U.S. patent application number 11/387217 was filed with the patent office on 2006-08-10 for olefin polymerization catalysts.
Invention is credited to Jo Ann Marie Canich.
Application Number | 20060178491 11/387217 |
Document ID | / |
Family ID | 27019705 |
Filed Date | 2006-08-10 |
United States Patent
Application |
20060178491 |
Kind Code |
A1 |
Canich; Jo Ann Marie |
August 10, 2006 |
Olefin polymerization catalysts
Abstract
The invention is a catalyst system including a Group IV B
transition metal component and an alumoxane component which may be
employed to polymerize olefins to produce a high molecular weight
polymer.
Inventors: |
Canich; Jo Ann Marie;
(Webster, TX) |
Correspondence
Address: |
Exxon Chemical Company
P. O. Box 5200
Baytown
TX
77522
US
|
Family ID: |
27019705 |
Appl. No.: |
11/387217 |
Filed: |
March 23, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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07676690 |
Mar 28, 1991 |
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11387217 |
Mar 23, 2006 |
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07533245 |
Jun 4, 1990 |
5055438 |
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07676690 |
Mar 28, 1991 |
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07406945 |
Sep 13, 1989 |
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07533245 |
Jun 4, 1990 |
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Current U.S.
Class: |
526/127 ;
526/160; 526/170; 526/335; 526/346; 526/348.6; 526/901;
526/943 |
Current CPC
Class: |
C08F 4/65916 20130101;
C08F 110/02 20130101; C08F 10/00 20130101; C07F 17/00 20130101;
C08F 4/6592 20130101; C08F 210/06 20130101; Y10S 526/943 20130101;
C08F 210/16 20130101; C08F 4/65908 20130101; C07F 7/10 20130101;
C08F 210/18 20130101; C08F 110/06 20130101; C08F 10/06 20130101;
C08F 4/65912 20130101; C08F 10/00 20130101; C08F 4/6592 20130101;
C08F 10/06 20130101; C08F 4/6592 20130101; C08F 110/02 20130101;
C08F 2500/01 20130101; C08F 2500/03 20130101; C08F 110/06 20130101;
C08F 2500/17 20130101; C08F 2500/03 20130101; C08F 2500/24
20130101; C08F 210/06 20130101; C08F 210/16 20130101; C08F 2500/17
20130101; C08F 2500/03 20130101; C08F 2500/24 20130101; C08F 210/16
20130101; C08F 232/08 20130101; C08F 2500/25 20130101; C08F 2500/10
20130101; C08F 2500/01 20130101; C08F 2500/03 20130101; C08F 210/16
20130101; C08F 210/08 20130101; C08F 2500/10 20130101; C08F 2500/01
20130101; C08F 2500/03 20130101; C08F 210/16 20130101; C08F 210/06
20130101; C08F 2500/10 20130101; C08F 2500/01 20130101; C08F
2500/03 20130101; C08F 210/16 20130101; C08F 232/08 20130101; C08F
2500/25 20130101; C08F 2500/01 20130101; C08F 2500/03 20130101;
C08F 2500/10 20130101; C08F 210/16 20130101; C08F 210/14 20130101;
C08F 2500/10 20130101; C08F 2500/01 20130101; C08F 2500/03
20130101; C08F 210/16 20130101; C08F 210/08 20130101; C08F 2500/01
20130101; C08F 2500/03 20130101; C08F 2500/10 20130101; C08F 210/16
20130101; C08F 210/14 20130101; C08F 2500/01 20130101; C08F 2500/03
20130101; C08F 2500/10 20130101; C08F 210/18 20130101; C08F 2500/25
20130101; C08F 2500/10 20130101; C08F 2500/01 20130101; C08F
2500/03 20130101; C08F 210/18 20130101; C08F 236/20 20130101; C08F
2500/01 20130101; C08F 2500/03 20130101; C08F 2500/10 20130101;
C08F 210/18 20130101; C08F 2500/25 20130101; C08F 2500/01 20130101;
C08F 2500/03 20130101; C08F 2500/10 20130101; C08F 210/18 20130101;
C08F 236/20 20130101; C08F 2500/10 20130101; C08F 2500/01 20130101;
C08F 2500/03 20130101 |
Class at
Publication: |
526/127 ;
526/170; 526/943; 526/901; 526/346; 526/335; 526/348.6;
526/160 |
International
Class: |
C08F 4/44 20060101
C08F004/44 |
Claims
1. A process for the polymerization of one or more olefins
comprising conducting the polymerization in the presence of a
catalyst system comprising: (A) a Group IVB transition metal
component of the formula: ##STR5## wherein "M" is Zr, Hf or Ti;
(C.sub.5H.sub.5-xR.sub.x) is a cyclopentadienyl ring which is
substituted with from zero to five substituent groups R, "x" is 0,
1, 2, 3, 4 or 5 denoting the degree of substitution, and each R is,
independently, a radical selected from a group consisting of
C.sub.1-C.sub.20 hydrocarbyl radicals, C.sub.1-C.sub.20 substituted
hydrocarbyl radicals wherein one or more hydrogen atoms is replaced
by a halogen atom, C.sub.1-C.sub.20 hydrocarbyl-substituted
metalloid radicals wherein the metalloid is selected from Group
IV-A of the Periodic Table of Elements, and halogen radicals or
(C.sub.5H.sub.5-xR.sub.x) is a cyclopentadienyl ring in which two
adjacent R-groups are joined forming a C.sub.4-C.sub.20 ring to
give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
(JR'.sub.z-1) is a heteroatom ligand in which "J" is an element
with coordination number of three from Group V-A or an element with
a coordination number of two from VI-A of the Periodic Table of
Elements, each "R'" is, independently a radical selected from a
group consisting of C.sub.1-C.sub.20 hydrocarbyl radicals,
substituted C.sub.1-C.sub.20 hydrocarbyl radicals wherein one or
more hydrogen atoms is replaced by a halogen atom, and "z" is the
coordination number of the element "J"; "y" is 1, T is a covalent
bridging group containing a Group IVA or VA element; each "Q" is,
independently, any univalent anionic ligand or two "Q'"s are a
divalent anionic chelating ligand, provided that "Q" is different
from (C.sub.5H.sub.5-xR.sub.x); "L" is a neutral Lewis base where
"w" is a number greater than 0 and up to 3; "M'" has the same
meaning as "M"; and "Q'" has the same meaning as "Q"; and (B) an
alumoxane.
2. The process of claim 1 wherein J is nitrogen, phosphorus, oxygen
or sulfur.
3. The process of claim 1 wherein Q is a halogen or a hydrocarbyl
radical and Q', if present, is a halogen or a hydrocarbyl
radical.
4. The process of claim 1 wherein J is nitrogen.
5. The process of claim 1 wherein M is zirconium or hafnium and M',
if present, is zirconium or hahnium.
6. The process of claim 1 wherein the mole ratio of Al:M is form
10:1 to 20,000:1.
7. The process of claim 1 wherein Q is independently halogen,
hydride, or a substituted or unsubstituted C1 to C20 hydrocarbyl,
alkoxide, aryl xoide, amide aryl amide, phosphide and
arylphosphide.
8. The process of claim 1 wherein the olefins are selected from
ethylene, alpha-olefin having from 3 to 20 carbon atoms, and
combinations thereof.
9. The process of claim 8 wherein the polymerization conducted is a
homopolymerization.
10. The process of claim 8 wherein the polymerization conducted is
a copolymerization.
11. The process of claim 8, wherein alpha-olefin is selected form
propylene, butene, styrene, diolefins, and combinations
thereof.
12. The process of claim 11 wherein the alpha-olefin is
styrene.
13. The process of claim 1 wherein the process utilized is liquid
phase, high pressure fluid phase, or gas phase.
14. The process of claim 13 wherein the polymerization process is
selected from slurry, solution, suspension, or bulk phase
polymerization.
15. The process of claim 13 wherein the process is employed in
series.
16. The process of claim 14 wherein the process is employed in
series.
17. The process of claim 1 wherein the polymer produced as an Mw/Mn
of 4 or less.
Description
[0001] This application is a continuation of U.S. Ser. No.
07/676,690, filed Mar. 28, 1991 which is a divisional of U.S. Ser.
No. 07/533,245, filed Jun. 4, 1990 which is a continuation-in-part
of U.S. Ser. No. 07/406,945, filed Sep. 13, 1989.
FIELD OF THE INVENTION
[0002] This invention relates to certain transition metal compounds
from Group IV B of the Periodic Table of Elements, to a catalyst
system comprising a Group IV B transition metal compound and an
alumoxane, and to a process using such catalyst system for the
production of polyolefins, particularly polyethylene, polypropylene
and .alpha.-olefin copolymers of ethylene and propylene having a
high molecular weight. The catalyst system is highly active at low
ratios of aluminum to the Group IV B transition metal, hence
catalyzes the production of a polyolefin product containing low
levels of catalyst residue.
BACKGROUND OF THE INVENTION
[0003] As is well known, various processes and catalysts exist for
the homopolymerization or copolymerization of olefins. For many
applications it is of primary importance for a polyolefin to have a
high weight average molecular weight while having a relatively
narrow molecular weight distribution. A high weight average
molecular weight, when accompanied by a narrow molecular weight
distribution, provides a polyolefin or an ethylene-.alpha.-olefin
copolymer with high strength properties.
