catalysts.
[0007] A further object of the subject invention is a catalyst
which permits better control over molecular weight, molecular
distribution, stereoselectivity, and comonomer incorporation.
[0008] Another object of the subject invention is a Ziegler-Natta
type catalyst system which reduces the use of excess cocatalyst and
activates previously unresponsive metallocenes.
[0009] These and other objects are attained by the subject
invention whereby in one embodiment, a strong organo-Lewis acid,
such as perfluorobiphenylborane (PBB) is utilized as a highly
efficient cocatalyst for metallocene-mediated olefin polymerization
and as a catalyst for a ring opening polymerization of THF. PBB can
be synthesized in much higher yield than B(C.sub.6F.sub.5).sub.3
and the anion generated with PBB is non-coordinating instead of
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..crclbar.. In addition, PBB exhibits
even higher catalytic activities in most cases.
[0010] In one embodiment of the subject invention a strong
organo-Lewis acid, such as perfluorobiphenylborane (PBB), is
utilized to synthesize stoichiometrically precise,
isolable/crystallographically characterizable, highly active
"cation-like" metallocene polymerization catalysts. The biphenyl
groups of PBB may be connected to the boron at the meta, para, or
ortho position.
[0011] PBB reacts with early transition metal or actinide alkyls to
yield highly reactive cationic complexes:
(CpCp'MR).sup..sym.(RBR'R".sub.2).sup- ..crclbar.
[0012] where
[0013] CpCp'=C.sub.5H.sub.nR.sub.5-n(n is 0-5), indenyl, allyl,
benzyl, C.sub.5H.sub.nR.sub.4-nXNR (n is 0-4);
[0014] M=early transition metal or actinide, e.g., Ti, Zr, Hf, Th,
U;
[0015] X=R'".sub.2Si, where R'" is an alkyl or aryl group
(C.ltoreq.10);
[0016] R, R'"=alkyl, benzyl, or aryl group (C.ltoreq.20), hydride,
silyl;
[0017] B=boron
[0018] R'=fluorinated biphenyl
[0019] R"=fluorinated phenyl, fluorinated biphenyl, or fluorinated
polycyclic fused rings such as naphthyl, anthracenyl, or
fluorenyl.
[0020] As a specific example of the above, the reaction of PBB with
a variety of zirconocene dimethyl complexes proceeds rapidly and
quantitatively to yield, after recrystallization from hydrocarbon
solvents, the catalytic complex of Eq. 1. 1
[0021] Such catalytic complexes have been found to be active
homogeneous catalysts for .alpha.-olefin polymerization and, more
particularly, the polymerization, copolymerization or
oligopolymerization of ethylene, .alpha.-olefins, dienes and
acetylenic monomers, as well as intramolecular C--H activation.
[0022] The cocatalyst of the subject invention may be referred to
as BR'R".sub.2, where B=boron; R' and R" represent at least one and
maybe more fluorinated biphenyls or other polycyclic groups, such
as naphthyl. Two of the biphenyls may be substituted with a phenyl
group. Both the biphenyls and the phenyl groups should be highly
fluorinated, preferably with only one or two hydrogens on a group,
and most preferably, as in PBB with no hydrogens and all
fluorines.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The cocatalyst system of the subject invention can be better
understood with reference to the drawings wherein:
[0024] FIG. 1 is a structural depiction of PBB;
[0025] FIG. 2 is a reaction pathway for the synthesis of PBB;
[0026] FIG. 3 shows the reaction pathway for a catalyst system
according to the subject invention;
[0027] FIG. 4 shows the reaction pathway for a second catalyst
system according to the subject invention;
[0028] FIG. 5 shows the reaction pathway for a third catalyst
system according to the subject invention;
[0029] FIG. 6 shows the reaction pathway for a fourth catalyst
system according to the subject invention; and
[0030] FIG. 7 shows the reaction pathway for a fifth catalyst
system according to the subject invention.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The reaction of perfluorobiphenylborane 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, after recrystallization,
complexes. This catalyst activation reaction may be used in the
polymerization, copolymerization, oligomerization and dimerization
of .alpha.-olefins. In addition, the catalyst of the subject
invention may be used in conjunction with aluminum alkyls, aluminum
aryls, (AlR.sub.3, R=Et, Me, Ph, naphthyl) or methyl alumoxane
(Al(CH.sub.3)O).sub.n for increased polymer yields.
