U.S. patent application number 10/464152 was filed with the patent office on 2004-04-22 for expanded anionic compounds comprising hydroxyl or quiescent reactive functionality and catalyst activators therefrom.
This patent application is currently assigned to The Dow Chemical Company. Invention is credited to Babb, David A., Campbell, Richard E. JR., Carnahan, Edmund M., Jacobsen, Grant B., Neithamer, David R..
Application Number | 20040077491 10/464152 |
Document ID | / |
Family ID | 22819499 |
Filed Date | 2004-04-22 |
United States Patent
Application |
20040077491 |
Kind Code |
A1 |
Babb, David A. ; et
al. |
April 22, 2004 |
Expanded anionic compounds comprising hydroxyl or quiescent
reactive functionality and catalyst activators therefrom
Abstract
A cocatalyst or cocatalyst component, including a compound
corresponding to the formula:
(A*.sup.+a).sub.b(Z*J*.sub.j).sup.-c.sub.d, wherein: A* is a cation
of from 1 to 80 atoms, not counting hydrogen atoms, Z* is an anion
group of from 1 to 50 atoms, not counting hydrogen atoms,
containing two or more Lewis base sites; J* is a Lewis acid of from
1 to 80, not counting hydrogen atoms, coordinated to at least one
Lewis base site, and optionally two or more such J* groups may be
joined together in a moiety having multiple Lewis acidic
functionality, j is from 2 to 12 and a, b, c, and d are integers
from 1 to 3, with the proviso that a.times.b is equal to c.times.d,
and provided further that one or more of A*, Z* or J* comprises a
hydroxyl group or a polar group containing quiescent reactive
functionality.
Inventors: |
Babb, David A.; (Lake
Jackson, TX) ; Neithamer, David R.; (Midland, MI)
; Campbell, Richard E. JR.; (Midland, MI) ;
Jacobsen, Grant B.; (Houston, TX) ; Carnahan, Edmund
M.; (Fresno, TX) |
Correspondence
Address: |
JENKENS & GILCHRIST
1401 MCKINNEY
SUITE 2700
HOUSTON
TX
77010
US
|
Assignee: |
The Dow Chemical Company
Midland
MI
48674
|
Family ID: |
22819499 |
Appl. No.: |
10/464152 |
Filed: |
June 18, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10464152 |
Jun 18, 2003 |
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09904422 |
Jul 12, 2001 |
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6627573 |
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60219496 |
Jul 20, 2000 |
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Current U.S.
Class: |
502/162 ;
526/135 |
Current CPC
Class: |
C08F 210/16 20130101;
C08F 210/16 20130101; C07F 5/066 20130101; C08F 10/00 20130101;
C08F 4/65916 20130101; C08F 4/65912 20130101; C08F 10/00 20130101;
C08F 4/6592 20130101; C07F 7/0803 20130101; C08F 4/65927 20130101;
C08F 10/00 20130101; C08F 2500/12 20130101; C08F 4/65908 20130101;
C08F 210/14 20130101; C08F 4/61908 20130101; C07F 5/027 20130101;
C07F 5/062 20130101 |
Class at
Publication: |
502/162 ;
526/135 |
International
Class: |
C08F 004/06; B01J
031/00 |
Claims
In the claims:
16. (New) A cocatalyst or cocatalyst component, comprising a
compound corresponding to the formula:
(A*.sup.+a).sub.b(Z*J*.sub.j).sup.-c.sub.d, wherein: A* is a cation
of from 1 to 80 atoms, not counting hydrogen atoms, said A* having
a charge +a, Z* is an anion group of from 1 to 50 atoms, not
counting hydrogen atoms, further containing two or more Lewis base
sites; J* independently each occurrence is a Lewis acid of from 1
to 80 atoms, not counting hydrogen atoms, coordinated to at least
one Lewis base site of Z*, and optionally two or more such J*
groups may be joined together in a moiety having multiple Lewis
acidic functionality, j is a nubmer from 2 to 12 and a, b, c, and d
are integers from 1 to 3, with the proviso that a.times.b is equal
to c.times.d, and provided further that one or more of A*, Z* or J*
comprises a hydroxyl group or a polar group containing quiescent
reactive functionality.
17. (New) The cocatalyst or cocatalyst component according to claim
16 wherein A*.sup.+a is selected from the group consisting of
ammonium, sulfonium, phosphonium, oxonium, carbonium, silylium,
ferrocenium, Ag.sup.+, and Pb.sup.+2 cations.
18. (New) The cocatalyst or cocatalyst component according to claim
16 wherein Z* is selected from the group consisting of
trialkylsiloxy-, trialkylsiloxyalkyl-, trialkylsiloxyaryl-, and
dialkylaluminoxyaryl-subst- ituted derivatives of
4,5-benzylimidazolide, 2-(C.sub.1-30hydrocarbyl)-4,5-
-benzimidazolide, 1,3,4-triazolide,
2-(C.sub.1-30hydrocarbyl)-1,3,4-triazo- lide, 1,2,3-triazolide,
4,5-benz-1,2,3-triazolide, imidazolinide,
2-(C.sub.1-30hydrocarbyl)imidazolinide, 4,5-dihaloimidazolinide,
and 5,6-dimethylbenzimidazolide.
19. (New) The cocatalyst or cocatalyst component according to claim
16 which is an ammonium, phosphonium, sulfonium, oxonium,
carbonium, silylium, lead (II), silver or ferrocenium salt of
hydroxylphenyl-, trimethylsiloxyphenyl-, and
dialkylaluminoxyphenyl-substituted derivatives of:
bis(tris(pentafluorophenyl)borane)imidazolinide,
bis(tris(pentafluorophenyl)-borane)-2-undecylimidazolinide,
bis(tris(pentafluorophenyl)borane)-4,5-benzimidazolide,
bis(tris(penta-fluorophenyl)borane)1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)-imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,
bis(tris-(pentafluorophenyl)alumane)-4,5-benzimidazolide,
bis(tris(pentafluorophenyl)alumane)-1,3,4-triazolide, or
bis(tris(pentafluorophenyl)alumane)-2-undecyl-1,3,4-triazolide.
20. (New) A salt compound according to claim 16 wherein the cation
is a trimethylammonium-, triethylammonium-, tripropylammonium-,
tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,
methyldi(tetradecyl)ammonium-,
methyl(tetradecyl)(octadecyl)ammonium-, N,N-dimethylanilinium-,
N,N-diethylanilinium-, N,N-dimethyl(2,4,6-trimeth- ylanilinium)-,
N,N-di(tetradecyl)lanilinium-, N,N-di(tetradecyl)-2,4,6-tri-
methylanilinium)-, N,N-di(octadecyl)lanilinium-,
N,N-di(octadecyl)-2,4,6-t- rimethylanilinium)-, or
methyldicyclohexylammonium-cation.
21. (New) A The cocatalyst or cocatalyst component according to
claim 16 corresponding to the formula: 10wherein: A*+is a
monovalent cation as previously defined in claim 16, R.sup.4,
independently each occurrence, is hydrogen or a hydroxyhydrocarbyl,
halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl,
or silyl group, (including mono-, di- and tri(hydrocarbyl)silyl)
group of up to 30 atoms not counting hydrogen, preferably
C.sub.1-20 alkyl group, or a quiescent reactive group, with the
proviso that at least one R.sup.4 group contains a
hydroxyhydrocarbyl group or a quiescent reactive group, and J*' is
tris(pentafluorophenyl)bo- rane or
tris(pentafluorophenyl)alumane).
22. (New) The cocatalyst or cocatalyst component according to claim
16 comprising trihydrocarbylammonium-salt of:
bis(tris(pentafluorophenyl)bor-
ane)-2-(p-hydroxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)--
2-(p-hydroxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-
-(p-hydroxyphenyl)-4,5-benzimidazolide;
bis(tris(pentafluorophenyl)borane)-
-2-(p-trimethylsiloxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)bora-
ne)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophen-
yl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-benzimidazolide;
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolin-
ide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-1,3,4-
-triazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxypheny-
l)-4,5-benzimidazolide;
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyph-
enyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl-
)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl-
)-4,5-benziimidazolide;
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethyl-
siloxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trime-
thylsiloxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)-2--
(p-trimethylsiloxyphenyl)-4,5-benzimidazolide,
bis(tris(pentafluorophenyl)-
alumane)-2-(p-diethylaluminoxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-1,3,4-tr-
iazolide, or
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphen-
yl)-4,5-benzimidazolide.
23. (New) A catalyst composition for polymerization of addition
polymerizable monomers comprising, in combination, 1) a Group 3-10
or Lanthanide metal complex, preferably a Group 4 metal complex, 2)
a cocatalyst or cocatalyst component according to claim 16, or the
reaction product of 1 and 2), and optionally 3) a solid,
particulated support.
24. (New) A catalyst composition for polymerization of
.alpha.-olefins comprising, in combination, 1) a Group 3-10 or
Lanthanide metal complex, preferably a Group 4 metal complex and 2)
a cocatalyst or cocatalyst component according to claim 16.
25. (New) A catalyst component for use in formation of
heterogeneous catalyst compositions, comprising, in combination, a
cocatalyst or cocatalyst component according to claim 16 and a
solid, particulated support.
26. (New) The cocatalyst or cocatalyst component of claim 25
wherein the support is silica.
27. (New) The cocatalyst or cocatalyst component of claim 26
wherein the silica is dried and reacted with a trialkylaluminum
compound to remove reactive functionality thereon before contacting
with the metal complex or compound.
28. (New) A polymerization process comprising contacting one or
more .alpha.-olefins under polymerization conditions with a
catalyst composition the catalyst or cocatalyst component according
to claim 23.
29. (New) The polymerization process according to claim 28 that is
a slurry polymerization.
30. (New) A polymerization process according to claim 28 that is a
gas phase polymerization.
31. (New) The cocatalyst or cocatalyst component as recited in
claim 16, wherein A* is a cation of from 1 to 60 atoms, not
counting hydrogen atoms.
32. (New) The cocatalyst or cocatalyst component as recited in
claim 16, wherein Z* is an anion group of from 1 to 30 atoms, not
counting hydrogen atoms.
33. (New) The cocatalyst or cocatalyst component as recited in
claim 16, wherein J* independently each occurrence is a Lewis acid
of from 1 to 60 atoms, not counting hydrogen atoms.
Description
PRIOR RELATED APPLICATIONS
[0001] This is a continuation application of U.S. patent
application Ser. No. 09/904,422, filed Jul. 12, 2001, which claims
benefit of U.S. Provisional Patent Application No. 60/219,496,
filed Jul. 20, 2000, both of which are incorporated by reference
herein in their entirety.
FEDERALLY SPONSORED RESEARCH STATEMENT
[0002] Not applicable.
REFERENCE TO MICROFICHE APPENDIX
[0003] Not applicable.
BACKGROUND INFORMATION
[0004] The present invention relates to compounds that are useful
as catalyst components. More particularly the present invention
relates to such compounds that are particularly adapted for use in
the coordination polymerization of unsaturated compounds comprising
an anion containing at least two Lewis basic sites which are
coordinated to Lewis acids, and further containing a hydroxyl group
or a polar group containing a quiescent reactive functionality.
Such compounds are particularly advantageous for use in forming
supported polymerization catalysts wherein at least the catalyst
activator is chemically attached to a substrate material.
[0005] It is previously known in the art to activate Ziegler-Natta
polymerization catalysts, particularly such catalysts comprising
Group 3-10 metal complexes containing delocalized .pi.-bonded
ligand groups, by the use of Bronsted acid salts capable of
transferring a proton to form a cationic derivative or other
catalytically active derivative of such Group 3-10 metal complex.