[0004] Traditional Ziegler-Natta catalyst systems--a transition
metal compound cocatalyzed by an aluminum alkyl--are capable of
producing polyolefins having a high molecular weight but a broad
molecular weight distribution.
[0005] More recently a catalyst system has been developed wherein
the transition metal compound has two or more cyclopentadienyl ring
ligands, such transition metal compound being referred to as a
metallocene--which catalyzes the production of olefin monomers to
polyolefins. Accordingly, metallocene compounds of the Group IV B
metals, particularly, titanocene and zirconocene, have been
utilized as the transition metal component in such "metallocene"
containing catalyst system for the production of polyolefins and
ethylene-.alpha.-olefin copolymers. When such metallocenes are
cocatalyzed with an aluminum alkyl--as is the case with a
traditional type Ziegler-Natta catalyst system--the catalytic
activity of such metallocene catalyst system is generally too low
to be of any commercial interest.
[0006] It has since become known that such metallocenes may be
cocatalyzed with an alumoxane--rather than an aluminum alkyl--to
provide a metallocene catalyst system of high activity which
catalyzes the production of polyolefins.
[0007] A wide variety of Group IV B transition metal compounds of
the metallocene type have been named as possible candidates for an
alumoxane cocatalyzed catalyst system. Hence, although
bis(cyclopentadienyl) Group IV B transition metal compounds have
been the most preferred and heavily investigated type metallocenes
for use in metallocene/alumoxane catalyst for polyolefin
production, suggestions have appeared that mono and
tris(cyclopentadienyl) transition metal compounds may also be
useful. See, for example, U.S. Pat. Nos. 4,522,982; 4,530,914 and
4,701,431. Such mono(cyclopentadienyl) transition metal compounds
as have heretofore been suggested as candidates for a
metallocene/alumoxane catalyst are mono(cyclopentadienyl)
transition metal trihalides and trialkyls.
[0008] More recently International Publication No. WO 87/03887 has
appeared which describes the use of a composition comprising a
transition metal coordinated to at least one cyclopentadienyl and
at least one heteroatom ligand as a metallocene type component for
use in a metallocene/alumoxane catalyst system for .alpha.-olefin
polymerization. The composition is broadly defined as a transition
metal, preferably of Group IV B of the Periodic Table which is
coordinated with at least one cyclopentadienyl ligand and one to
three heteroatom ligands, the balance of the coordination
requirement being satisfied with cyclopentadienyl or hydrocarbyl
ligands. The metallocene/alumoxane catalyst system described is
illustrated solely with reference to transition metal compounds
which are bis(cyclopentadienyl) Group IV B transition metal
compounds.
[0009] Even more recently, at the Third Chemical Congress of North
America held in Toronto, Canada in June 1988, John Bercaw reported
upon efforts to use a compound of a Group III B transition metal
coordinated to a single cyclopentadienyl heteroatom bridged ligand
as a catalyst system for the polymerization of olefins. Although
some catalytic activity was observed under the conditions employed,
the degree of activity and the properties observed in the resulting
polymer product were discouraging of a belief that such transition
metal compound could be usefully employed for commercial
polymerization processes.
[0010] A need still exists for discovering catalyst systems that
permit the production of higher molecular weight polyolefins and
desirably with a narrow molecular weight distribution.
SUMMARY OF THE INVENTION
[0011] The catalyst system of this invention comprises a transition
metal component from Group IV B of the Periodic Table of the
Elements (CRC Handbook of Chemistry and Physics, 68th ed.
1987-1988) and an alumoxane component which may be employed in
solution, slurry or bulk phase polymerization procedure to produce
a polyolefin of high weight average molecular weight and relatively
narrow molecular weight distribution.
[0012] The "Group IV B transition metal component" of the catalyst
system is represented by the general formula: ##STR1## wherein: M
is Zr, Hf or Ti and is in its highest formal oxidation state (+4,
d.sup.0 complex);
[0013] (C.sub.5H.sub.5-y-xR.sub.x) is a cyclopentadienyl ring which
is substituted with from zero to five substituent groups R, "x" is
0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each
substituent group R is, independently, a radical selected from a
group consisting of C.sub.1-C.sub.20 hydrocarbyl radicals,
substituted C.sub.1-C.sub.20 hydrocarbyl radicals wherein one or
more hydrogen atoms is replaced by a halogen atom, C.sub.1-C.sub.20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is
selected from the Group IV A of the Periodic Table of Elements, and
halogen radicals or (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ring in which two adjacent R-groups are joined
forming C.sub.4-C.sub.20 ring to give a saturated or unsaturated
polycyclic cyclopentadienyl ligand such as indenyl,
tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
[0014] (JR'.sub.z-1-y) is a heteroatom ligand in which J is an
element with a coordination number of three from Group V A or an
element with a coordination number of two from Group VI A of the
Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen
or sulfur, and each R' is, independently a radical selected from a
group consisting of C.sub.1-C.sub.20 hydrocarbyl radicals,
substituted C.sub.1-C.sub.20 hydrocarbyl radicals wherein one or
more hydrogen atoms is replaced by a halogen atom, and "z" is the
coordination number of the element J;
[0015] each Q may be independently any univalent anionic ligand
such as halogen, hydride, or substituted or unsubstituted
C.sub.1-C.sub.20 hydrocarbyl, alkoxide, aryloxide, amide,
arylamide, phosphide or arylphosphide, provided that where any Q is
a hydrocarbyl such Q is different from (C.sub.5H.sub.5-y-xR.sub.x)
or both Q together may be an alkylidene or a cyclometallated
hydrocarbyl or any other divalent anionic chelating ligand.
[0016] "y" is 0 or 1 when w is greater than 0; y is 1 when w is 0;
when "y" is 1, B is a covalent bridging group containing a Group IV
A or V A element such as, but not limited to, a dialkyl, alkylaryl
or diaryl silicon or germanium radical, alkyl or aryl phosphine or
amine radical, or a hydrocarbyl radical such as methylene, ethylene
and the like;
[0017] L is a Lewis base such as diethylether, tetraethylammonium
chloride, tetrahydrofuran, dimethylaniline, aniline,
trimethylphosphine, n-butylamine, and the like; and "w" is a number
from 0 to 3; L can also be a second transition metal compound of
the same type such that the two metal centers M and M' are bridged
by Q and Q', wherein M'has the same meaning as M and Q' has the
same meaning as Q. Such compounds are represented by the formula:
##STR2##
[0018] The alumoxane component of the catalyst may be represented
by the formulas: (R.sup.2--Al--O).sub.m;
R.sup.3(R.sup.4--Al--O).sub.m--AlR.sup.5 or mixtures thereof,
wherein R.sup.2-R.sup.5 are, independently, a univalent anionic
ligand such as a C.sub.1-C.sub.5 alkyl group or halide and "m" is
an integer ranging from 1 to about 50 and preferably is from about
13 to about 25.
[0019] Catalyst systems of the invention may be prepared by placing
the "Group IV B transition metal component" and the alumoxane
component in common solution in a normally liquid alkane or
aromatic solvent, which solvent is preferably suitable for use as a
polymerization diluent for the liquid phase polymerization of an
olefin monomer.
[0020] A typical polymerization process of the invention such as
for the polymerization or copolymerization of olefins comprises the
steps of contacting ethylene or C.sub.3-C.sub.20 .alpha.-olefins
alone or with other unsaturated monomers including C.sub.3-C.sub.20
.alpha.-olefins, C.sub.5-C.sub.20 diolefins, and/or acetylenically
unsaturated monomers either alone or in combination with other
olefins and/or other unsaturated monomers, with a catalyst
comprising, in a suitable polymerization diluent, the Group IV B
transition metal component illustrated above; and a methylalumoxane
in an amount to provide a molar aluminum to transition metal ratio
of from about 1:1 to about 20,000:1 or more; and reacting such
monomer in the presence of such catalyst system at a temperature of
from about -100.degree. C. to about 300.degree. C. for a time of
from about 1 second to about 10 hours to produce a polyolefin
having a weight average molecular weight of from about 1,000 or
less to about 5,000,000 or more and a molecular weight distribution
of from about 1.5 to about 15.0.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Catalyst Component
[0021] The Group IV B transition metal component of the catalyst
system is represented by the general formula: ##STR3## wherein: M
is Zr, Hf or Ti and is in its highest formal oxidation state (+4,
d.sup.0 complex);
[0022] (C.sub.5H.sub.5-y-xR.sub.x) is a cyclopentadienyl ring which
is substituted with from zero to five substituent groups R. "x" is
0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each
substituent group R is, independently, a radical selected from a
group consisting of C.sub.1-C.sub.20 hydrocarbyl radicals,
substituted C.sub.1-C.sub.20 hydrocarbyl radicals wherein one or
more hydrogen atoms is replaced by a halogen atom, C.sub.1-C.sub.20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is
selected from the Group IV A of the Periodic Table of Elements, and
halogen radicals or (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ring in which two adjacent R-groups are joined
forming C.sub.4-C.sub.20 ring to give a saturated or unsaturated
polycyclic cyclopentadienyl ligand such as indenyl,
tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
[0023] (JR'.sub.z-1-y) is a heteroatom ligand in which J is an
element with a coordination number of three from Group V A or an
element with a coordination number of two from Group VI A of the
Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen
or sulfur with nitrogen being preferred, and each R' is,
independently a radical selected from a group consisting of
C.sub.1-C.sub.20 hydrocarbyl radicals, substituted C.sub.1-C.sub.20
hydrocarbyl radicals wherein one or more hydrogen atoms is replaced
by a halogen atom, and "z" is the coordination number of the
element 3;
[0024] each Q is, independently any univalent anionic ligand such
as halogen, hydride, or substituted or unsubstituted
C.sub.1-C.sub.20 hydrocarbyl, alkoxide, aryloxide, amide,
arylamide, phosphide or arylphosphide, provided that where any Q is
a hydrocarbyl such Q is different from (C.sub.5H.sub.5-y-xR.sub.x)
or both Q together may be be an alkylidene or a cyclometallated
hydrocarbyl or any other divalent anionic chelating ligand;
[0025] "y" is 0 or 1 when w is greater than 0, and y is 1 when w=0;
when "y" is 1, B is a covalent bridging group containing a Group IV
A or V A element such as, but not limited to, a dialkyl, alkylaryl
or diaryl silicon or germanium radical, alkyl or aryl phosphine or
amine radical, or a hydrocarbyl radical such as methylene, ethylene
and the like. L is defined as heretofore. Examples of the B group
which are suitable as a constituent group of the Group IV B
transition metal component of the catalyst system are identified in
Column 1 of Table 1 under the heading "B".