[0032] PBB (FIG. 1) has been synthesized in quantitative yields of
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 (FIG. 2). 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 the catalyst shown in FIG. 3. The reaction of PBB with
a bis-Cp type of dimethyl zirconocenes forms a dinuclear
methyl-bridged zirconocene cation such as 2
[0033] (1:1 or 2:1)
[0034] where
[0035] Cp=C.sub.5H.sub.5
[0036] Cp=C.sub.5H.sub.3Me.sub.2 or
[0037] Cp=C.sub.5Me.sub.5
[0038] and a hydride-bridged analog such as 3
[0039] where
[0040] Cp=C.sub.5H.sub.5 or
[0041] Cp=C.sub.5H.sub.3Me.sub.2
[0042] More particularly, reaction of PBB with group 4 and Th
methyls proceeds cleanly to yield cationic complexes such as set
forth below.
1 4 Cp = .eta..sup.5-C.sub.5H.sub.5 1,
Cp*.sub.2ThMe.sup..sym.[MePBB].sup..crclbar. Cp* =
.eta..sup.5-Me.sub.5C.sub.5 2,
Cp.sub.2ZrCl.sup..sym.[MePBB].sup..crclbar- . Cp" =
.eta..sup.5-1,2-Me.sub.2C.sub.5H.sub.3 3,
[Cp.sub.2ZrMe(.mu.-Me)MeZrCp.sub.2].sup..sym.[MePBB].sup..crclbar.
CGC = (Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu 4,
[Cp".sub.2ZrMe(.mu.-Me)MeZ-
rCp".sub.2].sup..sym.[MePBB].sup..crclbar. M = Th, Zr, Hf, Ti 5,
[Cp.sub.2*ZrMe(.mu.-Me)MeZrCp.sub.2*].sup..sym.[MePBB].sup..crclbar.
6,
[(Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu]ZrMe.sup..sym.[MePBB].sup..-
crclbar. 7, [(Me.sub.4C.sub.5)SiMe.sub.2N.sup.tBu]TiMe.sup..sym.-
[MePBB].sup..crclbar. 8, Cp*ZrMe.sub.2.sup..sym.[MePBB].sup..crc-
lbar. 9, Cp*HfMe.sub.2.sup..sym.[MePBB].sup..crclbar.
[0043] For ethylene polymerization, catalytic activities of
dinuclear cations generated from PBB are greater than those of
monomeric cations generated from B(C.sub.6F.sub.5).sub.3 presumably
because (MePBB).sup..crclbar. is a non-coordinating anion as
compared to the weakly coordinating anion
MeB(C.sub.6F.sub.5).sub.3. The dinuclear cations have also been
found to catalyze the rapid ring-opening polymerization of THF to
produce poly(tetrahydrofuran), an important thermoplastic elastomer
and artificial leather. Monomeric zirconocene cations have also
been generated in situ by the reaction of Cp.sub.2ZrMe.sub.2 and
PBB at 60.degree. C.: 5
[0044] These attempts show very high activities for olefin
polymerization, and identify (MePBB).sup..crclbar. to be a truly
non-coordinating anion. The polymerization data with metallocene
cations having various anions are summarized in Table 1.
2TABLE 1 Polymerization Data Entry .mu.mol Polymer M.sub.wd.sup.c
No. Catalyst of cat Conditions Monomer(s).sup.a yield (g)
Activity.sup.b (10.sup.-3) M.sub.w/M.sub.n Remarks 1
(Cp.sub.2ZrMe).sub.2Me.sup..sym. 15 100 mL toluene ethylene 0.80
4.80 .times. 10.sup.6 559 3.06 MePBB.sup..crclbar. 25.degree. C.,
40 s 2 Cp.sub.2ZrMe.sup..sym. 15 100 mL toluene ethylene 1.00 4.00
.times. 10.sup.6 124 2.03 MeB(C.sub.6F.sub.5).sub.3.sup..crclbar.