Preferred Bronsted acid salts are such compounds containing a
cation/anion pair that is capable of rendering the Group 3-10 metal
complex catalytically active. Suitable activators comprise
fluorinated arylborate anions, such as tetrakis(pentafluoropheny-
l)borate. Additional suitable anions include sterically shielded
diboron anions of the formula: 1
[0006] wherein:
[0007] S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl,
Ar.sup.F is fluoroaryl, and X.sup.1 is either hydrogen or halide,
disclosed in U.S. Pat. No. 5,447,895. Additional examples include
carborane compounds such as are disclosed and claimed in U.S. Pat.
No. 5,407,884.
[0008] Examples of preferred charge separated (cation/anion pair)
activators are ammonium, sulfonium, or phosphonium salts capable of
transferring a hydrogen ion, disclosed in U.S. Pat. No. 5,198,401,
U.S. Pat. No. 5,132,380, U.S. Pat. No. 5,470,927 and U.S. Pat. No.
5,153,157, as well as oxidizing salts such as ferrocenium, silver
or lead salts, disclosed in U.S. Pat. No. 5,189,192 and U.S. Pat.
No. 5,321,106 and strongly Lewis acidic salts such as carbonium or
silylium salts, disclosed in U.S. Pat. No. 5,350,723 and U.S. Pat.
No. 5,625,087.
[0009] Further suitable activators for the above metal complexes
include strong Lewis acids including tris(perfluorophenyl)borane
and tris(perfluorobiphenyl)borane. The former composition has been
previously disclosed for the above stated end use in EP-A-520,732,
whereas the latter composition is similarly disclosed by Marks, et
al., in J. Am. Chem. Soc., 118, 12451-12452 (1996).
[0010] Despite the satisfactory performance of the foregoing
catalyst activators under a variety of polymerization conditions,
there is still a need for improved cocatalysts for use in the
activation of various metal complexes especially under a variety of
reaction conditions. Accordingly, it would be desirable if there
were provided compounds that could be employed in solution, slurry,
gas phase or high pressure polymerizations and under homogeneous or
heterogeneous process conditions having improved activation
properties. In particular, it would be desirable to provide
compounds that may be chemically bonded to support materials to
prepare supported catalyst components having improved resistance to
solvent removal and loss from the particle surface.
SUMMARY OF THE INVENTION
[0011] According to the present invention there are now provided
compounds useful as catalyst activators corresponding to the
formula: (A*+a)b(Z*J*j)-cd,
[0012] wherein:
[0013] A* is a cation of from 1 to 80, preferably 1 to 60 atoms,
not counting hydrogen atoms, said A* having a charge +a,
[0014] Z* is an anion group of from 1 to 50, preferably 1 to 30
atoms, not counting hydrogen atoms, further containing two or more
Lewis base sites;
[0015] J* independently each occurrence is a Lewis acid of from 1
to 80, preferably 1 to 60 atoms, not counting hydrogen atoms,
coordinated to at least one Lewis base site of Z*, and optionally
two or more such J* groups may be joined together in a moiety
having multiple Lewis acidic functionality,
[0016] j is a number from 2 to 12 and
[0017] a, b, c, and d are integers from 1 to 3, with the proviso
that a.times.b is equal to c.times.d, and provided further that one
or more of A*, Z* or J* comprises a hydroxyl group or a polar group
containing quiescent reactive functionality.
[0018] The foregoing compounds, in particular, those containing
quiescent reactive functionality may be utilized in combination
with one or more Group 3-10 or Lanthanide metal complexes to form
catalyst compositions for polymerization of addition polymerizable
monomers, especially ethylenically unsaturated monomers, most
preferably, C2-20,000 .alpha.-olefins. Additionally, the compounds
may be utilized to form latent activators, that is, compounds that
may themselves not cause a metal complex to become catalytically
active, but which may be converted to such a compound, by, for
example, in-situ reaction of the hydroxyl group or quiescent
reactive functionality or its derivative with a Lewis acid,
especially an aluminum hydrocarbyl compound, or an alkali metal
halide or ammonium halide salt. Moreover, the compounds may be
deposited onto solid supports, such as by impregnation, surface
deposition, physisorption or chemical reaction with the support,
reactive functionality of the support, or chemical modifiers
associated with the support, to form heterogeneous catalyst
components for use in preparing heterogeneous catalyst compositions
for use in polymerization of the foregoing monomers.
[0019] In one embodiment of the invention, the foregoing compounds
are used to form supported catalyst components by reaction of the
hydroxyl group thereof with reactive functionality of a support
material, or by conversion of the quiescent reactive functionality
to a reactive functionality and reaction thereof with reactive
functionality of a support material. The resulting supported
catalyst components are highly resistant to loss of activator
compound in a liquid reaction medium such as occurs in a slurry
polymerization. One or more Group 3-10 or Lanthanide metal
complexes, preferably a Group 4 metal complex, and additional
additives, modifiers and adjuvants may be added to the catalyst
component, either before, after or simultaneous with addition of
the cocatalyst of the present invention, to form the fully
formulated catalyst composition.
[0020] Additionally according to the present invention there is
provided a catalyst composition for polymerization of an
ethylenically unsaturated, polymerizable monomer comprising, in
combination, the above described activated derivative compound, a
Group 3-10 metal complex that is capable of activation to form an
addition polymerization catalyst, or the reaction product of such
combination, and optionally a support.
[0021] Additionally according to the present invention there is
provided a process for polymerization of one or more ethylenically
unsaturated, polymerizable monomers comprising contacting the same,
optionally in the presence of an inert aliphatic, alicyclic or
aromatic hydrocarbon, with the above catalyst composition or
supported catalyst composition.
[0022] The foregoing compounds are uniquely adapted for use in
activation of a variety of metal complexes, especially Group 4
metal complexes, under standard and atypical olefin polymerization
conditions. Because of this fact, the foregoing compounds are
capable of forming highly desirable olefin polymers in high
efficiency.
DETAILED DESCRIPTION OF THE INVENTION
[0023] All references herein to elements belonging to a certain
Group refer to the Periodic Table of the Elements published and
copyrighted by CRC Press, Inc., 1995. Also any reference to the
Group or Groups shall be to the Group or Groups as reflected in
this Periodic Table of the Elements using the IUPAC system for
numbering groups. When referred to herein, the teachings of any
patent, patent application or publication are hereby incorporated
by reference herein.
[0024] The catalyst activators of the invention are further
characterized in the following manner. A*+a is desirably chosen to
provide overall neutrality to the compound and to not interfere
with subsequent catalytic activity. Moreover, the cation may
participate in the formation of the active catalyst species,
desirably through a proton transfer, oxidation, or ligand
abstraction mechanism, or a combination thereof. Additionally,
certain cations beneficially improve the solubility of the
resulting activator in particular reaction media under use
conditions. For example, in the homopolymerization or
copolymerization of aliphatic olefins, particularly in the solution
phase, an aliphatic diluent is commonly used. Accordingly, cationic
species that are relatively soluble in such reaction media, or
render the catalyst activator more soluble therein are highly
preferred.
[0025] Examples of suitable cations include ammonium, sulfonium,
phosphonium, oxonium, carbonium, and silylium cations, preferably
those containing up to 80 atoms not counting hydrogen, as well as
ferrocenium, Ag+, Pb+2, or similar oxidizing cations. As previously
mentioned, the cation may also comprise a hydroxyl group or a polar
group containing quiescent reactive functionality. In a preferred
embodiment, a, b, c and d are all equal to one.
[0026] Z* can be any anionic moiety containing two or more Lewis
basic sites. Preferably, the Lewis base sites are on different
atoms of a polyatomic anionic moiety. Desirably, such Lewis basic
sites are relatively sterically accessible to the Lewis acid, J*.
Preferably the Lewis basic sites are on nitrogen or carbon atoms.
Examples of suitable Z* anions include cyanide, azide, amide and
substituted amide, amidinide and substituted amidinide,
dicyanamide, imidazolide, substituted imidazolide, imidazolinide,
substituted imidazolinide, tricyanomethide, tetracycanoborate,
puride, squarate, 1,2,3-triazolide, substituted 1,2,3-triazolide,
1,2,4-triazolide, substituted 1,2,4-triazolide, pyrimidinide,
substituted pyrimidinide, tetraimidazoylborate and substituted
tetraimidazoylborate anions, wherein each group, if present, is a
halo-, hydrocarbyl-, halohydrocarbyl-, silyl-, (including mono-,
di- and tri(hydrocarbyl)silyl-), silylhydrocarbyl-, halocarbyl- or
hydroxyl-group, or a polar group containing quiescent reactive
functionality, or two such groups together form a saturated or
unsaturated ring- or multiple ring-system.
[0027] Preferred Z* groups are: imidazolide,
2-nonadecylimidazolide, 2-undecylimidazolide,
2-tridecylimidazolide, 2-pentadecylimidazolide,
2-heptadecylimidazolide, 2-nonadecylimidazolide,
4,5-difluoroimidazolide, 4,5-dichloroimidazolide,
4,5-dibromoimidazolide, 4,5-bis(heptadecyl)imida- zolide,
4,5-bis(undecyl)imidazolide, imidazolinide,
2-nonadecylimidazolinide, 2-undecylimidazolinide,
2-tridecylimidazolinide- , 2-pentadecylimidazolinide,
2-heptadecylimidazolinide, 2-nonadecylimidazolinide,
4,5-difluoroimidazolinide, 4,5-dichloroimidazolinide,
4,5-dibromoimidazolinide, 4,5-bis(heptadecyl)imidazolinide,
4,5-bis(undecyl)imidazolinide, didecylamide, piperidinide,
4,4-dimethylimidazolinide, tetra-5-pyrimidinylborate, pyrimidinide,
5,6-dichlorobenzimidazolide, 4,5-dicyanoimidazolide, and
5,6-dimethylbenzimidazolide anions, or said Z* groups that are
further substituted with a hydroxyl group or a polar group
containing quiescent reactive functionality.
[0028] Coordinated to the Lewis base sites of the anion are from 2
to 12 Lewis acids, J*, two or more of which may be joined together
in a moiety having multiple Lewis acidic functionality. Optionally,
said J* group may comprise a hydroxyl group or a polar group
containing quiescent reactive functionality, so long as such
functionality does not interfere with the Lewis acid functionality
of the group. Preferably, from 2 to 4 J* groups having from 3 to
100 atoms not counting hydrogen are present.
[0029] More specific examples of the foregoing Lewis acid
compounds, J*, correspond to the formula: 2
[0030] wherein:
[0031] M* is aluminum, gallium or boron;
[0032] R.sup.1 and R.sup.2 independently each occurrence are
hydride, halide, or a hydrocarbyl, halocarbyl, halohydrocarbyl,
dialkylamido, alkoxide, or aryloxide group of up to 20 carbons,
optionally substituted with a hydroxyl group or a polar group
containing quiescent reactive functionality, and
[0033] Ar.sup.f1--Ar.sup.f2 in combination, independently each
occurrence, is a divalent fluoro-substituted aromatic group of from
6 to 20 carbons, optionally substituted with a hydroxyl group or a
polar group containing quiescent reactive functionality.
[0034] Highly preferred Lewis acids are aluminum or boron compounds
corresponding to the formula: AlR13, or BR13, wherein R1
independently each occurrence is selected from hydrocarbyl,
halocarbyl, and halohydrocarbyl radicals, or such groups further
substituted with a hydroxyl group or a polar group containing
quiescent reactive functionality, said R1 having up to 20 carbons.
In a more highly preferred embodiment, R1 is a fluorinated C1-20
hydrocarbyl group, most preferably, a fluorinated aryl group,
especially, pentafluorophenyl.