[0026] Exemplary hydrocarbyl radicals for the Q are methyl, ethyl,
propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl,
nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl
being preferred. Exemplary halogen atoms for Q include chlorine,
bromine, fluorine and iodine, with chlorine being preferred.
Exemplary alkoxides and aryloxides for Q are methoxide, phenoxide
and substituted phenoxides such as 4-methylphenoxide. Exemplary
amides for Q are dimethylamide, diethylamide, methylethylamide,
di-t-butylamide, diisopropylamide and the like. Exemplary aryl
amides are diphenylamide and any other substituted phenyl amides.
Exemplary phosphides for Q are diphenylphosphide,
dicyclohexylphosphide, diethylphosphide, dimethylphosphide and the
like. Exemplary alkyldiene radicals for both Q together are
methylidene, ethylidene and propylidene. Examples of the Q group
which are suitable as a constituent group or element of the Group
IV B transition metal component of the catalyst system are
identified in Column 4 of Table 1 under the heading "Q".
[0027] Suitable hydrocarbyl and substituted hydrocarbyl radicals,
which may be substituted as an R group for at least one hydrogen
atom in the cyclopentadienyl ring, will contain from 1 to about 20
carbon atoms and include straight and branched alkyl radicals,
cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon
radicals, aromatic radicals, alkyl-substituted aromatic radicals
and cyclopentadienyl rings containing 1 or more fused saturated or
unsaturated rings. Suitable organometallic radicals, which may be
substituted as an R group for at least one hydrogen atom in the
cyclopentadienyl ring, include trimethylsilyl, triethylsilyl,
ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl,
trimethylgermyl and the like. Examples of cyclopentadienyl ring
groups (C.sub.5H.sub.5-y-xR.sub.x) which are suitable as a
constituent group of the Group IV B transition metal component of
the catalyst system are identified in Column 2 of Table 1 under the
heading (C.sub.5H.sub.5-y-xR.sub.x).
[0028] Suitable hydrocarbyl and substituted hydrocarbyl radicals,
which may be substituted as an R' group for at least one hydrogen
atom in the heteroatom J ligand group, will contain from 1 to about
20 carbon atoms and include straight and branched alkyl radicals,
cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon
radicals, aromatic radicals and alkyl-substituted aromatic
radicals. Examples of heteroatom ligand groups (JR'.sub.z-1-y)
which are suitable as a constituent group of the Group IV B
transition metal component of the catalyst system are identified in
Column 3 of Table 1 under the heading (JR'.sub.z-1-y).
[0029] Table 1 depicts representative constituent moieties for the
"Group IV B transition metal component", the list is for
illustrative purposes only and should not be construed to be
limiting in any way. A number of final components may be formed by
permuting all possible combinations of the constituent moieties
with each other. Illustrative compounds are:
dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium
dichloride,
dimethylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium
dichloride,
dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido zirconium
dichloride,
dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido hafnium
dichloride,
dimethylsilyltrimethylsilylcyclopentadienyl-tert-butylamido
zirconium dichloride,
dimethylsilyltetramethylcyclopentadienylphenylamido zirconium
dichloride, dimethylsilyltetramethylcyclopentadienylphenylamido
hafnium dichloride,
methylphenylsilyltetramethylcyclopentadienyltert-butylamido
zirconium dichloride,
methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido
hafnium dichloride,
methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido
hafnium dimethyl,
dimethylsilyltetramethylcyclopentadienyl-p-n-butylphenylamido
zirconium dichloride,
dimethylsilyltetramethylcyclopentadienyl-p-n-butylphenylamido
hafnium dichloride. For illustrative purposes, the above compounds
and those permuted from Table 1 does not include the Lewis base
ligand (L). The conditions under which complexes containing Lewis
base ligands such as ether or those which form dimers is determined
by the steric bulk of the ligands about the metal center. For
example, the t-butyl group in
Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)ZrCl.sub.2 has greater steric
requirements than the phenyl group in
Me.sub.2Si(Me.sub.4C.sub.5)(NPh)ZrCl.sub.2.Et.sub.2O thereby not
permitting ether coordination in the former compound. Similarly,
due to the decreased steric bulk of the
trimethylsilylcyclopentadienyl group in
[Me.sub.2Si(Me.sub.3SiC.sub.5H.sub.3)(N-t-Bu)ZrCl.sub.2].sub.2
versus that of the tetramethylcyclopentadienyl group in
Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)--ZrCl.sub.2, the former
compound is dimeric and the latter is not. TABLE-US-00001 TABLE 1
##STR4## B (when y = 1) (C.sub.5M.sub.5-y-xR.sub.x) (JR'.sub.z-1-y)
Q M dimethylsilyl cyclopentadienyl t-butylamido hydride zirconium
diethylysilyl methylcyclopentadienyl phenylamido chloro hafnium
di-n-propylsilyl 1,2-dimethylcyclopentadienyl p-n-butylphenylamido
methyl titanium diisopropylsilyl 1,3-dimethylcyclopentadienyl
cyclohexylamido ethyl di-n-butylsilyl indenyl perflurophenylamido
phenyl di-t-butylsilyl 1,2-diethylcyclopentadienyl n-butylamido
fluoro di-n-hexylsilyl tetramethylcyclopentadienyl methylamido
bromo methylphenylsilyl ethylcyclopentadienyl ethylamido iodo
ethylmethylsilyl n-butylcyclopentadienyl n-propylamido n-propyl
diphenylsilyl cyclohexylmethylcyclopentadienyl isopropylamido
isopropyl di(p-t-butylphenethylsilyl) n-octylcyclopentadienyl
benzylamido n-butyl n-hexylmethylsilyl
.beta.-phenylpropylcyclopentadienyl t-butylphospheido amyl
cyclopentamethylenesilyl tetrahydroindenyl ethylphosphido isoamyl
cyclotetramethylenesilyl propylcyclopentadienyl phenylphosphido
hexyl cyclotrimethylenesilyl t-butylcyclopentadienyl
cyclohexylphosphido isobutyl dimethylgermanyl
benzylcyclopentadienyl oxo (when y = 1) heptyl diethylgermanyl
diphenylmethylcyclopentadienyl sulfido (when y = 1) octyl
phenylamido trimethylgermylcyclopentadienyl methoxide (when y = 0)
nonyl t-butylamido trimethylstannylcyclopentadienyl ethoxide (when
y = 0) decyl methylamido triethylplumbylcyclopentadienyl methylthio
(when y = 0) cetyl t-butylphosphido trifluromethylcyclopentadienyl
ethylthio (when y = 0) methoxy ethylphosphido
trimethylsilylcyclopentadienyl ethoxy phenylphosphido
pentamethylcycloopentadienyl (when y = 0) propoxy methylene
fluorenyl butoxy dimethylmethylene octahydrofluorenyl phenoxy
diethylmethylene dimethylamido ethylene diethylamido
dimethylethylene methylethylamido diethylethylene di-t-butylamido
dipropylethylene diphenylamido propylene diphenylphosphido
dimethylpropylene dicyclohexylphosphido diethylpropylene
dimethylphosphido 1,1-dimethyl-3,3,-dimethylpropylene methylidene
(both Q) tetramethyldisilexene ethylidene (both Q)
1,1,4,4-tetramethylidisilylethylene propylidene (both Q)
ethyleneglycol dianion
[0030] Generally the bridged species of the Group IV B transition
metal compound ("y"=1) are preferred. These compounds can be
prepared by reacting a cyclopentadienyl lithium compound with a
dihalo compound whereupon a lithium halide salt is liberated and a
monohalo substituent becomes covalently bound to the
cyclopentadienyl compound. The so substituted cyclopentadienyl
reaction product is next reacted with a lithium salt of a
phosphide, oxide, sulfide or amide (for the sake of illustrative
purposes, a lithium amide) whereupon the halo element of the
monohalo substituent group of the reaction product reacts to
liberate a lithium halide salt and the amine moiety of the lithium
amide salt becomes covalently bound to the substituent of the
cyclopentadienyl reaction product. The resulting amine derivative
of the cyclopentadienyl product is then reacted with an alkyl
lithium reagent whereupon the labile hydrogen atoms, at the carbon
atom of the cyclopentadienyl compound and at the nitrogen atom of
the amine moiety covalently bound to the substituent group, react
with the alkyl of the lithium alkyl reagent to liberate the alkane
and produce a dilithium salt of the cyclopentadienyl compound.