25.degree. C., 60 s 3 (Cp".sub.2ZrMe).sub.2Me.sup..sym. 15 100 mL
toluene ethylene 1.30 7.80 .times. 10.sup.6 392 2.72
MePBB.sup..crclbar. 25.degree. C., 40s 4 Cp".sub.2ZrMe.sup..sym. 15
100 mL toluene ethylene 1.50 6.00 .times. 10.sup.6 321 1.42
MeB(C.sub.6F.sub.5).sub.3.sup..crclbar. 25.degree. C., 60 s 5
(Cp*.sub.2ZrMe).sub.2Me.sup..sym. 15 100 mL toluene ethylene 1.07
4.30 .times. 10.sup.6 370 2.28 MePBB.sup..crclbar. 25.degree. C.,
60 s 6 Cp*.sub.2ZrMe.sup..sym. 15 100 mL toluene ethylene 0.80 3.20
.times. 10.sup.6 136 2.54 MeB(C.sub.6F.sub.5).sub.3.sup..crclbar.
25.degree. C., 60 s 7 Cp*TiMe.sup..sym..sub.2 50 5 mL toluene
styrene 0.35 1.61 .times. 10.sup.6 170 2.56 [rrrr] > 98%
MePBB.sup..crclbar. 25.degree. C., 15 min 8 Cp*ZrMe.sup..sym..sub.2
50 5 mL toluene styrene 1.45 1.00 .times. 10.sup.7 27.6 2.63
atactic MePBB.sup..crclbar. 25.degree. C., 10 min 9
Cp*HfMe.sup..sym..sub.2 50 5 mL toluene styrene 0.69 3.17 .times.
10.sup.6 24.8 2.98 atactic MeB(C6F).sub.3.sup..crclbar. 25.degree.
C., 15 min 10 Cp*HfMe.sup..sym..sub.2 50 5 mL toluene styrene 1.16
5.33 .times. 10.sup.6 22.9 2.78 atactic MePBB.sup..crclbar.
25.degree. C., 15 min 11 Cp*TiMe.sup..sym..sub.2 50 25 mL toluene
ethylene 0.70 1.70 .times. 10.sup.5 848 23.7 39.5% hexene
MeB(C.sub.6F.sub.5).sub.3.- sup..crclbar. 25.degree. C., 5 min
1-hexene incorporation 12 Cp*TiMe.sup..sym..sub.2 50 25 mL toluene
ethylene 4.51 1.08 .times. 10.sup.6 151 4.32 43.6% hexene
MePBB.sup..crclbar. 25.degree. C., 5 min 1-hexene incorporation 13
CGCZrMe.sup..sym. 15 100 mL toluene ethylene 0 -- -- --
MeB(C.sub.6F.sub.5).sub.3.sup..crc- lbar. 25.degree. C., 20 min 14
CGCZrMe.sup..sym. 15 100 mL toluene ethylene 1.56 1.56 .times.
10.sup.6 7.69 2.78 MePBB.sup..crclbar. 25.degree. C., 4 min 15
CGCTiMe.sup..sym. 15 100 mL toluene ethylene 0.21 8.40 .times.
10.sup.4 1058 9.54 MeB(C.sub.6F.sub.5).sub.3.sup..crclbar.
25.degree. C., 10 min 16 CGCTiMe.sup..sym. 15 100 mL toluene
ethylene 0.83 4.98 .times. 10.sup.6 305 2.56 MePBB.sup..crclbar.
25.degree. C., 40 s 17 CGCZrMe.sup..sym. 50 25 mL toluene ethylene
0 -- -- -- MeB(C.sub.6F.sub.5).sub.3.sup..crclbar. 25.degree. C.,
15 min 1-hexene 18 CGCZrMe.sup..sym. 50 25 mL toluene ethylene 6.97
5.58 .times. 10.sup.5 10.0 2.68 33.6% hexene MePBB.sup..crclbar.
25.degree. C., 15 min 1-hexene incorporation 19 CGCTiMe.sup..sym.
25 25 mL toluene ethylene 0.05 1.20 .times. 10.sup.4 63.2% hexene
MeB(C.sub.6F.sub.5).sub.3.sup..crclbar. 25.degree. C., 10 min
1-hexene incorporation 20 CGCTiMe.sup..sym. 25 25 mL toluene
ethylene 1.95 4.68 .times. 10.sup.5 105 1.86 65.3% hexene
MePBB.sup..crclbar. 25.degree. C., 10 min 1-hexene incorporation
.sup.a1 atm ethylene pressure; 17.4 mmol of styrene, & 44.5
mmol of 1-hexene. .sup.bg polymer/[(mol of cationic metallocene)
.multidot. atm.multidot. h], except in entries 7-10:
polystyrene/[(mol catalyst) .multidot. (mol monomer) .multidot. h]
(reproducibility between runs .apprxeq. 10.about.15%). .sup.cGPC
relative to polystyrene standards.