[0035] Preferred examples of the foregoing Lewis acid groups
containing multiple Lewis acid sites are: 3
[0036] By the term "polar group containing quiescent reactive
functionality" is meant an oxygen, nitrogen, sulfur, or phosphorus
containing ligand group that is capped or protected and thereby
rendered relatively inert to reaction conditions used in the
synthesis or use of the present compounds, but wherein the capping
or protecting groups may be later removed, if desired, thereby
generating a reactive polar functional group, especially a hydroxyl
group or metallated derivative thereof. Suitable reactive polar
functional groups include hydroxyl, thiol, amine, and phosphine
groups, or hydrocarbyl-, alkali metal- or Bronsted acid
salt-derivatives thereof. Suitable quiescent reactive functionality
includes the trihydrocarbyllsilyl-, trihydrocarbylgermyl-,
dihydrocarbylaluminum-, hydrocarbylzinc- or
hydrocarbylmagnesium-function- alized derivative of the foregoing
polar groups. Particularly preferred polar containing quiescent
reactive functional groups are trihydrocarbylsiloxy,
trihydrocarbylsiloxy-substituted hydrocarbyl,
dihydrocarbylaluminoxy and dihydrocarbylaluminoxy substituted
hydrocarbyl groups. Especially preferred are the trialkylsiloxy- or
dialkylaluminoxy-derivatives of such polar functional groups,
containing from 1 to 6 carbon in each alkyl group. Especially
preferred quiescent reactive functional groups are
trimethylsiloxy-groups and diethylaluminoxy-groups.
[0037] Such polar group containing quiescent reactive functionality
is activated by reaction with a metal hydrocarbyl-, metal
halocarbyl-, hydrocarbylmetaloxy- or metal halohydrodarbyl-compound
under ligand exchange conditions, thereby producing a neutral
hydrocarbon, halohydrocarbon, trimethylsilylhydrocarbon,
trimethylsilylhalohydrocarbon or trimethylsilylhalocarbon compound
as a by-product. The hydroxyl group or polar group containing
quiescent reactive functionality may also be employed to react with
hydroxyl-, alkylmetal-, hydrocarbylsilyl-, or
hydrocarbylsiloxy-functionality of a solid, particulated, support
material, optionally after conversion to a metallated or protonated
intermediate. This results in tethering or chemically attaching the
activator to the surface of the solid, particulated, support
material. The resulting substance demonstrates enhanced resistance
to loss or removal when exposed to liquids in a polymerization
process.
[0038] In a preferred embodiment, the foregoing hydroxyl group or
polar group containing quiescent reactive functionality is located
in the Z* ligand. Examples include hydroxyl, trialkylsiloxy-,
trialkylsiloxyalkyl-, trialkylsiloxyaryl-, and
dialkylaluminoxyaryl-substituted derivatives of imidazolide,
2-(C1-30hydrocarbyl)imidazolide, 4,5-dihaloimidazolide,
4,5-di(C1-30hydrocarbyl)imidazolide, 4,5-benzylimidazolide,
2-(C1-30hydrocarbyl)-4,5-benzimidazoline, 1,3,4-triazolide,
2-(C1-30hydrocarbyl-1,3,4-triazolide, 1,2,3-triazolide,
4,5-benz-1,2,3-triazolide, imidazolinide,
2-(C1-30hydrocarbyl)-imidazolin- ide, 4,5-dihaloimidazolinide, and
5,6-dimethylbenzimidazolide. Especially preferred examples include
hydroxyaryl, trimethylsiloxyaryl-, and
dialkylaluminoxyaryl-substituted derivatives of imidazolide,
2-(C1-30alkyl)imidazolide, 4,5-di(C1-30alkyl)-imidazolide,
4,5-benzimidazolide, 1,3,4-triazolide,
2-(C1-30alkyl-1,3,4-triazolide, and 1,2,3-triazolide.
[0039] Especially suitable expanded anion compounds according to
the present invention include the ammonium, phosphonium, sulfonium,
oxonium, carbonium, silylium, lead (II), silver or ferrocenium
salts of hydroxylphenyl-, trimethylsiloxyphenyl-, and
dialkylaluminoxyphenyl-subst- ituted derivatives of:
bis(tris(penta-fluorophenyl)borane)-imidazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-imidazolide,
bis(tris(pentafluorophenyl)borane)imidazolinide,
bis(tris(pentafluorophen- yl)-borane)-2-undecylimidazolinide,
bis(tris(pentafluorophenyl)borane)-4,5- -benzimidazolide,
bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)im-
idazolide, bis(tris(penta-fluorophenyl)borane)1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)imidazolide,
bis(tris(penta-fluorophen- yl)alumane)-2-undecylimidazolide,
bis(tris(pentafluorophenyl)alumane)-imid- azolinide,
bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,
bis(tris-(pentafluorophenyl)alumane)-4,5-benzimidazolide,
bis(tris(pentafluoro-phenyl)alumane)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-1,3,4-triazolide, and
bis(tris(pentafluorophenyl)alumane)-2-undecyl-1,3,4-triazolide.
[0040] Preferred expanded anion compounds are the ammonium salts of
the foregoing derivatives, especially those which comprise
trihydrocarbyl-substituted ammonium cations, especially
trimethylammonium-, triethylammonium-, tripropylammonium-,
tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,
methyldi(tetradecyl)ammonium-,
methyl(tetradecyl)(octadecyl)ammonium-, N,N-dimethylanilinium-,
N,N-diethylanilinium-, N,N-dimethyl(2,4,6-trimeth- ylanilinium)-,
N,N-di(tetradecyl)lanilinium-, N,N-di(tetradecyl)-2,4,6-tri-
methylanilinium)-, N,N-di(octadecyl)lanilinium-,
N,N-di(octadecyl)-2,4,6-t- rimethylanilinium)-, and
methyldicyclohexylammonium-cations, or mixtures thereof.
[0041] Most preferred ammonium cation containing salts are those
containing trihydrocarbyl-substituted ammonium cations containing
one or two C10-C40 alkyl groups, especially
methylbis(octadecyl)ammonium- and
methylbis(tetradecyl)ammonium-cations. It is further understood
that the cation may comprise a mixture of hydrocarbyl groups of
differing lengths. For example, the protonated ammonium cation
derived from the commercially available long chain amine comprising
a mixture of two C14, C16 or C18 alkyl groups and one methyl group.
Such amines are available from Witco Corp., under the trade name
Kemamine.TM. T9701, and from Akzo-Nobel under the trade name
Armeen.TM. M2HT.
[0042] The foregoing cocatalysts (illustrated by those having
substituted-imidazolide, imidazolinide, benzimidazolide,
1,3,4-triazolide, 1,2,3-triazolide, or 4,5-benzi-1,2,3-triazolide
anions containing one or more hydroxyl-, trimethylsiloxy-,
trimethylsiloxyalkyl-, or trimethylsiloxyaryl-groups) may be
depicted schematically as follows: 4
[0043] wherein:
[0044] A*.sup.+ is a monovalent cation as previously defined, and
preferably is a trihydrocarbyl ammonium cation, containing one or
two C.sub.10-40 alkyl groups, especially the
methylbis(tetradecyl)ammonium- or
methylbis(octadecyl)ammonium-cation,
[0045] R.sup.4, independently each occurrence, is hydrogen or a
hydroxyhydrocarbyl, halo, hydrocarbyl, halocarbyl, halohydrocarbyl,
silylhydrocarbyl, or silyl group, (including mono-, di- and
tri(hydrocarbyl)silyl) group of up to 30 atoms not counting
hydrogen, preferably C.sub.1-20 alkyl group, or a quiescent
reactive group, with the proviso that at least one R.sup.4 group
contains a hydroxyhydrocarbyl group or a quiescent reactive group,
preferably a hydroxyaryl, trialkylsiloxy-, trialkylsiloxyalkyl-,
trialkylsiloxyaryl-, or dialkyllaluminoxyaryl-ligand, more
preferably a trimethylsiloxy-, trimethylsiloxymethyl-,
trimethylsiloxyphenyl-, or diethylaluminoxyphenyl-ligand, and
[0046] J*' is tris(pentafluorophenyl)borane or
tris(pentafluorophenyl)alum- ane).
[0047] Examples of the most highly preferred catalyst activators
herein include the forgoing trihydrocarbylammonium-, especially,
methylbis(tetradecyl)ammonium- or
methylbis(octadecyl)ammonium-salts of:
[0048]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolide,
[0049]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxybiphenyl)imidazolide-
,
[0050]
bis(tris(pentafluorophenyl)borane)-5-(p-hydroxynaphthyl)imidazolide-
,
[0051]
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-hydroxyphenyl)imi-
dazolide,
[0052]
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-hydroxyphenyl)-
imidazolide,
[0053]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(unde-
cyl)imidazolide,
[0054]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(hept-
adecyl)imidazolide,
[0055]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolinide-
,
[0056]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-1,3,4-triazo-
lide,
[0057]
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-benziimi-
dazolide;
[0058]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imida-
zolide,
[0059]
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-trimethylsiloxyph-
enyl)imidazolide,
[0060]
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-trimethylsilox-
yphenyl)imidazolide,
[0061]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5--
bis(undecyl)imidazolide,
[0062]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5--
bis(heptadecyl)imidazolide,
[0063]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imida-
zolinide,
[0064]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-1,3,-
4-triazolide,
[0065]
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5--
benziimidazolide;
[0066]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imid-
azolide,
[0067]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxybiphenyl)im-
idazolide,
[0068]
bis(tris(pentafluorophenyl)borane)-5-(p-diethylaluminoxynaphthyl)im-
idazolide,
[0069]
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-diethylaluminoxyp-
henyl)imidazolide,
[0070]
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-diethylalumino-
xyphenyl)imidazolide,
[0071]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-
-bis(undecyl)imidazolide,
[0072]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-
-bis(heptadecyl)imidazolide,
[0073]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imid-
azolinide,
[0074]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-1,3-
,4-triazolide,
[0075]
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-
-benziimidazolide;
[0076]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolide,
[0077]
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-hydroxyphenyl)im-
idazolide,
[0078]
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-hydroxyphenyl-
)imidazolide,
[0079]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(und-
ecyl)imidazolide,
[0080]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(hep-
tadecyl)imidazolide,
[0081]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolinid-
e,
[0082]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-1,3,4-triaz-
olide,
[0083]
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-benziim-
idazolide;
[0084]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imid-
azolide,
[0085]
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-trimethylsiloxyp-
henyl)imidazolide,
[0086]
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-trimethylsilo-
xyphenyl)imidazolide,
[0087]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-
-bis(undecyl)imidazolide,
[0088]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-
-bis(heptadecyl)imidazolide,
[0089]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imid-
azolinide,
[0090]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-1,3-
,4-triazolide,
[0091]
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-
-benziimidazolide,
[0092]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imi-
dazolide,
[0093]
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-diethylaluminoxy-
phenyl)imidazolide,
[0094]
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-diethylalumin-
oxyphenyl)-imidazolide,
[0095]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,-
5-bis(undecyl)imidazolide,
[0096]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,-
5-bis(heptadecyl)imidazolide,
[0097]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imi-
dazolinide,
[0098]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-1,-
3,4-triazolide, and
[0099]
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,-
5-benziimidazolide.