Thereafter the bridged species of the Group IV B transition metal
compound is produced by reacting the dilithium salt
cyclopentadienyl compound with a Group IV B transition metal
preferably a Group IV B transition metal halide.
[0031] Unbridged species of the Group IV B transition metal
compound can be prepared from the reaction of a cyclopentadienyl
lithium compound and a lithium salt of an amine with a Group IV B
transition metal halide.
[0032] Suitable, but not limiting, Group IV B transition metal
compounds which may be utilized in the catalyst system of this
invention include those bridged species ("y"=1) wherein the B group
bridge is a dialkyl, diaryl or alkylaryl silane, or methylene or
ethylene. Exemplary of the more preferred species of bridged Group
IV B transition metal compounds are dimethylsilyl,
methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl,
ethylene or methylene bridged compounds. Most preferred of the
bridged species are dimethylsilyl, diethylsilyl and
methylphenylsilyl bridged compounds.
[0033] Suitable Group IV B transition metal compounds which are
illustrative of the unbridged ("y"=0) species which may be utilized
in the catalyst systems of this invention are exemplified by
pentamethylcyclopentadienyldi-t-butylphosphinodimethyl hafnium;
pentamethylcyclopentadienyldi-t-butylphosphinomethylethyl hafnium;
cyclopentadienyl-2-methylbutoxide dimethyl titanium.
[0034] To illustrate members of the Group IV B transition metal
component, select any combination of the species in Table 1. An
example of a bridged species would be
dimethylsilylcyclopentadienyl-t-butylamidodichloro zirconium; an
example of an unbridged species would be
cyclopentadienyldi-t-butylamidodichloro zirconium.
[0035] The alumoxane component of the catalyst system is an
oligomeric compound which may be represented by the general formula
(R.sup.2--Al--O).sub.m which is a cyclic compound, or may be
R.sup.3(R.sup.4--Al--O--).sub.m--AlR.sub.2.sup.5 which is a linear
compound. An alumoxane is generally a mixture of both the linear
and cyclic compounds. In the general alumoxane formula R.sup.2,
R.sup.3, R.sup.4, and R.sup.5 are, independently a univalent
anionic ligand such as a C.sub.1-C.sub.5 alkyl radical, for
example, methyl, ethyl, propyl, butyl, pentyl or halide and "m" is
an integer from 1 to about 50. Most preferably, R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 are each methyl and "m" is at least 4. When an
alkyl aluminum halide is employed in the preparation of alumoxane,
one or more of R.sup.2-5 could be halide.
[0036] As is now well known, alumoxanes can be prepared by various
procedures. For example, a trialkyl aluminum may be reacted with
water, in the form of a moist inert organic solvent; or the
trialkyl aluminum may be contacted with a hydrated salt, such as
hydrated copper sulfate suspended in an inert organic solvent, to
yield an alumoxane. Generally, however prepared, the reaction of a
trialkyl aluminum with a limited amount of water yields a mixture
of both the linear and cyclic species of alumoxane.
[0037] Suitable alumoxanes which may be utilized in the catalyst
systems of this invention are those prepared by the hydrolysis of a
alkylaluminum reagent; such as trimethylaluminum, triethyaluminum,
tripropylaluminum; trisobutylaluminum, dimethylaluminumchloride,
diisobutylaluminumchloride, diethylaluminumchloride, and the like.
The most preferred alumoxane for use is methylalumoxane (MAO),
particularly methylalumoxanes having a reported average degree of
oligomerization of from about 4 to about 25 ("m"=4 to 25) with a
range of 13 to 25 being most preferred.
Catalyst Systems
[0038] The catalyst systems employed in the method of the invention
comprise a complex formed upon admixture of the Group IV B
transition metal component with an alumoxane component. The
catalyst system may be prepared by addition of the requisite Group
IV B transition metal and alumoxane components to an inert solvent
in which olefin polymerization can be carried out by a solution,
slurry or bulk phase polymerization procedure.
[0039] The catalyst system may be conveniently prepared by placing
the selected Group IV B transition metal component and the selected
alumoxane component, in any order of addition, in an alkane or
aromatic hydrocarbon solvent--preferably one which is also suitable
for service as a polymerization diluent. Where the hydrocarbon
solvent utilized is also suitable for use as a polymerization
diluent, the catalyst system may be prepared in situ in the
polymerization reactor. Alternatively, the catalyst system may be
separately prepared, in concentrated form, and added to the
polymerization diluent in a reactor. Or, if desired, the components
of the catalyst system may be prepared as separate solutions and
added to the polymerization diluent in a reactor, in appropriate
ratios, as is suitable for a continuous liquid polymerization
reaction procedure. Alkane and aromatic hydrocarbons suitable as
solvents for formation of the catalyst system and also as a
polymerization diluent are exemplified by, but are not necessarily
limited to, straight and branched chain hydrocarbons such as
isobutane, butane, pentane, hexane, heptane, octane and the like,
cyclic and alicyclic hydrocarbons such as cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane and the like,
and aromatic and alkyl-substituted aromatic compounds such as
benzene, toluene, xylene and the like. Suitable solvents also
include liquid olefins which may act as monomers or comonomers
including ethylene, propylene, 1-butene, 1-hexene and the like.
[0040] In accordance with this invention optimum results are
generally obtained wherein the Group IV B transition metal compound
is present in the polymerization diluent in a concentration of from
about 0.0001 to about 1.0 millimoles/liter of diluent and the
alumoxane component is present in an amount to provide a molar
aluminum to transition metal ratio of from about 1:1 to about
20,000:1. Sufficient solvent should be employed so as to provide
adequate heat transfer away from the catalyst components during
reaction and to permit good mixing.
[0041] The catalyst system ingredients--that is, the Group IV B
transition metal, the alumoxane, and polymerization diluent can be
added to the reaction vessel rapidly or slowly. The temperature
maintained during the contact of the catalyst components can vary
widely, such as, for example, from -10.degree. to 300.degree. C.
Greater or lesser temperatures can also be employed. Preferably,
during formation of the catalyst system, the reaction is maintained
within a temperature of from about 25.degree. to 100.degree. C.,
most preferably about 25.degree. C.
[0042] At all times, the individual catalyst system components, as
well as the catalyst system once formed, are protected from oxygen
and moisture. Therefore, the reactions are performed in an oxygen
and moisture free atmosphere and, where the catalyst system is
recovered separately it is recovered in an oxygen and moisture free
atmosphere. Preferably, therefore, the reactions are performed in
the presence of an inert dry gas such as, for example, helium or
nitrogen.
Polymerization Process
[0043] In a preferred embodiment of the process of this invention
the catalyst system is utilized in liquid phase (slurry, solution,
suspension or bulk phase and combination thereof), high pressure
fluid phase or gas phase polymerization of an olefin monomer. These
processes may be employed singularly or in series. The liquid phase
process comprises the steps of contacting an olefin monomer with
the catalyst system in a suitable polymerization diluent and
reacting said monomer in the presence of said catalyst system for a
time and at a temperature sufficient to produce a polyolefin of
high molecular weight.
[0044] The monomer for such process may comprise ethylene alone,
for the production of a homopolyethylene, or ethylene in
combination with an .alpha.-olefin having 3 to 20 carbon atoms for
the production of an ethylene-.alpha.-olefin copolymer.
Homopolymers of higher .alpha.-olefin such as propylene, butene,
styrene and copolymers thereof with ethylene and/or C.sub.4 or
higher .alpha.-olefins and diolefins can also be prepared.
Conditions most preferred for the homo- or co-polymerization of
ethylene are those wherein ethylene is submitted to the reaction
zone at pressures of from about 0.019 psia to about 50,000 psia and
the reaction temperature is maintained at from about -100.degree.
to about 300.degree. C. The aluminum to transition metal molar
ratio is preferably from about 1:1 to 18,000 to 1. A preferable
range would be 1:1 to 1000:1. The reaction time is preferably from
about 1 min to about 1 hr. Without limiting in any way the scope of
the invention, one means for carrying out the process of the
present invention is as follows: in a stirred-tank reactor liquid
1-butene monomer is introduced. The catalyst system is introduced
via nozzles in either the vapor or liquid phase. Feed ethylene gas
is introduced either into the vapor phase of the reactor, or
sparged into the liquid phase as is well known in the art. The
reactor contains a liquid phase composed substantially of liquid
1-butene together with dissolved ethylene gas, and a vapor phase
containing vapors of all monomers. The reactor temperature and
pressure may be controlled via reflux of vaporizing .alpha.-olefin
monomer (autorefrigeration), as well as by cooling coils, jackets
etc. The polymerization rate is controlled by the concentration of
catalyst. The ethylene content of the polymer product is determined
by the ratio of ethylene to 1-butene in the reactor, which is
controlled by manipulating the relative feed rates of these
components to the reactor.