[0045] Other types of cationic metallocene catalyst systems can
also be created with PBB. Metallocene cations of mono-Cp type
(FIGS. 4 and 5) have been formed by the reaction of
mono-pentamethyl Cp trimethyl group IV complexes with PBB. These
are very good syndiospecific styrene polymerization catalysts.
Constrained geometry types of zirconocene and titanocene cations
such as those in FIG. 6 where m=Zr, Ti, are readily produced by the
reaction of the corresponding dimethyl metallocenes with PBB. They
are highly naked cations and much more active catalysts than those
generated with B(C.sub.6F.sub.5).sub.3.
EXAMPLE 1
Synthesis of Perfluorobiphenylborane (PBB)
[0046] n-Butyllithium (1.6 M 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-ether 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.
[0047] 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 (1.6 M in
hexanes, 12.8 mmol) at -78.degree. C. The mixture was stirred for
an additional 2 h, and boron trichloride (4.0 mL, 1.0 M 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.3J.sub.F-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,
.sup.1J.sub.C-F=251.8 Hz, .sup.2J.sub.C-F=10.1 Hz, 3 C),146.35 (dd,
.sup.J.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.C-F=12.0 Hz, 3 C),
141.98 (tt, .sup.1J.sub.C-F=261.4 Hz, .sup.2J.sub.C-F=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=11.7 Hz, 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.36BF.sub.27: C, 45.22; H, 0.00.
Found: C, 45.44; H, 0.05.
EXAMPLE 2
Synthesis of Cp*.sub.2ThMe.sup..sym.(MePBB).sup..crclbar.
[0048] Cp*.sub.2ThMe.sub.2 (0.106 g, 0.199 mmol) and PBB (0.191 g,
0.199 mmol) were in the glove box charged into a 25-mL reaction
flask with a filter plug, and the flask was attached to the 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=21.4 Hz, 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.58
H.sub.36 BF.sub.27 Th: C, 46.79; H, 2.44; N, 0.00. Found: C, 46.68;
H, 2.24; N. 0.00.
EXAMPLE 3
Synthesis of
Cp.sub.2Zr(Me)(.mu.-Me)(Me)ZrCp.sub.2.sup..sym.(MePBB).sup..c-
rclbar.(Cp=C.sub.5H.sub.5, C.sub.5H.sub.3Me.sub.2, or
C.sub.5Me.sub.5
[0049] 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 Cp=C.sub.5H.sub.5 are as
follows. .sup.1H NMR (C.sub.6D.sub.6, 23.degree. C.): .delta.5.65
(s, 20 H, 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.
[0050] 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.): 65.51 (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.1J.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.
[0051] Analytical and spectroscopic data for Cp=C.sub.5Me.sub.5 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, 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 4
Synthesis of
Cp.sub.2Zr(H)(.mu.-H)(H)ZrCp.sub.2.sup..sym.(MePBB).sup..crcl-
bar.; Cp=C.sub.5H.sub.5, C.sub.5H.sub.3Me.sub.2
[0052] The procedure here is similar to that of Example 3, 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
3 (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.
[0053] 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, 1 H, Zr--H--Zr). The chemical shifts
and splitting patterns of .sup.19F NMR are same as those of Example
3 (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 5
Preparation of Cp.sub.2ZrMe.sup..sym.(MePBB).sup..crclbar.
[0054] 5(a) Cp=C.sub.5H.sub.5. In a J-Young NMR tube, a small
amount of a mixture of Cp.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
structures were obtained by the reaction of the product of Example
3 with excess of PBB at 60.degree. C. for 0.5 h. In a real
polymerization test, these species were also generated in situ by
mixing Cp.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). The .sup.19F NMR is similar to that of the
corresponding dinuclear species of Example 3
(Cp=C.sub.5H.sub.5).
[0055] 5(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.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.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 3
(Cp=C.sub.5Me.sub.5). .sup.13C NMR (C.sub.7D.sub.8, 60.degree. C.):
.delta.117.74 (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).
[0056] (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,
Zi--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
3, Cp=C.sub.5Me.sub.5.