[0100] The compounds may be prepared by a condensation reaction
between the alkali metal salt of the anion, Z*, and a Lewis acid,
J*, preferably under phase transfer conditions, using for example a
crown ether to solubilize the alkali metal salt if necessary,
followed by a metathesis reaction with the corresponding halide
salt of the cation, A*.sup.+a. Certain of the cocatalysts are also
amenable to preparation via a one step, single reactor process. For
example, the ammonium- or phosphonium-substituted hydroxyl group or
quiescent reactive group-substituted imidiazolide salts can be
prepared by contacting the Lewis acid, J*, or its Lewis base
adduct, such as an etherate, with the neutral compound
corresponding to the anion, Z*. Both reactants are desirably
relatively lipophilic, such that the reaction can be performed in
non-polar solvents. Addition of the free base corresponding to the
cation, A*.sup.+a, results in formation of the charge separated
species, which may be recovered from the reaction mixture by
devolatilization or used without further purification.
[0101] The corresponding reactive hydroxyl-, thiol, amine, or
phosphine containing compound (or its metal or ammonium salt
derivative) may be generated or produced in situ by reaction of the
quiescent reactive groups of the present compounds with any
suitable reactant, such as a hydrocarbon, a metal fluoride, an
ammonium fluoride, or an acid, thereby removing the capping or
protecting group(s).
[0102] Due to the presence of the hydroxyl group or quiescent
reactive functionality in the compounds of the present invention,
or reactive derivatives thereof, the present compounds may be
readily attached to a reactive substrate, such as a particulated
solid containing reactive hydrocarbyl groups, especially
hydrocarbylmetal- or hydrocarbylmetalloid-functionality. Examples
include alumina, silica, aluminosilicates, and aluminum magnesium
silicate materials, containing reactive hydroxyl- or
hydrocarbyl-functionality, and such materials treated with any
substance to impart reactive metal-hydrocarbyl or
metalloid-hydrocarbyl functionality. Examples of such treating
substances include trihydrocarbyl aluminum compounds, chlorosilane
compounds, and mono- or di-hydrocarbylsilane compounds that react
with a portion or all of reactive surface hydroxyl functionality of
the substrate to form a "capped" derivative. This technique is
known in the art and disclosed for example in U.S. Pat. No.
6,087,293.
[0103] Suitable catalysts for use in combination with the foregoing
cocatalysts include any compound or complex of a metal of Groups
3-10 of the Periodic table of the Elements capable of being
activated to polymerize ethylenically unsaturated compounds by the
present activators. Examples include Group 10 diimine derivatives
corresponding to the formula: 5
[0104] wherein
[0105] M* is Ni(II) or Pd(II);
[0106] K is halo, hydrocarbyl, or hydrocarbyloxy;
[0107] and the two nitrogen atoms are linked by a bridging
system.
[0108] Such catalysts have been previously disclosed in J. Am.
Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415
(1995), and Organometallics, 16, 1514-1516, (1997).
[0109] Additional catalysts include derivatives of Group 3, 4, or
Lanthanide metals which are in the +2, +3, or +4 formal oxidation
state. Preferred compounds include metal complexes containing from
1 to 3 .pi.-bonded anionic or neutral ligand groups, which may be
cyclic or non-cyclic delocalized .pi.-bonded anionic ligand groups.
Exemplary of such .pi.-bonded anionic ligand groups are conjugated
or nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups,
boratabenzene groups, phosphole, and arene groups. By the term
".pi.-bonded" is meant that the ligand group is bonded to the
transition metal by a sharing of electrons from a partially
delocalized .pi.-bond.
[0110] Each atom in the delocalized .pi.-bonded group may
independently be substituted with a radical selected from the group
consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl,
hydrocarbyl-substituted metalloid radicals wherein the metalloid is
selected from Group 14 of the Periodic Table of the Elements, and
such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals
further substituted with a Group 15 or 16 hetero atom containing
moiety. Included within the term "hydrocarbyl" are C.sub.1-20
straight, branched and cyclic alkyl radicals, C.sub.6-20 aromatic
radicals, C.sub.7-20 alkyl-substituted aromatic radicals, and
C.sub.7-20 aryl-substituted alkyl radicals. In addition two or more
such radicals may together form a fused ring system, including
partially or fully hydrogenated fused ring systems, or they may
form a metallocycle with the metal. Suitable
hydrocarbyl-substituted organometalloid radicals include mono-, di-
and tri-substituted organometalloid radicals of Group 14 elements
wherein each of the hydrocarbyl groups contains from 1 to 20 carbon
atoms. Examples of suitable hydrocarbyl-substituted organometalloid
radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl,
methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.
Examples of Group 15 or 16 hetero atom containing moieties include
amine, phosphine, ether or thioether moieties or divalent
derivatives thereof, e. g. amide, phosphide, ether or thioether
groups bonded to the transition metal or Lanthanide metal, and
bonded to the hydrocarbyl group or to the hydrocarbyl-substituted
metalloid containing group.
[0111] Examples of suitable anionic, delocalized .pi.-bonded groups
include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,
tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl,
cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl,
decahydroanthracenyl groups, phosphole, and boratabenzene groups,
as well as hydrocarbyl- silyl- (including mono-, di-, or
tri(hydrocarbyl)silyl) substituted derivatives thereof. Preferred
anionic, delocalized .pi.-bonded groups are cyclopentadienyl,
pentamethylcyclopentadienyl, tetramethylcyclopentadieny- l,
tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl,
2,3-dimethylindenyl, fluorenyl, 2-methylindenyl,
2-methyl-4-phenylindenyl- , tetrahydrofluorenyl,
octahydrofluorenyl, and tetrahydroindenyl.
[0112] The boratabenzenes are anionic ligands that are boron
containing analogues to benzene. They are previously known in the
art having been described by G. Herberich, et al., in
Organometallics, 14,1, 471-480 (1995). Preferred boratabenzenes
correspond to the formula: 6
[0113] wherein R" is selected from the group consisting of
hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said R"
having up to 20 non-hydrogen atoms. In complexes involving divalent
derivatives of such delocalized .pi.-bonded groups one atom thereof
is bonded by means of a covalent bond or a covalently bonded
divalent group to another atom of the complex thereby forming a
bridged system.
[0114] Phospholes are anionic ligands that are phosphorus
containing analogues to a cyclopentadienyl group. They are
previously known in the art having been described by WO 98/50392,
and elsewhere. Preferred phosphole ligands correspond to the
formula: 7
[0115] wherein R" is selected from the group consisting of
hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said R"
having up to 20 non-hydrogen atoms, and optionally one or more R"
groups may be bonded together forming a multicyclic fused ring
system, or form a bridging group connected to the metal. In
complexes involving divalent derivatives of such delocalized
.pi.-bonded groups one atom thereof is bonded by means of a
covalent bond or a covalently bonded divalent group to another atom
of the complex thereby forming a bridged system.
[0116] Phosphinimine/cyclopentadienyl complexes are disclosed in
EP-A-890581 and correspond to the formula
[(R***).sub.3-P=N].sub.bM**(Cp)- (L.sup.1).sub.3-b, wherein:
[0117] R*** is a monovalent ligand, illustrated by hydrogen,
halogen, or hydrocarbyl, or two R*** groups together form a
divalent ligand,
[0118] M** is a Group 4 metal,
[0119] Cp is cyclopentadienyl, or similar delocalized .pi.-bonded
group,
[0120] L.sup.1 is a monovalent ligand group, illustrated by
hydrogen, halogen or hydrocarbyl,
[0121] b is a number from 1 to 3; and
[0122] n is 1 or 2.
[0123] A suitable class of catalysts are transition metal complexes
corresponding to the formula:
[0124] L.sub.p1MX.sub.mX'.sub.nX".sub.p, or a dimer thereof
[0125] wherein:
[0126] Lp is an anionic, delocalized, .pi.-bonded group that is
bound to M, containing up to 50 non-hydrogen atoms, optionally two
Lp groups may be joined together forming a bridged structure, and
further optionally one Lp may be bound to X;
[0127] M is a metal of Group 4 of the Periodic Table of the
Elements in the +2, +3 or +4 formal oxidation state;
[0128] X is an optional, divalent group of up to 50 non-hydrogen
atoms that together with Lp forms a metallocycle with M;
[0129] X' is an optional neutral ligand having up to 20
non-hydrogen atoms;
[0130] X" each occurrence is a monovalent, anionic moiety having up
to 40 non-hydrogen atoms, optionally, two X" groups may be
covalently bound together forming a divalent dianionic moiety
having both valences bound to M, or, optionally 2 X" groups may be
covalently bound together to form a neutral, conjugated or
nonconjugated diene that is .pi.-bonded to M (whereupon M is in the
+2 oxidation state), or further optionally one or more X" and one
or more X' groups may be bonded together thereby forming a moiety
that is both covalently bound to M and coordinated thereto by means
of Lewis base functionality;
[0131] l is 0, 1 or 2;
[0132] m is 0 or 1;
[0133] n is a number from 0 to 3;
[0134] p is an integer from 0 to 3; and
[0135] the sum, l+m+p, is equal to the formal oxidation state of M,
except when 2 X" groups together form a neutral conjugated or
non-conjugated diene that is .pi.-bonded to M, in which case the
sum l+m is equal to the formal oxidation state of M.
[0136] Preferred complexes include those containing either one or
two Lp groups. The latter complexes include those containing a
bridging group linking the two Lp groups. Preferred bridging groups
are those corresponding to the formula (ER*.sub.2).sub.x,
B(NR**.sub.2), or B(NR**.sub.2).sub.2, wherein E is silicon,
germanium, tin, or carbon, R* independently each occurrence is
hydrogen or a group selected from silyl, hydrocarbyl,
hydrocarbyloxy, and combinations thereof, said R* having up to 30
carbon or silicon atoms, R** independently each occurrence is a
group selected from silyl, hydrocarbyl, and combinations thereof,
said R** having up to 30 carbon or silicon atoms, and x is 1 to 8.
Preferably, R* independently each occurrence is methyl, ethyl,
propyl, benzyl, butyl, phenyl, methoxy, ethoxy, or phenoxy, and R**
is methyl, ethyl, propyl, benzyl or butyl.
[0137] Examples of the complexes containing two Lp groups are
compounds corresponding to the formula: 8
[0138] wherein:
[0139] M is titanium, zirconium or hafnium, preferably zirconium or
hafnium, in the +2 or +4 formal oxidation state;
[0140] R.sup.3 in each occurrence independently is selected from
the group consisting of hydrogen, hydrocarbyl, silyl, germyl,
cyano, halo and combinations thereof, said R.sup.3 having up to 20
non-hydrogen atoms, or adjacent R.sup.3 groups together form a
divalent derivative (that is, a hydrocarbadiyl, siladiyl or
germadiyl group) thereby forming a fused ring system, and
[0141] X" independently each occurrence is an anionic ligand group
of up to 40 non-hydrogen atoms, or two X" groups together form a
divalent anionic ligand group of up to 40 non-hydrogen atoms or
together are a conjugated diene having from 4 to 30 non-hydrogen
atoms forming a .pi.-complex with M, whereupon M is in the +2
formal oxidation state, and
[0142] R*, R**, E and x are as previously defined, preferably
(ER*.sub.2).sub.x is dimethylsilandiyl or ethylene, and BNR**.sub.2
is di(isopropyl)aminoborandiyl.
[0143] The foregoing metal complexes are especially suited for the
preparation of polymers having stereoregular molecular structure.
In such capacity it is preferred that the complex possesses C.sub.s
symmetry or possesses a chiral, stereorigid structure. Examples of
the first type are compounds possessing different delocalized
.pi.-bonded systems, such as one cyclopentadienyl group and one
fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were
disclosed for preparation of syndiotactic olefin polymers in Ewen,
et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral
structures include rac bis-indenyl complexes. Similar systems based
on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic
olefin polymers in Wild et al., J. Organomet. Chem., 232, 233-47,
(1982).