EXAMPLES
[0045] In the examples which illustrate the practice of the
invention the analytical techniques described below were employed
for the analysis of the resulting polyolefin products. Molecular
weight determinations for polyolefin products were made by Gel
Permeation Chromatography (GPC) according to the following
technique. Molecular weights and molecular weight distributions
were measured using a Waters 150 gel permeation chromatograph
equipped with a differential refractive index (DRI) detector and a
Chromatix KMX-6 on-line light scattering photometer. The system was
used at 135.degree. C. with 1,2,4-trichlorobenzene as the mobile
phase. Shodex (Showa Denko America, Inc.) polystyrene gel columns
802, 803, 804 and 805 were used. This technique is discussed in
"Liquid Chromatography of Polymers and Related Materials III", J.
Cazes editor, Marcel Dekker, 1981, p. 207 which is incorporated
herein by reference. No corrections for column spreading were
employed; however, data on generally accepted standards, e.g.
National Bureau of Standards Polyethylene 1484 and anionically
produced hydrogenated polyisoprenes (an alternating
ethylene-propylene copolymer) demonstrated that such corrections on
Mw/Mn (=MWD) were less than 0.05 units. Mw/Mn was calculated from
elution times. The numerical analyses were performed using the
commercially available Beckman/CIS customized LALLS software in
conjunction with the standard Gel Permeation package, run on a HP
1000 computer.
[0046] The following examples are intended to illustrate specific
embodiments of the invention and are not intended to limit the
scope of the invention.
[0047] All procedures were performed under an inert atmosphere of
helium or nitrogen. Solvent choices are often optional, for
example, in most cases either pentane or 30-60 petroleum ether can
be interchanged. The lithiated amides were prepared from the
corresponding amines and either n-BuLi or MeLi. Published methods
for preparing LiHC.sub.5Me.sub.4 include C. M. Fendrick et al.
Organometallics, 3, 819 (1984) and F. H. Kohler and K. H. Doll, Z.
Naturforsch, 376, 144 (1982). Other lithiated substituted
cyclopentadienyl compounds are typically prepared from the
corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by
reaction of MeLi with the proper fulvene. ZrCl.sub.4 and HfCl.sub.4
were purchased from either Aldrich Chemical Company or Cerac.
Amines, silanes and lithium reagents were purchased from Aldrich
Chemical Company or Petrarch Systems. Methylalumoxane was supplied
by either Sherring or Ethyl Corp.
EXAMPLES A-L OF GROUP IV B TRANSITION METAL COMPONENTS
Example A
[0048] Compound A: Part 1. Me.sub.4HC.sub.5Li (10.0 g, 0.078 mol)
was slowly added to a Me.sub.2SiCl.sub.2 (11.5 ml, 0.095 mol, in
225 ml of tetrahydrofuran (thf) solution). The solution was stirred
for 1 hour to assure complete reaction. The thf solvent was then
removed via a vacuum to a cold trap held at -196.degree. C. Pentane
was added to precipitate out the LiCl. The mixture was filtered
through Celite. The solvent was removed from the filtrate.
Me.sub.4HC.sub.5SiMe.sub.2Cl (15.34 g, 0.071 mol) was recovered as
a pale yellow liquid.
[0049] Part 2. Me.sub.4HC.sub.5SiMe.sub.2Cl (10.0 g, 0.047 mol) was
slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol,
.about.100 ml thf). The mixture was stirred overnight. The thf was
then removed via a vacuum to a cold trap held at -196.degree. C.
Petroleum ether (-100 ml) was added to precipitate out the LiCl.
The mixture was filtered through Celite. The solvent was removed
from the filtrate. Me.sub.2Si(Me.sub.4HC.sub.5)(HN-t-Bu) (11.14 g,
0.044 mol) was isolated as a pale yellow liquid.
[0050] Part 3. Me.sub.2Si(Me.sub.4HC.sub.5)(HN-t-Bu) (11.14 g,
0.044 mol) was diluted with .about.100 ml Et.sub.2O. MeLi (1.4 M,
64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir
for 1/2 hour after the final addition of MeLi. The ether was
reduced in volume prior to filtering off the product. The product,
[Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)]Li.sub.2, was washed with
several small portions of ether, then vacuum dried.
[0051] Part 4. [Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)]Li.sub.2 (3-0
g, 0.011 mol) was suspended in .about.150 ml Et.sub.2O. ZrCl.sub.4
(2.65 g, 0.011 mol) was slowly added and the resulting mixture was
allowed to stir overnight. The ether was removed via a vacuum to a
cold trap held at -196.degree. C. Pentane was added to precipitate
out the LiCl. The mixture was filtered through Celite twice. The
pentane was significantly reduced in volume and the pale yellow
solid was filtered off and washed with solvent.
[0052] Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)ZrCl.sub.2 (1.07 g,
0.0026 mole) was recovered. Additional
Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)ZrCl.sub.2 was recovered from
the filtrate by repeating the recrystallization procedure. Total
yield, 1.94 g, 0.0047 mol).
Example B
[0053] Compound B: The same procedure of Example A for preparing
compound A was followed with the exception of the use of HfCl.sub.4
in place of ZrCl.sub.4 in Part 4. Thus, when
[Me.sub.2Si(Me.sub.4C.sub.5)--(N-t-Bu)]Li.sub.2 (2.13 g, 0.0081
mol) and HfCl.sub.4 (2.59 g, 0.0081 mol) were used,
Me.sub.2Si(Me.sub.4C.sub.5)(N-t-Bu)HfCl.sub.2 (0.98 g, 0.0020 mol)
was produced.
Example C
[0054] Compound C: Part 1. Me.sub.2SiCl.sub.2 (7.5 ml, 0.062 mol)
was diluted with .about.30 ml thf. A t-BuH.sub.4C.sub.5Li solution
(7.29 g, 0.056 mol, .about.100 ml thf) was slowly added, and the
resulting mixture was allowed to stir overnight. The thf was
removed via a vacuum to a trap held at -196.degree. C. Pentane was
added to precipitate out the LiCl, and the mixture was filtered
through Celite. The pentane was removed from the filtrate leaving
behind a pale yellow liquid, t-BuH.sub.4C.sub.5SiMe.sub.2Cl (10.4
g, 0.048 mol).
[0055] Part 2. To a thf solution of LiHN-t-Bu (3.83 g, 0.048 mol,
.about.125 ml), t-BuH.sub.4C.sub.5SiMe.sub.2Cl (10.4 g, 0.048 mol)
was added drop wise. The resulting solution was allowed to stir
overnight. The thf was removed via a vacuum to a trap held at
-196.degree. C. Pentane was added to precipitate out the LiCl, and
the mixture was filtered through Celite. The pentane was removed
from the filtrate leaving behind a pale yellow liquid,
Me.sub.2Si(t-BuH.sub.4C.sub.5)(NH-t-Bu) (11.4 g, 0.045 mol).
[0056] Part 3. Me.sub.2Si(t-BuH.sub.4C.sub.5)(NH-t-Bu) (11.4 g,
0.045 mol) was diluted with .about.100 ml Et.sub.2O. MeLi (1.4 M,
70 ml, 0.098 mol) was slowly added. The mixture was allowed to stir
overnight. The ether was removed via a vacuum to a trap held at
-19.6.degree. C., leaving behind a pale yellow solid,
[Me.sub.2Si(t-BuH.sub.3C.sub.5)(N-t-Bu)]Li.sub.2 (11.9 g, 0.045
mol).
[0057] Part 4. [Me.sub.2Si(t-BuH.sub.3C.sub.5)(N-t-Bu)]Li.sub.2
(3.39 g, 0.013 mol) was suspended in .about.100 ml Et.sub.2O.
ZrCl.sub.4 (3.0 g, 0.013 mol) was slowly added. The mixture was
allowed to stir overnight. The ether was removed and pentane was
added to precipitate out the LiCl. The mixture was filtered through
Celite. The pentane solution was reduced in volume, and the pale
tan solid was filtered off and washed several times with small
quantities of pentane. The product of empirical formula
Me.sub.2Si(t-BuH.sub.3C.sub.5)(N-t-Bu)ZrCl.sub.2 (2.43 g, 0.0059
mol) was isolated.
Example D
[0058] Compound D: The same procedure of Example C for preparing
compound C was followed with the exception of the use of HfCl.sub.4
in Part 4. Thus, when
[Me.sub.2Si(t-BuH.sub.3C.sub.5)(N-t-Bu)]Li.sub.2 (3.29 g, 0.012
mol) and HfCl.sub.4 (4.0 g, 0.012 mol) were used, the product of
the empirical formula
Me.sub.2Si(t-BuH.sub.3C.sub.5)(N-t-Bu)HfCl.sub.2 (1.86 g, 0.0037
mol) was produced.