EXAMPLE 6
Synthesis of CpM(Me).sub.2.sup..sym.(MePBB).sup..crclbar.;
Cp=C.sub.5Me.sub.5
[0057] M=Ti. The catalyst product of FIG. 5 was generated in the
NMR tube reaction by mixing C.sub.5Me.sub.5TiMe.sub.3 and PBB at
1:1 molar ratio in C.sub.6D.sub.6for2h. .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 7
Synthesis of
Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)MMe.sup..sym.(MePBB).su-
p..crclbar.
[0058] M=Zr. Me.sub.2Si(.sup.tBuN)(C.sub.5Me.sub.4)MMe.sub.2 (0.199
mmol) and PBB (0.199 mmol) were treated in the same manner as in
the preparation of Example 2 except for the different reaction
times (2 h). This procedure yields 73.1 % (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-.sup.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--CMe.sub.3), 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.
EXAMPLE 8
Ethylene Polymerization
[0059] The reaction was conducted in a 250 mL flamed round bottom
flask attached to a high vacuum line. The flask was equipped with a
large magnetic stirring bar and a straight-bore high vacuum
stopcock. The exterior connecting tube of the stopcock (Ca. 10 mm
in length) is sealed with a new serum cap. The reaction vessel is
then evacuated for several hours, back-filled with inert gas (Ar),
the stopcock closed, and the reaction flask reevacuated. A measured
amount of a nonpolar solvent such as benzene or toluene is vacuum
transferred into the flask. Gaseous ethylene is admitted to the
reaction flask through the purification column. The gas pressure is
continuously maintained at 1 atm. Rapid stirring of the solution is
initiated and after several minutes (to allow the saturation of the
solvent with ethylene), the stopcock is opened and a small aliquot
of catalyst solution (in the same solvent as used for the reaction)
is injected by a gas-tight syringe just above the rapidly stirring
solution through a serum cap (the syringe needle had been flattened
so that the catalyst solution exits in a fine spray). Solid
polyethylene is formed immediately. The reaction is quenched after
a certain amount of time by injecting methanol through the serum
cap on the stopcock. The solid polyethylene was collected by
filtration, washed with methanol and then dried under vacuum at
100.degree. C. Copolymerization may occur with the addition of a
second monomer such as another .alpha.-olefin.
[0060] 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 3 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. In the case of the catalysts prepared in Example 3, the
catalyst solution was generated in situ by mixing
Cp.sub.2ZrMe.sub.2 and PBB in 2 mL of toluene after aging for 0.5 h
at 60.degree. C., and then quickly injected into respective flasks
under an ethylene atmosphere using a pre-warmed gas-tight syringe.
The polymerization was quenched with acidic CH.sub.3OH after a
short time period (10-60 s) at which point voluminous quantities of
polyethylene precipitated out. The respective polymeric products
were collected by filtration, washed with methanol and dried under
high vacuum to a constant weight.
EXAMPLE 9
Ring-Opening Polymerization of THF
[0061] A small amount of
[(C.sub.5H.sub.3Me.sub.2).sub.2(Me)Zr--Me--Zr(Me)-
(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 polytetrahydrofuran by .sup.1H
analysis.
EXAMPLE 10
Propylene Polymerization
[0062] This reaction is 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 in 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 resulting oily liquid is removed from the vessel,
washed with methanol and water and dried under vacuum at
90-100.degree. C. for ten hours to result in a colorless oil.
[0063] Table II sets forth the relevant data concerning propylene
polymerization utilizing the catalyst prepared according to the
enumerated example.
3 TABLE II Example 3 5 Metallocene
(Cp.sub.2ZrMe).sub.2Me.sup..sym./ (Cp.sub.2ZrMe.sup..sym.)/
Cation/Anion* (MePBB).sup..crclbar. (MePBB).sup..crclbar. Catalyst
(mM) 0.15 0.15 Reaction Time (m) 40 40 Yield (g) 4.0 5.0 *Cp =
C.sub.5H.sub.5
[0064] While the invention has been described with reference to a
preferred embodiment, it will be understood by those skilled in the
art that various changes may be made and equivalents may be
substituted for elements thereof without departing from the scope
of the invention. In addition, many modifications may be made to
adapt a particular situation or material to the teachings of the
invention without departing from the essential scope thereof.
Therefore, it is intended that the invention not be limited to the
particular embodiment disclosed as the best mode contemplated for
carrying out this invention, but that the invention will include
all embodiments and equivalents falling within the scope of the
appended claims.
[0065] Various features of the invention are set forth in the
following claims.
* * * * *