[0144] Exemplary bridged ligands containing two .pi.-bonded groups
are:
[0145] dimethylbis(cyclopentadienyl)silane,
dimethylbis(tetramethylcyclope- ntadienyl)silane,
[0146] dimethylbis(2-ethylcyclopentadien-1-yl)silane,
dimethylbis(2-t-butylcyclopentadien-1-yl)silane,
[0147] 2,2-bis(tetramethylcyclopentadienyl)propane,
dimethylbis(inden-1-yl)silane,
[0148] dimethylbis(tetrahydroinden-1-yl)silane,
dimethylbis(fluoren-1-yl)s- ilane,
[0149] dimethylbis(tetrahydrofluoren-1-yl)silane,
dimethylbis(2-methyl-4-p- henylinden-1-yl)-silane,
[0150] dimethylbis(2-methylinden-1-yl)silane,
di(isopropyl)aminobis(cyclop- entadien-1-yl)borandiyl,
[0151]
di(isopropyl)aminobis(2-methyl-4-phenylinden-1-yl)-borandiyl,
di(isopropyl)aminobis(2-methylinden-1-yl)borandiyl,
dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,
[0152] dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,
[0153] dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,
(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,
(1,2-bis(cyclopentadienyl)ethane, and
dimethyl(cyclopentadienyl)-1-(fluor- en-1-yl)methane.
[0154] Preferred X" groups are selected from hydride, hydrocarbyl,
silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and
aminohydrocarbyl groups, or two X" groups together form a divalent
derivative of a conjugated diene or else together they form a
neutral, .pi.-bonded, conjugated diene. Most preferred X" groups
are C.sub.1-20 hydrocarbyl groups.
[0155] Complexes containing two Lp groups including bridged
complexes suitable for use in the present invention include:
[0156] bis(cyclopentadienyl)zirconiumdimethyl,
[0157] bis(cyclopentadienyl)zirconium dibenzyl,
[0158] bis(cyclopentadienyl)zirconium methyl benzyl,
[0159] bis(cyclopentadienyl)zirconium methyl phenyl,
[0160] bis(cyclopentadienyl)zirconiumdiphenyl,
[0161] bis(cyclopentadienyl)titanium-allyl,
[0162] bis(cyclopentadienyl)zirconiummethylmethoxide,
bis(cyclopentadienyl)zirconiummethylchloride,
[0163] bis(pentamethylcyclopentadienyl)zirconiumdimethyl,
[0164] bis(pentamethylcyclopentadienyl)titaniumdimethyl,
[0165] bis(indenyl)zirconiumdimethyl,
[0166] indenylfluorenylzirconiumdimethyl,
[0167] bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),
[0168] bis(indenyl)zirconiummethyltrimethylsilyl,
[0169] bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,
[0170] bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,
[0171] bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,
[0172]
bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,
[0173] bis(pentamethylcyclopentadienyl)zirconiummethylchloride,
[0174] bis(methylethylcyclopentadienyl)zirconiumdimethyl,
[0175] bis(butylcyclopentadienyl)zirconiumdibenzyl,
[0176] bis(t-butylcyclopentadienyl)zirconiumdimethyl,
[0177] bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,
[0178] bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,
[0179] bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,
[0180] dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,
[0181] dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III)
allyl
[0182]
dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdibenzyl,
[0183] dimethylsilyl-bis(n-butylcyclopentadienyl)zirconium
bis(trimethylsilyl),
[0184] (methylene-bis(tetramethylcyclopentadienyl)titanium(III)
2-(dimethylamino)benzyl,
[0185] (methylene-bis(n-butylcyclopentadienyl)titanium(III)
2-(dimethylamino)benzyl,
[0186] dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,
[0187] dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,
[0188]
dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,
[0189]
dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadi-
ene,
[0190] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II)
1,4-diphenyl-1,3-butadiene,
[0191] dimethylsilyl-bis(tetrahydroindenyl)zirconium(II)
1,4-diphenyl-1,3-butadiene,
[0192]
di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconium
dimethyl,
[0193] dimethylsilyl-bis(tetrahydrofluorenyl)zirconium
bis(trimethylsilyl),
[0194]
(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl,
and
[0195]
dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium
dimethyl.
[0196] A further class of metal complexes utilized in the present
invention corresponds to the preceding formula LplMXmX'nX"p, or a
dimer thereof, wherein X is a divalent group of up to 50
non-hydrogen atoms that together with Lp forms a metallocycle with
M.
[0197] Preferred divalent X groups include groups containing up to
30 non-hydrogen atoms comprising at least one atom that is oxygen,
sulfur, boron or a member of Group 14 of the Periodic Table of the
Elements directly attached to the delocalized .pi.-bonded group,
and a different atom, selected from the group consisting of
nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to
M.
[0198] A preferred class of such Group 4 metal coordination
complexes used according to the present invention corresponds to
the formula: 9
[0199] wherein:
[0200] M is titanium or zirconium, preferably titanium in the +2,
+3, or +4 formal oxidation state;
[0201] R.sup.3 in each occurrence independently is selected from
the group consisting of hydrogen, hydrocarbyl, silyl, germyl,
cyano, halo and combinations thereof, said R.sup.3 having up to 20
non-hydrogen atoms, or adjacent R.sup.3 groups together form a
divalent derivative (that is, a hydrocarbadiyl, siladiyl or
germadiyl group) thereby forming a fused ring system,
[0202] each X" is a halo, hydrocarbyl, hydrocarbyloxy or silyl
group, said group having up to 20 non-hydrogen atoms, or two X"
groups together form a neutral C.sub.5-30 conjugated diene or a
divalent derivative thereof;
[0203] Y is --O--, --S--, --NR*--, --PR*--; and
[0204] Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2SiR*.sub.2,
CR*.sub.2CR*.sub.2, CR*.dbd.CR*, CR*.sub.2SiR*.sub.2, GeR*.sub.2,
or B(NR**.sub.2) wherein R* and R** are as previously defined.
[0205] Illustrative Group 4 metal complexes of the latter formula
that may be employed in the practice of the present invention
include:
[0206] cyclopentadienyltitaniumtrimethyl,
[0207] indenyltitaniumtrimethyl,
[0208] octahydrofluorenyltitaniumtrimethyl,
[0209] tetrahydroindenyltitaniumtrimethyl,
[0210] tetrahydrofluorenyltitaniumtrimethyl,
[0211]
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahyd-
ronaphthalenyl)dimethylsilanetitaniumdimethyl,
[0212]
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8--
hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,
[0213] (tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)
dimethylsilanetitanium dibenzyl,
[0214]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium dimethyl,
[0215]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)-1,2-eth-
anediyltitanium dimethyl,
[0216]
(tert-butylamido)(tetramethyl-.eta..sup.5-indenyl)dimethylsilanetit-
anium dimethyl,
[0217]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silane titanium (III) 2-(dimethylamino)benzyl;
[0218]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (III) allyl,
[0219]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (III) 2,4-dimethylpentadienyl,
[0220]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (II) 1,4-diphenyl-1,3-butadiene,
[0221]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (II) 1,3-pentadiene,
[0222] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl-1,3butadiene,
[0223] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 2,4-hexadiene,
[0224] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) 2,3-dimethyl-1,3-butadiene,
[0225] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) isoprene,
[0226] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) 1,3-butadiene,
[0227] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) 2,3-dimethyl-1,3-butadiene,
[0228] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) isoprene
[0229] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) dimethyl
[0230] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) dibenzyl
[0231] tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(IV) 1,3-butadiene,
[0232] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0233] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl-1,3-butadiene,
[0234] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0235] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) dimethyl,
[0236] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium
(IV) dibenzyl,
[0237]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 1,4-diphenyl1,3-butadiene,
[0238]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 1,3-pentadiene,
[0239]
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium
(II) 2,4-hexadiene,
[0240]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
-silanetitanium (IV) 1,3-butadiene,
[0241]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
[0242]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (IV) isoprene,
[0243]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
-silanetitanium (II) 1,4-dibenzyl-1,3-butadiene,
[0244]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
silanetitanium (II) 2,4-hexadiene,
[0245]
(tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl)dimethyl-
-silanetitanium (II) 3-methyl-1,3-pentadiene,
[0246]
(tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitanium-
dimethyl,
[0247]
(tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniu-
mdimethyl,
[0248]
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahyd-
ronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,
[0249]
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8--
hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl
[0250] (tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl
methylphenylsilanetitanium (IV) dimethyl,
[0251] (tert-butylamido)(tetramethyl-.eta..sup.5-cyclopentadienyl
methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,
[0252]
1-(tert-butylamido)-2-(tetramethyl-.eta..sup.5-cyclopentadienyl)eth-
anediyltitanium (IV) dimethyl,
[0253]
1-(tert-butylamido)-2-(tetramethyl-.eta..sup.5-cyclopentadienyl)eth-
anediyl titanium (II) 1,4-diphenyl-1,3butadiene
[0254]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV)
2,3-dimethyl-1,3-butadiene,
[0255]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV)
isoprene
[0256]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV)
dimethyl
[0257]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV)
dibenzyl
[0258]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV)
1,3-butadiene,
[0259]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (II)
1,3-pentadiene,
[0260]
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (II)
1,4-diphenyl-1,3-butadiene, and
[0261]
(tert-butylamido)(3-N-pyrrolidinylinden-1-yl)dimethylsilanetitanium
(IV) dimethyl.
[0262] Other catalysts, especially catalysts containing other Group
4 metals, will, of course, be apparent to those skilled in the art.