Example E
[0059] Compound E: Part 1. Me.sub.2SiCl.sub.2 (7.0 g, 0.054 mol)
was diluted with .about.100 ml of ether. Me.sub.3SiC.sub.5H.sub.4Li
(5.9 g, 0.041 mol) was slowly added. Approximately 75 ml of thf was
added and the mixture was allowed to stir overnight. The solvent
was removed via a vacuum to a cold trap held at -196.degree. C.
Pentane was added to precipitate out the LiCl. The mixture was
filtered through Celite. The solvent was removed from the filtrate
giving Me.sub.2Si(Me.sub.3SiC.sub.5H.sub.4)Cl (8.1 g, 0.035 mol) as
a pale yellow liquid.
[0060] Part 2. Me.sub.2Si(Me.sub.3SiC.sub.5H.sub.4)Cl (3.96 g,
0.017 mol) was diluted with .about.50 ml of ether. LiHN-t-Bu (1.36
g, 0.017 mol) was slowly added, and the mixture was allowed to stir
overnight. The ether was removed via a vacuum and pentane was added
to precipitate the LiCl. The mixture was filtered through Celite,
and the pentane was removed from the filtrate.
Me.sub.2Si--(Me.sub.3SiC.sub.5H.sub.4)(NH-t-Bu) (3.7 g, 0.014 mol)
was isolated as a pale yellow liquid.
[0061] Part 3. Me.sub.2 Si(Me.sub.3SiC.sub.5H.sub.4)(NH-t-Bu) (3.7
g, 0.014 mol) as diluted with ether. MeLi (25 ml, 1.4M in ether,
0.035 mol) was slowly added. The mixture was allowed to stir for
1.5 hours after the final addition of MeLi. The ether was removed
via vacuum producing 4.6 g of a white solid formulated as
Li.sub.2[Me.sub.2Si--(Me.sub.3SiC.sub.5H.sub.3)(N-t-Bu)].3/4Et.sub.2O
and unreacted MeLi which was not removed from the solid.
[0062] Part 4.
Li.sub.2[Me.sub.2Si(Me.sub.3SiC.sub.5H.sub.3)(N-t-Bu)].3/4Et.sub.2O
(1.44 g, 0.0043 mol) was suspended in .about.50 ml of ether.
ZrCl.sub.4 (1.0 g, 0.0043 mol) was slowly added and the reaction
was allowed to stir for a few hours. The solvent was removed via
vacuum and pentane was added to precipitate the LiCl. The mixture
was filtered through Celite, and the filtrate was reduced in
volume. The flask was placed in the freezer (-40.degree. C.) to
maximize precipitation of the product. The solid was filtered off
giving 0.273 g of an off white solid. The filtrate was again
reduced in volume, the precipitate filtered off to give an
additional 0.345 g for a total of 0.62 g of the compound with
empirical formula
Me.sub.2Si(Me.sub.3SiC.sub.5H.sub.3)(N-t-Bu)ZrCl.sub.2. The x-ray
crystal structure of this product reveals that the compound is
dimeric in nature.
Example F
[0063] Compound F: Part 1. Me.sub.4HC.sub.5SiMe.sub.2Cl was
prepared as described in Example A for the preparation of compound
A, Part 1.
[0064] Part 2. LiHNPh (4.6 g, 0.0462 mol) was dissolved in
.about.100 ml of thf. Me.sub.4HC.sub.5SiMe.sub.2Cl (10.0 g, 0.0466
mol) was slowly added. The mixture was allowed to stir overnight.
The thf was removed via a vacuum. Petroleum ether and toluene were
added to precipitate the LiCl, and the mixture was filtered through
Celite. The solvent was removed, leaving behind a dark yellow
liquid, Me.sub.2Si(Me.sub.4HC.sub.5)(NHPh) (10.5 g, 0.0387
mol).
[0065] Part 3. Me.sub.2Si(Me.sub.4HC.sub.5)(NHPh) (10.5 g, 0.0387
mol) was diluted with .about.60 ml of ether. MeLi (1.4 M in ether,
56 ml, 0.0784 mol) was slowly added and the reaction was allowed to
stir overnight. The resulting white solid,
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)(NPh).3/4Et.sub.2O (11.0 g),
was filtered off and was washed with ether.
[0066] Part 4.
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)(NPh).3/4Et.sub.2O (2.81 g,
0.083 mol) was suspended in .about.40 ml of ether. ZrCl.sub.4 (1.92
g, 0.0082 mol) was slowly added, and the mixture was allowed to
stir overnight. The ether was removed via a vacuum, and a mixture
of petroleum ether and toluene was added to precipitate the LiCl.
The mixture was filtered through Celite, the solvent mixture was
removed via vacuum, and pentane was added. The mixture was placed
in the freezer at -40.degree. C. to maximize the precipitation of
the product. The solid was then filtered off and washed with
pentane. Me.sub.2Si(Me.sub.4C.sub.5)(NPh)ZrCl.sub.2.Et.sub.2O was
recovered as a pale yellow solid (1.89 g).
Example G
[0067] Compound G: The same procedure of Example F for preparing
compound F was followed with the exception of the use of HfCl.sub.4
in place of ZrCl.sub.4 in Part 4. Thus, when
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)--(NPh)].3/4Et.sub.2O (2.0 g,
0.0059 mol) and HfCl.sub.4 (1.89 g, 0.0059 mol) were used,
Me.sub.2Si(Me.sub.4C.sub.5)(NPh)HfCl.sub.2.1/2Et.sub.2O (1.70 g)
was produced.
Example H
[0068] Compound H: Part 1. MePhSiCl.sub.2 (14.9 g, 0.078 mol) was
diluted with .about.250 ml of thf. Me.sub.4C.sub.5HLi (10.0 g,
0.078 mol) was slowly added as a solid. The reaction solution was
allowed to stir overnight. The solvent was removed via a vacuum to
a cold trap held at -196.degree. C. Petroleum ether was added to
precipitate out the LiCl. The mixture was filtered through Celite,
and the pentane was removed from the filtrate.
MePhSi(Me.sub.4C.sub.5H)Cl (20.8 g, 0.075 mol) was isolated as a
yellow viscous liquid.
[0069] Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in
.about.100 ml of thf. MePhSi(Me.sub.4C.sub.5H)Cl (15.0 g, 0.054
mol) was added drop wise. The yellow solution was allowed to stir
overnight. The solvent was removed via vacuum. Petroleum ether was
added to precipitate out the LiCl. The mixture was filtered through
Celite, and the filtrate was evaporated down.
MePhSi(Me.sub.4C.sub.5H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered
as an extremely viscous liquid.
[0070] Part 3. MePhSi(Me.sub.4C.sub.5H)(NH-t-Bu) (16.6 g, 0.053
mol) was diluted with .about.100 ml of ether. MeLi (76 ml, 0.106
mol, 1.4 M) was slowly added and the reaction mixture was allowed
to stir for .about.3 hours. The ether was reduced in volume, and
the lithium salt was filtered off and washed with pentane producing
20.0 g of a pale yellow solid formulated as
Li.sub.2[MePhSi(Me.sub.4C.sub.5)(N-t-Bu)].3/4Et.sub.2O.
[0071] Part 4.
Li.sub.2[MePhSi(Me.sub.4C.sub.5)(N-t-Bu)].3/4Et.sub.2O (5.0 g,
0.0131 mol) was suspended in .about.100 ml of Et.sub.2O. ZrCl.sub.4
(3.06 g, 0.0131 mol) was slowly added. The reaction mixture was
allowed to stir at room temperature for .about.1.5 hours over which
time the reaction mixture slightly darkened in color. The solvent
was removed via vacuum and a mixture of petroleum ether and toluene
was added. The mixture was filtered through Celite to remove the
LiCl. The filtrate was evaporated down to near dryness and filtered
off. The off white solid was washed with petroleum ether. The yield
of product, MePhSi(Me.sub.4C.sub.5)(N-t-Bu)ZrCl.sub.2, was 3.82 g
(0.0081 mol).
Example I
[0072] Compound I:
Li.sub.2[MePhSi(Me.sub.4C.sub.5)(N-t-Bu)].3/4Et.sub.2O was prepared
as described in Example H for the preparation of compound H, Part
3.
[0073] Part 4.
Li.sub.2[MePhSi(Me.sub.4C.sub.5)(N-t-Bu)].3/4Et.sub.2O (5.00 g,
0.0131 mol) was suspended in .about.100 ml of Et.sub.2O. HfCl.sub.4
(4.20 g, 0.0131 mol) was slowly added and the reaction mixture was
allowed to stir overnight. The solvent was removed via vacuum and
petroleum ether was added to precipitate out the LiCl. The mixture
was filtered through Celite. The filtrate was evaporated down to
near dryness and filtered off. The off white solid was washed with
petroleum ether. MePhSi(Me.sub.4C.sub.5)(N-t-Bu)HfCl.sub.2 was
recovered (3.54 g, 0.0058 mole).
Example J
[0074] Compound J: MePhSi(Me.sub.4C.sub.5)(N-t-Bu)HfMe.sub.2 was
prepared by adding a stoichiometric amount of MeLi (1.4 M in ether)
to MePhSi(Me.sub.4C.sub.5)(N-t-Bu)HfCl.sub.2 suspended in ether.