Most highly preferred metal complexes for use herein are the
following metal complexes:
[0263]
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
dimethyl,
[0264]
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
(II) 1,3-pentadiene,
[0265]
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
(II) 1,4 diphenyl-1,3-butadiene,
[0266]
(cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniu-
m dimethyl,
[0267]
cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
(II) 1,3-pentadiene,
[0268]
cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
(II) 1,4 diphenyl-1,3-butadiene,
[0269]
(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitan-
ium dimethyl,
[0270]
(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitan-
ium (II) 1,3-pentadiene,
[0271]
(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitan-
ium (II) 1,4 diphenyl-1,3-butadiene,
[0272]
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium
dimethyl,
[0273]
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II)
1,3-pentadiene,
[0274]
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II)
1,4 diphenyl-1,3-butadiene,
[0275]
(cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium
dimethyl,
[0276]
cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium
(II) 1,3-pentadiene,
[0277]
cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)
1,4 diphenyl-1,3-butadiene,
[0278]
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium
dimethyl,
[0279]
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(-
II) 1,3-pentadiene,
[0280]
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(-
II) 1,4 diphenyl-1,3-butadiene,
[0281]
(t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetit-
anium dimethyl,
[0282]
(t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetit-
anium(II) 1,3-pentadiene,
[0283]
(t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetit-
anium(II) 1,4 diphenyl-1,3-butadiene,
[0284]
(cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silane-
titanium dimethyl,
[0285]
cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanet-
itanium(II) 1,3-pentadiene,
[0286]
cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanet-
itanium(II) 1,4 diphenyl-1,3-butadiene,
[0287]
(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)sila-
netitanium dimethyl,
[0288]
(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)sila-
netitanium(II) 1,3-pentadiene,
[0289]
(cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)sila-
netitanium(II) 1,4 diphenyl-1,3-butadiene,
[0290]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium
dimethyl,
[0291]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(I-
I) 1,3-pentadiene,
[0292]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(I-
I) 1,4 diphenyl-1,3-butadiene,
[0293]
(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniu-
m dimethyl,
[0294]
cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium-
(II) 1,3-pentadiene,
[0295]
cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium-
(II) 1,4 diphenyl-1,3-butadiene,
[0296]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium dimethyl,
[0297]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium(II) 1,3-pentadiene,
[0298]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium(II) 1,4 diphenyl-1,3-butadiene,
[0299]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium
dimethyl,
[0300]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium
(II) 1,3-pentadiene,
[0301]
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium
(II) 1,4 diphenyl-1,3-butadiene,
[0302]
(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniu-
m dimethyl,
[0303]
cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium-
(II) 1,3-pentadiene,
[0304]
cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium-
(II) 1,4 diphenyl-1,3-butadiene,
[0305]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium dimethyl,
[0306]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium(II) 1,3-pentadiene,
[0307]
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitan-
ium(II) 1,4 diphenyl-1,3-butadiene,
[0308]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium
dimethyl,
[0309]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(-
II) 1,3-pentadiene,
[0310]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(-
II) 1,4 diphenyl-1,3-butadiene,
[0311]
(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitani-
um dimethyl,
[0312]
cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniu-
m(II) 1,3-pentadiene,
[0313]
cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniu-
m(II) 1,4 diphenyl-1,3-butadiene,
[0314]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium dimethyl,
[0315]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium(II) 1,3-pentadiene,
[0316]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium(II) 1,4 diphenyl-1,3-butadiene,
[0317]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium
dimethyl,
[0318]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium
(II) 1,3-pentadiene,
[0319]
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium
(II) 1,4 diphenyl-1,3-butadiene,
[0320]
(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitani-
um dimethyl,
[0321]
cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniu-
m(II) 1,3-pentadiene,
[0322]
cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniu-
m(II) 1,4 diphenyl-1,3-butadiene,
[0323]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium dimethyl,
[0324]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium(II) 1,3-pentadiene,
[0325]
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetita-
nium(II) 1,4 diphenyl-1,3-butadien
[0326] 1,2-ethanebis(inden-1-yl)zirconium dimethyl,
[0327] 1,2-ethanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,
[0328] 1,2-ethanebis(inden-1-yl)zirconium(II) 1,4
diphenyl-1,3-butadiene,
[0329] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium
dimethyl,
[0330] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)
1,3-pentadiene,
[0331] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4
diphenyl-1,3-butadiene,
[0332] dimethylsilanebis(inden-1-yl)zirconium dimethyl,
[0333] dimethylsilanebis(inden-1-yl)zirconium(II)
1,3-pentadiene,
[0334] dimethylsilanebis(inden-1-yl)zirconium(II) 1,4
diphenyl-1,3-butadiene,
[0335] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium
dimethyl,
[0336] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)
1,3-pentadiene, and
[0337] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)
1,4 diphenyl-1,3-butadiene.
[0338] The expanded anion cocatalysts of the invention may also be
used in combination with an oligomeric or polymeric alumoxane
compound, a tri(hydrocarbyl)aluminum compound, a
di(hydrocarbyl)(hydrocarbyloxy)alumi- num compound, a
di(hydrocarbyl)(dihydrocarbyl-amido)aluminum compound, a
bis(dihydrocarbyl-amido)(hydrocarbyl)aluminum compound, a
di(hydrocarbyl)amido(disilyl)aluminum compound, a
di(hydrocarbyl)amido(hy- drocarbyl)(silyl)aluminum compound, a
bis(dihydrocarbylamido)(silyl)alumin- um compound, or a mixture of
the foregoing compounds, having from 1 to 20 non-hydrogen atoms in
each hydrocarbyl, hydrocarbyloxy, or silyl group, if desired. these
aluminum compounds are usefully employed for their beneficial
ability to scavenge impurities such as oxygen, water, and aldehydes
from the polymerization mixture as well as to react with the
hydroxyl group or quiescent reactive functionality of the compounds
or the reactive derivatives thereof.
[0339] Preferred aluminum compounds include C.sub.1-20 trialkyl
aluminum compounds, especially those wherein the alkyl groups are
ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or
isopentyl, dialkyl(aryloxy)aluminum compounds containing from 1-6
carbons in the alkyl group and from 6 to 18 carbons in the aryl
group (especially
(3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum),
methylalumoxane, modified methalumoxane, especially isobutyl
modified alumoxane, and tri(ethylaluminum)-,
tris(pentafluorophenyl)borane-, or
tris(pentafluorophenyl)aluminum-modified alumoxanes or supported
derivatives thereof. (The latter compositions are previously known,
having been disclosed in WO99/15534. Additional species include
mixtures of aluminum containing Lewis acids as disclosed in pending
U.S. patent application Ser. Nos., 09/330673 and 09/330675. The
molar ratio of activator to aluminum compound is preferably from
1:10,000 to 1000:1, more preferably from 1:5000 to 100:1, most
preferably from 1:100 to 100:1.
[0340] The cocatalysts of the present invention are capable of
activating a wide variety of metal complexes. Moreover, the
cocatalysts can be optimized in their ability to activate different
metal complexes through combination of anions, Z*, having Lewis
base sites of varying base strength, and Lewis acids, J*, having
varying acidity. Thus, use of derivatives of weakly basic anions
such as dicyanamide, 1,2,4-triazolide and 4,5-dichloroimidazolide
give expanded anion salts which are less active cocatalysts, all
other variables being the same, than do derivatives of moderately
basic anions, such as cyanide, azide, benzotriazolide,
benzimidazolide and tetraimidazoylborate, which in turn give less
active cocatalalysts than derivatives of even more basic anions,
such as 4,4-dimethylimidazolinide, imidazolide,
5,6-dimethylbenzimidazolide and 2-undecylimidazolide.
[0341] The equivalent ratio of catalyst/cocatalyst (calculated
based on quantity of metal in the catalyst and anionic charges on
the cocatalyst) employed preferably ranges from 1:10 to 10:1, more
preferably from 1:5 to 2:1, most preferably from 1:4 to 1:1.
Mixtures of the activating cocatalysts of the present invention may
also be employed if desired.
[0342] Suitable addition polymerizable monomers include
ethylenically unsaturated monomers, acetylenic compounds,
conjugated or non-conjugated dienes, and polyenes. Preferred
monomers include olefins, for examples alpha-olefins having from 2
to 20,000, preferably from 2 to 20, more preferably from 2 to 8
carbon atoms and combinations of two or more of such alpha-olefins.
Particularly suitable alpha-olefins include, for example, ethylene,
propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1dodecene
1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof,
as well as long chain vinyl terminated oligomeric or polymeric
reaction products formed during the polymerization, and C.sub.10-30
.alpha.-olefins specifically added to the reaction mixture in order
to produce relatively long chain branches in the resulting
polymers. Preferably, the alpha-olefins are ethylene, propene,
1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene, and combinations
of ethylene and/or propene with one or more of such other
alpha-olefins. Other preferred monomers include styrene, halo- or
alkyl substituted styrenes, vinylbenzocyclobutene, 1,4-hexadiene,
dicyclopentadiene, ethylidene norbornene, and 1,7-octadiene.
Mixtures of the above-mentioned monomers may also be employed.
[0343] In general, the polymerization may be accomplished at
conditions well known in the prior art for Ziegler-Natta or
Kaminsky-Sinn type polymerization reactions. Suspension, solution,
slurry, gas phase or high pressure, whether employed in batch or
continuous form or other process conditions, may be employed if
desired. Examples of such well known polymerization processes are
depicted in WO 88/02009, U.S. Pat. Nos. 5,084,534, 5,405,922,
4,588,790, 5,032,652, 4,543,399, 4,564,647, 4,522,987, and
elsewhere. Preferred polymerization temperatures are from
0-250.degree. C. Preferred polymerization pressures are from
atmospheric to 3000 atmospheres.
[0344] Suitable processing conditions include solution
polymerization, more preferably continuous solution polymerization
processes, conducted in the presence of an aliphatic or alicyclic
liquid diluent, preferably using the unsupported, quiescent
reactive functionality containing compounds. by the term
"continuous polymerization" is meant that at least the products of
the polymerization are continuously removed from the reaction
mixture, such as for example by devolatilization of a portion of
the reaction mixture. Preferably one or more reactants are also
continuously added to the polymerization mixture during the
polymerization. Examples of suitable aliphatic or alicyclic liquid
diluents include straight and branched-chain C.sub.4-12
hydrocarbons and mixtures thereof; alicyclic hydrocarbons such as
cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane,
and mixtures thereof; and perfluorinated hydrocarbons such as
perfluorinated C.sub.4-10 alkanes. Suitable diluents also include
aromatic hydrocarbons (particularly for use with aromatic
.alpha.-olefins such as styrene or ring alkyl-substituted styrenes)
including toluene, ethylbenzene or xylene, as well as liquid
olefins (which may act as monomers or comonomers) including
ethylene, propylene, butadiene, cyclopentene, 1-hexene,
3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,
1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene
(including all isomers alone or in admixture). Mixtures of the
foregoing are also suitable. The foregoing diluents may also be
advantageously employed during the synthesis of the metal complexes
and catalyst activators of the present invention.
[0345] In most polymerization reactions the molar ratio of
catalyst:polymerizable compounds employed is from 10-12:1 to 0.1:1,
more preferably from 10-12:1 to 10-5:1.
[0346] The catalyst composition of the invention may also be
utilized in combination with at least one additional homogeneous or
heterogeneous polymerization catalyst in separate reactors
connected in series or in parallel to prepare polymer blends having
desirable properties. An example of such a process is disclosed in
WO 94/00500.
[0347] Molecular weight control agents can be used in combination
with the present cocatalysts. Examples of such molecular weight
control agents include hydrogen, trialkyl aluminum compounds or
other known chain transfer agents. a particular benefit of the use
of the present cocatalysts is the ability (depending on reaction
conditions) to produce narrow molecular weight distribution
.alpha.-olefin homopolymers and copolymers in greatly improved
catalyst efficiencies. Preferred polymers have Mw/Mn of less than
2.5, more preferably less than 2.3. Such narrow molecular weight
distribution polymer products are highly desirable due to improved
tensile strength properties.
[0348] The catalyst composition of the present invention can also
be employed to advantage in the gas phase polymerization and
copolymerization of olefins. Gas phase processes for the
polymerization of olefins, especially the homopolymerization and
copolymerization of ethylene and propylene, and the
copolymerization of ethylene with higher alpha olefins such as, for
example, 1-butene, 1-hexene, 4-methyl-1-pentene are well known in
the art. Such processes are used commercially on a large scale for
the manufacture of high density polyethylene (HDPE), medium density
polyethylene (MDPE), linear low density polyethylene (LLDPE) and
polypropylene.
[0349] The gas phase process employed can be, for example, of the
type which employs a mechanically stirred bed or a gas fluidized
bed as the polymerization reaction zone. Preferred is the process
wherein the polymerization reaction is carried out in a vertical
cylindrical polymerization reactor containing a fluidized bed of
polymer particles supported above a perforated plate, the
fluidisation grid, by a flow of fluidisation gas.
[0350] The gas employed to fluidize the bed comprises the monomer
or monomers to be polymerized, and also serves as a heat exchange
medium to remove the heat of reaction from the bed. The hot gases
emerge from the top of the reactor, normally via a tranquilization
zone, also known as a velocity reduction zone, having a wider
diameter than the fluidized bed and wherein fine particles
entrained in the gas stream have an opportunity to gravitate back
into the bed. It can also be advantageous to use a cyclone to
remove ultra-fine particles from the hot gas stream. The gas is
then normally recycled to the bed by means of a blower or
compressor and one or more heat exchangers to strip the gas of the
heat of polymerization.
[0351] A preferred method of cooling of the bed, in addition to the
cooling provided by the cooled recycle gas, is to feed a volatile
liquid to the bed to provide an evaporative cooling effect. The
volatile liquid employed in this case can be, for example, a
volatile inert liquid, for example, a saturated hydrocarbon having
3 to 8, preferably 4 to 6, carbon atoms. In the case that the
monomer or comonomer itself is a volatile liquid, or can be
condensed to provide such a liquid this can be suitably be fed to
the bed to provide an evaporative cooling effect. Examples of
olefin monomers which can be employed in this manner are olefins
containing from 3 to eight, preferably from 3 to six carbon atoms.
The volatile liquid evaporates in the hot fluidized bed to form gas
which mixes with the fluidizing gas. If the volatile liquid is a
monomer or comonomer, it will undergo some polymerization in the
bed. The evaporated liquid then emerges from the reactor as part of
the hot recycle gas, and enters the compression/heat exchange part
of the recycle loop. The recycle gas is cooled in the heat
exchanger and, if the temperature to which the gas is cooled is
below the dew point, liquid will precipitate from the gas. This
liquid is desirably recycled continuously to the fluidized bed. It
is possible to recycle the precipitated liquid to the bed as liquid
droplets carried in the recycle gas stream, as described, for
example, in EP-A-89691, U.S. Pat. No. 4,543,399, WO 94/25495 and
U.S. Pat. No. 5,352,749. A particularly preferred method of
recycling the liquid to the bed is to separate the liquid from the
recycle gas stream and to reinject this liquid directly into the
bed, preferably using a method which generates fine droplets of the
liquid within the bed. This type of process is described in WO
94/28032.
[0352] The polymerization reaction occurring in the gas fluidized
bed is catalyzed by the continuous or semi-continuous addition of
catalyst. Such catalyst can be supported on an inorganic or organic
support material if desired. The catalyst can also be subjected to
a prepolymerization step, for example, by polymerizing a small
quantity of olefin monomer in a liquid inert diluent, to provide a
catalyst composite comprising catalyst particles embedded in olefin
polymer particles.
[0353] The polymer is produced directly in the fluidized bed by
catalyzed (co)polymerization of the monomer(s) on the fluidized
particles of catalyst, supported catalyst or prepolymer within the
bed. Start-up of the polymerization reaction is achieved using a
bed of preformed polymer particles, which, preferably, is similar
to the target polyolefin, and conditioning the bed by drying with
inert gas or nitrogen prior to introducing the catalyst, the
monomer(s) and any other gases which it is desired to have in the
recycle gas stream, such as a diluent gas, hydrogen chain transfer
agent, or an inert condensable gas when operating in gas phase
condensing mode. The produced polymer is discharged continuously or
discontinuously from the fluidized bed as desired, optionally
exposed to a catalyst kill and optionally pelletized.
[0354] Slurry polymerization conditions and supported catalyst
preparation techniques for use therein are well known from the
published literature. Generally such catalysts are prepared by the
same techniques as are employed for making supported catalysts used
in gas phase polymerizations. Slurry polymerization conditions
generally encompass polymerization of a C.sub.2-20 olefin,
diolefin, cycloolefin, or mixture thereof in an aliphatic solvent
at a temperature below that at which the polymer is readily soluble
in the presence of a supported catalyst. Slurry phase processes
particularly suited for the polymerization of C.sub.2-6 olefins,
especially the homopolymerization and copolymerization of ethylene
and propylene, and the copolymerization of ethylene with C.sub.3-8
.alpha.-olefins such as, for example, 1-butene, 1-hexene,
4-methyl-1-pentene and 1-octene are well known in the art. Such
processes are used commercially on a large scale for the
manufacture of high density polyethylene (HDPE), medium density
polyethylene (MDPE), linear low density polyethylene (LLDPE) and
polypropylene, especially isotactic polypropylene.
EXAMPLES
[0355] It is understood that the present invention is operable in
the absence of any component which has not been specifically
disclosed. The following examples are provided in order to further
illustrate the invention and are not to be construed as limiting.
Unless stated to the contrary, all parts and percentages are
expressed on a weight basis. The term "overnight", if used, refers
to a time of approximately 16-18 hours, "room temperature", if
used, refers to a temperature of 20-25.degree. C., and "mixed
alkanes" refers to a mixture of mostly C.sub.6-C.sub.12 alkanes
available commercially under the trademark Isopar E.TM. from Exxon
Chemicals Inc.
[0356] All manipulation of air sensitive materials was performed in
an argon filled, vacuum atmospheres, glove box or on a high vacuum
line using standard Shlenk techniques. Toluene was purified by
passage through columns packed with activated alumina (Kaiser A-2)
and supported copper (Engelhard, Cu-0224 S). Hexanes were purified
by distillation from sodium benzophenone ketyl.
Tris(pentafluorophenyl)borane was purchased from Boulder
Scientific. Potassium azide was purchased from Atomergic Chemetals
Corp., and used as received. Dioctadecylmethylamine is a
bis(hydrogenated tallow) alkylamine of approximate formulation
(C.sub.18H.sub.35).sub.2CH.sub.3N, available commercially under the
tradename Armeen.TM. M2HT from Akzo Nobel, Inc., and was used as
received.
Example 1
[0357] A) Synthesis of
2-(4-hydroxyphenyl)imidazole--HOC.sub.6H.sub.4C.sub-
.3H.sub.3N.sub.2
[0358] A flask was charged with 4-hydroxybenzaldehyde (30.0 g,
0.246 mol) and conc. ammonium hydroxide (36 mL). The solution was
cooled to 0.degree. C. and glyoxal (45 mL, 0.392 mol) was added
dropwise via syringe over 30 minutes. A yellow precipitate formed
and the slurry was stirred and allowed to warm to 25.degree. C. for
two hours. The product was collected on a frit, washed with cold
water, and dried under reduced pressure to give a yellow powder
(29.4 g, 75 percent yield). The solid was recrystallized from
dimethylformamide (DMF) to give a tan powder.
[0359] .sup.1H NMR (DMSO) 12.23 (br s, 1H, NH), 9.72 (br s, 1H,
OH), 7.74 (d, J=8.6 Hz, 2H, Ph), 7.04 (s, 2H, imidazole CH.dbd.CH),
6.81 (d, J=8.6 Hz, 2H, Ph).
[0360] .sup.3C NMR (DMSO) 157.46 (Ph COH), 146.06 (Ph
CCN.sub.2HCH.sub.2), 132.17 (CN.sub.2HC.sub.2H.sub.2), 126.37 (Ph
CH), 122.26 (CN.sub.2HC.sub.2H.sub.2), 115.41 (Ph CH). MS
(M+H.sup.+ 161.0).
[0361] B) Synthesis of
2-(4-trimethylsiloxyphenyl)imidazole--TMSOC.sub.6H.-
sub.4C.sub.3H.sub.3N.sub.2
[0362] A flask was charged with the 2-(4-hydroxyphenyl)imidazole
(1.00 g, 6.24 mmol) and 25 mL of CH.sub.2Cl.sub.2. To the slurry
was added trimethylsilylchloride and triethylamine via syringe. The
mixture clarified to give an amber soluiton. After stirring for 3
hours at 25.degree. C., the volatiles were removed and the residue
triturated once with hexanes and then dissolved in toluene.
Filtration through diatomaceous earth filter aid and
recystallizaiton from toluene yielded 0.914 g (63 percent yield) of
the desired product as a tan solid.
[0363] .sup.1H NMR (CH.sub.2Cl.sub.2) 12.63 (s, 1H, NH), 7.80 (d,
J=8.5 Hz, 2H, Ph), 7.11 (s, 2H, imidazole CH.dbd.CH), 6.81 (d,
J=8.5 Hz, 2H, Ph), 0.26 (s, 9H, SiMe.sub.3).
[0364] .sup.13C NMR (CH.sub.2Cl.sub.2) 156.32 (Ph COSiMe.sub.3),
147.74 (Ph CCN.sub.2HCH.sub.2), 127.62 (Ph CH), 124.70
(CN.sub.2HC.sub.2H.sub.2)- , 123.28 (CN.sub.2HC.sub.2H.sub.2),
120.89 (Ph CH), 0.39 (SiMe.sub.3).
[0365] MS (M.sup.+ 232.1).
[0366] C) Preparation of
[H(C.sub.18H.sub.35).sub.2(CH.sub.3)N].sup.+{(HOC-
.sub.6H.sub.4C.sub.3H.sub.2N.sub.2)[B(C.sub.6F.sub.5).sub.3].sub.2}.sup.-
[0367] A vial was charged with 2-(4-hydroxyphenyl)imidazole (20.2
mg, 0.126 mmol), tris(pentafluorophenyl)borane (128.7 mg, 0.251
mmol), di(octadecyl)methylamine (66.8 mg, 0.128 mmol), and 2.0 mL
of d8-toluene. The mixture was stirred for 10 minutes until all of
the solids dissolved and then analyzed to determine the product's
identity.
[0368] .sup.1H NMR (d.sub.8-toluene) 6.82 (br s, 1H, OH), 6.47 (d,
J=8.8 Hz, 2H, Ph), 6.85 (d, J=8.6 Hz, 2H, Ph), 5.85 (t, J=2.3 Hz,
2H, imidazole CH.dbd.CH), 4.07 (v br s, 1H, NH), 2.24 (m, 2H,
HNCH.sub.2), 2.05 (partially obsured m, 2H, HNCH.sub.2), 1.91 (d,
J=5.1 Hz, 3H, NMe), 1.4-1.0 (amine CH.sub.2), 0.93 (t, J=6.7 Hz,
6H, N(CH.sub.2).sub.nCH.sub.- 3).
[0369] .sup.19F NMR (d.sub.8-toluene) o-CF[-127.29 ("d", 1F),
-132.72 ("d", 1F), -133.45 & -133.75 (br m & "d"), 10F],
p-CF [-156.66 (t, J=19.8 Hz, 1F), -159.09 (t, J=19.3 Hz, 2F),
-160.79 (t, J=22.0 Hz, 3F)], m-CF [-162.96 ("br t", J=22.9 Hz, 1F),
-163.64 ("br t", J=21.4 Hz, 1F), -165.78 & -166.12 (m & br
m, 10 F)].
[0370] MS cation [(M.sup.+ 537.5) fragments 536.5, 509.5, 508.5
(base), 480.5)], anion {(M.sup.- 1182.6) fragments 872.7, 670.6
[base, (M-B(C.sub.6F.sub.5).sub.3.sup.-)], 632.6}.
Example 2
[0371] Large Scale Preparation of
[H(C.sub.18H.sub.35).sub.2(CH.sub.3)N].s-
up.+{(HOC.sub.6H.sub.4C.sub.3H.sub.2N.sub.2)[B(C.sub.6F.sub.5).sub.3].sub.-
2}.sup.-
[0372] A 250 mL flask was charged with 2-(4-hydroxyphenyl)imidazole
(03.16 g, 1.97 mmol), tris(pentafluorophenyl)borane (2.02 g, 3.95
mmol), dioctadecylmethylamine (1.02 g, 1.96 mmol), and 100 mL of
toluene. The mixture was stirred for 1 hour and then filtered
through a frit. The volatiles were removed under reduced pressure
to give a viscous, brown oil (3.10 g, 92.4 percent yield).
Example 3
[0373] Preparation of
[H(C.sub.6H.sub.5)(CH.sub.3).sub.2N].sup.+{(Me.sub.3-
SiOC.sub.6H.sub.4C.sub.3H.sub.2N.sub.2)[B(C.sub.6F.sub.5).sub.3].sub.2}.su-
p.-
[0374] A vial was charged with 2-(4-trimethylsiloxyphenyl)imidazole
(20.4 mg, 0.088 mmol), tris(pentafluorophenyl)borane (90.0 mg,
0.176 mmol), ), dioctadecylmethylamine (47.0 mg, 0.090 mmol), and
2.0 mL of d8-toluene. The cloudy mixture was stirred for 10 minutes
until dissolved. The solution was analyzed for product
identity.