The white solid could be isolated in near quantitative yield.
Example K
[0075] Compound K: Part 1. Me.sub.4C.sub.5SiMe.sub.2Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
[0076] Part 2. Me.sub.4C.sub.5SiMe.sub.2Cl (10.0 g, 0.047 mol) was
diluted with .about.25 ml Et.sub.2O. LiHNC.sub.5H.sub.4-p-n-Bu.
1/10Et.sub.2O (7.57 g, 0.047 mol) was added slowly. The mixture was
allowed to stir for .about.3 hours. The solvent was removed via
vacuum. Petroleum ether was added to precipitate out the LiCl, and
the mixture was filtered through Celite. The solvent was removed
leaving behind an orange viscous liquid,
Me.sub.2Si(Me.sub.4C.sub.5H)(HNC.sub.6H.sub.4-p-n-Bu) (12.7 g,
0.039 mol).
[0077] Part 3.
Me.sub.2Si(Me.sub.4C.sub.5H)(HNC.sub.6H.sub.4-p-n-Bu) (12.7 g,
0.039 mol) was diluted with .about.50 ml of Et.sub.2O. MeLi (1.4 M,
55 ml, 0.077 mol) was slowly added. The mixture was allowed to stir
for .about.3 hours. The product was filtered off and washed with
Et.sub.2O producing
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)(NC.sub.6H.sub.4-p-n-Bu)].3/4Et.sub.2-
O as a white solid (13.1 g, 0.033 mol).
[0078] Part 4.
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)(NC.sub.6H.sub.4-p-n-Bu)].3/4Et.sub.2-
O (3.45 g, 0.0087 mol) was suspended in .about.50 ml of Et.sub.2O.
ZrCl.sub.4 (2.0 g, 0.0086 mol) was slowly added and the mixture was
allowed to stir overnight. The ether was removed via vacuum, and
petroleum ether was added to precipitate out the LiCl. The mixture
was filtered through Celite. The filtrate was evaporated to dryness
to give a yellow solid which was recrystallized from pentane and
identified as
Me.sub.2Si(Me.sub.4C.sub.5)(NC.sub.6H.sub.4-p-n-Bu)ZrCl.sub.2.2/3Et.sub.2-
O (4.2 g).
Example L
[0079] Compound L: Li.sub.2[Me.sub.2Si
(Me.sub.4C.sub.5)(NC.sub.6H.sub.4-p-n-Bu)].3/4Et.sub.2O was
prepared as described in Example K for the preparation of compound
K, Part 3.
[0080] Part 4.
Li.sub.2[Me.sub.2Si(Me.sub.4C.sub.5)(NC.sub.6H.sub.4-p-n-Bu)].3/4Et.sub.2-
O (3.77 g, 0.0095 mol) was suspended in .about.50 ml of Et.sub.2O.
HfCl.sub.4 (3.0 g, 0.0094 mol) was slowly added as a solid and the
mixture was allowed to stir overnight. The ether was removed via
vacuum and petroleum ether was added to precipitate out the LiCl.
The mixture was filtered through Celite. Petroleum ether was
removed via a vacuum giving an off white solid which was
recrystallized from pentane. The product was identified as
Me.sub.2Si(Me.sub.4C.sub.5)--(NC.sub.6H.sub.4-p-n-Bu)HfCl.sub.2
(1.54 g, 0.0027 mol).
EXAMPLES 1-34 OF POLYMERIZATION
Example 1
Polymerization--Compound A
[0081] The polymerization run was performed in a 1-liter autoclave
reactor equipped with a paddle stirrer, an external water jacket
for temperature control, a regulated supply of dry nitrogen,
ethylene, propylene, 1-butene and hexane, and a septum inlet for
introduction of other solvents, transition metal compound and
alumoxane solutions. The reactor was dried and degassed thoroughly
prior to use. A typical run consisted of injecting 400 ml of
toluene, 6 ml of 1.5 M MAO, and 0.23 mg of compound A (0.2 ml of a
11.5 mg in 10 ml of toluene solution) into the reactor. The reactor
was then heated to 80.degree. C. and the ethylene (60 psi) was
introduced into the system. The polymerization reaction was limited
to 30 minutes. The reaction was ceased by rapidly cooling and
venting the system. The solvent was evaporated off of the polymer
by a stream of nitrogen. Polyethylene was recovered (9.2 g,
MN=257,200, MWD=2.275).
Example 2
[0082] Polymerization--Compound A
[0083] The polymerization was carried out as in Example 1 with the
following changes: 300 ml of toluene, 3 ml of 1.5 M MAO, and 0.115
mg of compound A (0.1 ml of a 11.5 mg in 10 ml of toluene
solution). Polyethylene was recovered (3.8 g, MN=359,800,
MWD=2.425).
Example 3
Polymerization--Compound A
[0084] The polymerization was carried out as in Example 2 using the
identical concentrations. The difference involved running the
reaction at 40.degree. C. rather than 80.degree. C. as in the
previous example. Polyethylene was recovered (2.4 g, MW=635,000,
MWD=3.445).
Example 4
Polymerization--Compound A
[0085] The polymerization was carried out as in Example 1 except
for the use of 300 ml of hexane in place of 400 ml of toluene.
Polyethylene was recovered (5.4 g, MW=212,600, MWD=2.849).
Example 5
Polymerization--Compound A
[0086] Using the same reactor design and general procedure as in
Example 1, 300 ml of toluene, 200 ml of propylene, 6.0 ml of 1.5 M
MAO, and 0.46 mg of compound A (0.4 ml of a 11.5 mg in 10 ml of
toluene solution) was introduced into the reactor. The reactor was
heated to 80.degree. C., the ethylene was added (60 psi), and the
reaction was allowed to run for 30 minutes, followed by rapidly
cooling and venting the system. After evaporation of the solvent,
13.3 g of an ethylene-propylene copolymer was recovered (MW=24,900,
MWD 2.027, 73.5 SCB/1000C by IR).
Example 6
Polymerization--Compound A
[0087] The polymerization was carried out as in Example 5 except
with the following changes: 200 ml of toluene and 0.92 mg of
compound A (0.8 ml of a 11.5 mg in 10 ml of toluene solution). The
reaction temperature was also reduced to 50.degree. C. An
ethylene-propylene copolymer was recovered (6.0 g, MW=83,100,
MWD=2.370, 75.7 SCB/1000C by IR).
Example 7
Polymerization--Compound A
[0088] Using the same reactor design and general procedure as in
Example 1, 150 ml of toluene, 100 ml of 1-butene, 6.0 ml of 1.5 M
MAO, and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 50.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 30 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
25.4 g of an ethylene-butene copolymer was recovered (MW=184,500,
MWD=3.424, 23.5 SCB/1000C by .sup.13C NMR and 21.5 SCB/1000C by
IR).
Example 8
Polymerization--Compound A
[0089] The polymerization was carried out as in Example 7 except
with the following changes: 100 ml of toluene and 150 ml of
1-butene. An ethylene-butene copolymer was recovered (30.2 g,
MW=143,500, MWD=3.097, 30.8 SCB/1000C by .sup.13C NMR and 26.5
SCB/1000C by IR).
Example 9
Polymerization--Compound A
[0090] The polymerization was carried out as in Example 7 except
with the following changes: 200 ml of toluene, 8.0 ml of 1.0 M MAO,
and 50 ml of 1-butene. An ethylene-butene copolymer was recovered
(24.9 g, MW=163,200, MWD=3.290, 23.3 SCB/1000C by .sup.13C NMR and
18.9 SCB/1000C by IR).
Example 10
Polymerization--Compound A
[0091] The polymerization was carried out as in Example 9 except
for the replacement of 200 ml of toluene with 200 ml of hexane. An
ethylene-butene copolymer was recovered (19.5 g, MW=150,600,
MWD=3.510, 12.1 SCB/1000 C by .sup.13C NMR and 12.7 SCB/1000C by
IR).
Example 11
Polymerization--Compound A
[0092] The polymerization was carried out as in Example 10 except
with the following changes: 150 ml of hexane, and 100 ml of
1-butene. An ethylene-butene copolymer was recovered (16.0 g,
MW=116,200, MWD=3.158, 19.2 SCB/1000C by .sup.13C NMR and 19.4
SCB/1000C by IR).
Example 12
Polymerization--Compound A
[0093] Using the same reactor design and general procedure already
described, 400 ml of toluene, 5.0 ml of 1.0 M MAO, and 0.2 ml of a
preactivated compound A solution (11.5 mg of compound A dissolved
in 9.0 ml of toluene and 1.0 ml of 1.0 M MAO) were added to the
reactor. The reactor was heated to 80.degree. C., the ethylene was
introduced (60 psi), and the reaction was allowed to run for 30
minutes, followed by rapidly cooling and venting the system. After
evaporation of the solvent, 3.4 g of polyethylene was recovered
(MW=285,000, MWD=2.808).
Example 13
Polymerization--Compound A
[0094] A polymerization was carried out as in Example 12 with
exception of aging the preactivated compound A solution by one day.
Polyethylene was recovered (2.0 g, MW=260,700, MWD=2.738).