[0375] .sup.1H NMR (d.sub.8-toluene) 7.21 (br s, 2H, imidazole
CH.dbd.CH), 6.65 (br d, J=7.8 Hz, 2H, Ph), 6.39 (d, J=8.8 Hz, 2H,
Ph), 3.95 (v br s, 1H, NH), 2.04 (br m, 4H, HNCH.sub.2), 1.77 (s,
3H, NMe), 1.4-1.0 (amine CH.sub.2), 0.93 (t, J=6.8 Hz,
N(CH.sub.2).sub.nCH.sub.3 overlaps with some amine resonances),
0.12 (s, 9H, SiMe.sub.3).
[0376] .sup.19F NMR (d.sub.8-toluene) o-CF [-125.71 (br s, 2F),
-132.5 & -132.43 (v br m & br s), 10F], p-CF [-157.85 (t,
J=21.4 Hz, 2F), -160.28 (br "t", 4F)], m-CF [-163.78 ("br t", 2F),
-164.37 (br, s, 2F), -166.50 (v br s, 8 F)].
[0377] MS cation [(M.sup.+ 537.6) fragments 536.5, 509.6, 508.6
(base), 480.6)], anion {(M.sup.-1254.8) fragments 742.6 [base,
(M-B(C.sub.6F.sub.5).sub.3.sup.-)]}.
Example 4
[0378] Preparation of
[H(C18H.sub.35).sub.2(CH.sub.3)N].sup.+{(Me.sub.3SiO-
C.sub.6H.sub.4C.sub.3H.sub.2N.sub.2)[Al(C.sub.6F.sub.5).sub.3].sub.2}.sup.-
-
[0379] A vial was charged with 2-(4-trimethylsiloxyphenyl)imidazole
(20.5 mg, 0.088 mmol),
tris(pentafluorophenyl)aluminane.1/2(toluene) (103.1 mg, 0.180
mmol), di(octadecyl)methylamine (46.0 mg, 0.088 mmol), and 2.0 mL
of d8-toluene. The mixture was stirred for 15 minutes until all of
the solids dissolved and then analyzed.
[0380] .sup.1H NMR (d.sub.8-toluene) 7.40 (s, 2H, imidazole
CH.dbd.CH), 7.31 (d, J=8.5 Hz, 2H, Ph), 6.36 (d, J=8.6 Hz, 2H, Ph),
4.35 (v br s, 1H, NH), 2.01 (br m, 4H, HNCH.sub.2), 1.73 (s, 3H,
NMe), 1.4-1.0 (amine CH.sub.2), 0.93 (t, J=6.6 Hz,
N(CH.sub.2).sub.nCH.sub.3 overlaps with some amine resonances),
0.12 (s, 9H, SiMe.sub.3).
[0381] .sup.19F NMR (d.sub.8-toluene) -121.79 (dd, J=27.4 &
18.3, 2F, o-CF), -155.02 (t, J=19.8 Hz, 1F, p-CF ), -162.73 (m, 2F,
m-CF).
[0382] MS cation [(M.sup.+ 537.8) fragments 536.8, 509.8, 508.8,
(base), 480.7], anion [M.sup.- 1286.9 (base)].
Example 5
[0383] Preparation of
[H(C.sub.18H.sub.35).sub.2(CH.sub.3)N].sup.+{(Et.sub-
.2AlOC.sub.6H.sub.4C.sub.3H.sub.2N.sub.2)[B(C.sub.6F.sub.5).sub.3].sub.2}.-
sup.-
[0384] (di(octadecyl)methylammonium
2-(4-diethylaluminoxyphenyl)imidazolat- e bis
[tris(pentafluorophenyl)borane])
[0385] Under an argon atmosphere, a toluene solution of
di(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] ([H(C18H5) 2(CH3)
N]+{(HOC6H4C3H2N2)[B(C6F5)3]2}, 825 .mu.l, 0.040M, 33.0 .mu.mol)
and a toluene solution of triethyl aluminum (363 .mu.l, 0.10M, 36.3
.mu.mol) were added to a vial and mixed for 30 seconds. Formation
of the desired product can be identified by nuclear magnetic
resonance spectroscopy.
Example 6a and 6b
[0386] Preparation of Supported Catalyst System
[0387] Di(octadecyl)methylammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] on TEA/silica
[0388] Under an argon atmosphere, a toluene solution of
di(octadecyl)methyl ammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane]
([H(C18H35)2(CH3)N]+{(HOC6H4C3H2N2)[B(- C6F5)3]2}-, 825 .mu.l,
0.040M, 33.0 .mu.mol) was diluted to 1500 .mu.l with toluene and
added to 1.00 g of triethylaluminum (TEA)-treated silica
(Grace-Davison 948 silica, available from Grace-Davison Company,
heated at 250.degree. C. for 4 h, treated with 1.5 mmol TEA/g,
washed with toluene and hexanes and dried under reduced pressure).
The mixture was shaken by hand to break-up clumps and then
mechanically agitated for 5 minutes. The volatiles were then
removed under reduced pressure. A toluene solution of
(t-butylamido)dimethyl(tetramethylcyclopenta-dienyl)s- ilane
titanium 1,3-pentadiene (1500 .mu.l, 0.020M, 30.0 .mu.mol) was
added to the TEA-treated silica. The mixture was shaken by hand to
break-up clumps and then mechanically agitated for 5 minutes. The
volatiles were then removed under reduced pressure to give an olive
green solid (0.988 g).
Example 7
[0389] Preparation of Supported Catalyst System
[0390] Di(octadecyl)methylammonium
2-(4-diethylaluminoxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] On TEA/Silica
[0391] Under an argon atmosphere, a toluene solution of
di(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] (825 .mu.l, 0.040M, 33.0
.mu.mol) and a toluene solution of triethyl aluminum (363 .mu.l,
0.10M, 36.3 .mu.mol) were added to a vial and mixed for 30 seconds.
This solution was then added to 1.00 g of TEA-treated silica
(Grace-Davison 948, heated at 250.degree. C. for 4 h, treated with
1.5 mmol TEA/g, washed with toluene and hexanes and dried under
reduced pressure). The mixture was shaken by hand to break-up
clumps and then mechanically agitated for 5 minutes. The volatiles
were then removed under reduced pressure. A toluene solution of
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium
1,3-pentadiene (1500 .mu.l, 0.020M, 30.0 .mu.mol) was added to the
silica. The mixture was shaken by hand to break-up clumps and then
mechanically agitated for 5 minutes. The volatiles were then
removed under reduced pressure to give the desired supported
catalyst product as an olive green solid (1.00 g).
Example 8
[0392] Preparation of Supported Catalyst System
[0393] Di(octadecyl)methylammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] w/(EBI)Zr(DPB) On TEA/Silica
[0394] Under an argon atmosphere, a toluene solution of
di(octadecyl)methyl ammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane]
([H(C18H35)2(CH3)N]+{(HOC6H4C3H2N2)[B(- C6F5)3]2}-, 825 .mu.l,
0.040M, 33.0 .mu.mol) was diluted to 1500 .mu.l with toluene and
added to 1.00 g of triethylaluminum (TEA)-treated silica
(Grace-Davison 948 silica, available from Grace-Davison Company
heated at 250.degree. C. for 4 h, treated with 1.5 mmol TEA/g,
washed with toluene and hexanes and dried under reduced pressure).
The mixture was shaken by hand to break-up clumps and then
mechanically agitated for 5 minutes. The volatiles were then
removed under reduced pressure. A toluene solution
rac-ethylenebis(indenyl)zirconium(1,4-diphenylbutadene)(1500 .mu.l,
0.020M, 30.0 .mu.mol) was added to the TEA-treated silica. The
mixture was shaken by hand to break-up clumps and then mechanically
agitated for 5 minutes. The volatiles were then removed under
reduced pressure to give a purple-gray solid (1.061 g).
Example 9
[0395] Preparation of Supported Catalyst System
[0396] Di(octadecyl)methylammonium
2-(4-diethylaluminoxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] w/(EBI)Zr(DPB) On TEA/Silica
[0397] Under an argon atmosphere, a toluene solution of
di(octadecyl)methyl-ammonium 2-(4-hydroxyphenyl)imidazolate
bis[tris(pentafluorophenyl)borane] (825 .mu.l, 0.040M, 33.0
.mu.mol) and a toluene solution of triethyl aluminum (363 .mu.l,
0.10M, 36.3 .mu.mol) were added to a vial and mixed for 30 seconds.
This solution was then added to 1.00 g of TEA-treated silica
(Grace-Davison 948, heated at 250.degree. C. for 4 h, treated with
1.5 mmol TEA/g, washed with toluene and hexanes and dried under
reduced pressure). The mixture was shaken by hand to break-up
clumps and then mechanically agitated for 5 minutes. The volatiles
were then removed under reduced pressure. A toluene solution
rac-ethylenebis(indenyl)zirconium(1,4-diphenylbutadene) (1500
.mu.l, 0.020M, 30.0 .mu.mol) was added to the silica. The mixture
was shaken by hand to break-up clumps and then mechanically
agitated for 5 minutes. The volatiles were then removed under
reduced pressure to give the desired supported catalysts product as
a purple-gray solid (1.065 g).
[0398] Gas Phase Polymerizations
[0399] A 2.5-L stirred, fixed bed autoclave was charged with 200 g
dry NaCl containing 0.1 g of KH as a scavenger. Stirring was begun
at 300 rpm. The reactor was pressurized to 0.8 MPa ethylene and
heated to 70.degree. C. 1-hexene (7000 ppm) was introduced to the
reactor followed by the addition of hydrogen (when used). In a
separate vessel, 0.05 g of catalyst was mixed with an additional
0.1 g KH scavenger. The combined catalyst and scavenger were
subsequently injected into the reactor. Ethylene pressure was
maintained on demand while hexene and hydrogen (where used) were
fed to the reactor to maintain their respective concentrations. The
temperature of the reactor was regulated by a circulating water
bath. After 90 minutes the reactor was depressurized, and the salt
and polymer were removed. The polymer was washed with copious
quantities of distilled water to remove the salt, dried at
60.degree. C., and then stabilized by addition of a hindered phenol
antioxidant (Irganox.TM. 1010 from Ciba Geigy Corporation) and 133
mg of a phosphorus stabilizer. Activity values were calculated
based on ethylene uptake. Results are shown in Table 1.
1TABLE 1 Cata- Cocat- Activity Run lyst alyst H.sub.2 (ppm)
(g/ghb).sup.3 Density I.sub.2 Mw 1 T.sup.1 Ex 6 2000 18.0 0.912
0.296 139,000 2 E.sup.2 Ex 8 0 59.9 0.922 <0.300 210,000 3 " "
2000 36.7 0.92 1.017 92,500 4 T.sup.1 Ex. 7 2000 25.3 0.914 0.92
117,000 5 E.sup.2 Ex 9 0 75.7 0.924 <1.04 191,000 6 " " 2000
47.8 0.927 3.22 110,000 7 " " 0 64.3 0.924 <1.233 193,000
.sup.1(t-butylamido)dimethyl(tetramethylcyclopentadienyl)titanium
1,3-pentadiene .sup.2ethylenebis(inden-1-yl)zirconium
1,4-diphenyl-1,3-butadiene .sup.3grams polymer per gram (solid
catalyst) .multidot. hour .multidot. (MPa .times. 0.1)
* * * * *