Example 14
Polymerization--Compound A
[0095] Using the same reactor design and general procedure already
described, 400 ml of toluene, 0.25 ml of 1.0 M MAO, and 0.2 ml of a
preactivated compound A solution (11.5 mg of compound A dissolved
in 9.5 ml of toluene and 0.5 ml of 1.0 M MAO) were added into the
reactor. The reactor was heated to 80.degree. C., the ethylene was
introduced (60 psi), and the reaction was allowed to run for 30
minutes, followed by rapidly cooling and venting the system. After
evaporation of the solvent, 1.1 g of polyethylene was recovered
(MW=479,600, MWD=3.130).
Example 15
Polymerization--Compound A
[0096] Using the same reactor design and general procedure already
described, 400 ml of toluene and 2.0 ml of a preactivated compound
A solution (11.5 mg of compound A dissolved in 9.5 ml of toluene
and 0.5 ml of 1.0 M MAO) were added into the reactor. The reactor
was heated to 80.degree. C., the ethylene was introduced (60 psi),
and the reaction was allowed to run for 30 minutes, followed by
rapidly cooling and venting the system. After evaporation of the
solvent, 1.6 g of polyethylene was recovered (MW=458,800, MWD
2.037).
Example 16
Polymerization--Compound A
[0097] Using the general procedure already described, 400 ml of
toluene, 5.0 ml of 1.0 M MAO, 0.23 mg of compound A (0.2 ml of a
11.5 mg in 10 ml of toluene solution) was added to the reactor. The
reactor was heated to 80.degree. C. the ethylene introduced (400
psi), and the reaction was allowed to run for 30 minutes, followed
by rapidly cooling and venting the system. After evaporation of the
solvent, 19.4 g of polyethylene was recovered (MW=343,700,
MWD=3.674).
Example 17
Polymerization--Compound A
[0098] The polymerization was performed in a stirred 100 ml
stainless steel autoclave which was equipped to perform
polymerizations at pressures up to 40,000 psi and temperatures up
to 300.degree. C. The reactor was purged with nitrogen and heated
to 160.degree. C. Compound A and alumoxane solutions were prepared
in separate vials. A stock solution was prepared by dissolving 26
mg of compound A in 100 ml of toluene. The compound A solution was
prepared by diluting 0.5 ml of the stock solution with 5.0 ml of
toluene. The alumoxane solution consisted of 2.0 ml of a 4% MAO
solution added to 5.0 ml of toluene. The compound A solution was
added to the alumoxane solution, then 0.43 ml of the mixed
solutions were transferred by nitrogen pressure into a
constant-volume injection tube. The autoclave was pressurized with
ethylene to 1784 bar and was stirred at 1500 rpm. The mixed
solutions were injected into the stirred reactor with excess
pressure, at which time a temperature rise of 4.degree. C. was
observed. The temperature and pressure were recorded continuously
for 120 seconds, at which time the contents of the autoclave were
rapidly vented into a receiving vessel. The reactor was washed with
xylene to recover any additional polymer remaining within. These
washings were combined with the polymer released when the autoclave
was vented to yield 0.7 g of polyethylene (MW=245,500,
MWD=2.257).
Example 18
Polymerization--Compound B
[0099] Using the general procedure described in Example 1, 400 ml
of toluene, 5.0 ml of 1.0 M MAO and 0.278 mg compound B (0.2 ml of
a 13.9 mg in 10 ml of toluene solution) was added to the reactor.
The reactor was heated to 80.degree. C. and the ethylene (60 psi)
was introduced into the system. The polymerization reaction was
limited to 10 minutes. The reaction was ceased by rapidly cooling
and venting the system. The solvent was evaporated off the polymer
by a stream of nitrogen. Polyethylene was recovered (9.6 g, MN
241,200, MWD=2.628).
Example 19
Polymerization--Compound C
[0100] Using the general procedures described in Example 1, 300 ml
of toluene, 4.0 ml of 1.0 M MAO and 0.46 mg compound C (0.4 ml of a
11.5 mg in 10 ml of toluene solution) was added to the reactor. The
reactor was heated to 80.degree. C. and the ethylene (60 psi) was
introduced into the system. The polymerization reaction was limited
to 30 minutes. The reaction was ceased by rapidly cooling and
venting the system. The solvent was evaporated off the polymer by a
stream of nitrogen. Polyethylene was recovered (1.7 g, MW=278,400,
MWD=2.142).
Example 20
Polymerization--Compound D
[0101] Using the general procedure described in Example 1, 400 ml
of toluene, 5.0 ml of 1.0 M MAO and 0.278 mg compound D (0.2 ml of
a 13.9 mg in 10 ml of toluene solution) was added to the reactor.
The reactor was heated to 80.degree. C. and the ethylene (60 psi)
was introduced into the system. The polymerization reaction was
limited to 30 minutes. The reaction was ceased by rapidly cooling
and venting the system. The solvent was evaporated off the polymer
by a stream of nitrogen. Polyethylene was recovered (1.9 g,
MW=229,700, MWD=2.618).
Example 21
Polymerization--Compound E
[0102] Using the general procedure described in Example 1, 300 ml
of hexane, 9.0 ml of 1.0 M MAO and 0.24 mg compound E (0.2 ml of a
12.0 mg in 10 ml of toluene solution) was added to the reactor. The
reactor was heated to 80.degree. C. and the ethylene (60 psi) was
introduced into the system. The polymerization reaction was limited
to 30 minutes. The reaction was ceased by rapidly cooling and
venting the system. The solvent was evaporated off the polymer by a
stream of nitrogen. Polyethylene was recovered (2.2 g, MW 258,200,
MWD=2.348).
Example 22
Polymerization--Compound E
[0103] The polymerization was carried out as in Example 1 with the
following reactor contents: 200 ml of toluene, 100 ml 1-butene, 9.0
ml of 1.0 M MAO and 2.4 mg of compound E (2.0 ml of a 12.0 mg in 10
ml of toluene solution) at 50.degree. C. The reactor was
pressurized with ethylene (65 psi), and the reaction was allowed to
run for 30 minutes, followed by rapidly cooling and venting the
system. After evaporation of the solvent, 1.8 g of an
ethylene-butene copolymer was recovered (MW=323,600, MWD=2.463,
33.5 SCB/1000C by IR technique).
Example 23
Polymerization--Compound F
[0104] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.242 mg of compound F (0.2 ml of a 12.1 mg in 10 ml of
toluene solution), 80.degree. C., 60 psi ethylene, 30 minutes. The
run provided 5.3 g of polyethylene (MW 319,900, MWD=2.477).
Example 24
Polymerization--Compound F
[0105] The polymerization was carried out as in Example 1 with the
following reactor conditions: 150 ml of toluene, 1.00 ml of
1-butene, 9.0 ml of 1.0 M MAO, 2.42 mg of compound F (2.0 ml of a
12.1 mg in 10 ml of toluene solution), 50.degree. C., 65 psi
ethylene, 30 minutes. The run provided 3.5 g of an ethylene-butene
copolymer (MW=251,300, MWD=3.341, 33.28 SCB/1000C by IR
technique).
Example 25
Polymerization--Compound G
[0106] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.29 mg of compound G (0.2 ml of a 14.5 mg in 10 ml of toluene
solution), 80.degree. C., 60 psi ethylene, 30 minutes. The run
provided 3.5 g of polyethylene (MW=237,300, MWD=2.549).
Example 26
Polymerization--Compound G
[0107] The polymerization was carried out in Example 1 with the
following reactor conditions: 150 ml of toluene, 100 ml of
1-butene, 7.0 ml of 1.0 M MAO, 2.9 mg of compound G (2.0 ml of a
14.5 mg in 10 ml of toluene solution), 50.degree. C., 65 psi
ethylene, 30 minutes. The run provided 7.0 g of an ethylene-butene
copolymer (MW=425,000, MWD 2.816, 27.11 SCB/1000C by IR
technique).
Example 27
Polymerization--Compound H
[0108] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.266 mg of compound H (0.2 ml of a 13.3 mg in 10 ml of
toluene solution), 80.degree. C., 60 psi ethylene, 30 minutes. The
run provided 11.1 g of polyethylene (MW=299,800, MWD=2.569).
Example 28
Polymerization--Compound H
[0109] The polymerization was tarried out as in Example 1 with the
following reactor conditions: 150 ml of toluene, 100 ml of
1-butene, 7.0 ml of 1.0 M MAO, 2.66 mg of compound H (2.0 ml of a
13.3 mg in 10 ml of toluene solution), 50.degree. C., 65 psi
ethylene, 30 minutes. The run provided 15.4 g of an ethylene-butene
copolymer (MW=286,600, MWD=2.980, 45.44 SCB/1000C by IR
technique).
Example 29
Polymerization--Compound I
[0110] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 MAO,
and 0.34 mg of compound I (0.2 ml of a 17.0 mg in 10 ml of toluene
solution) was added to the reactor. The reactor was heated to
80.degree. C., the ethylene was introduced (60 psi), and the
reaction was allowed to run for 30 minutes, followed by rapidly
cooling and venting the system. After evaporation of the solvent,
0.9 g of polyethylene was recovered (MW=377,000, MWD=1.996).
Example 30
Polymerization--Compound J
[0111] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.318 mg of compound J (0.2 ml of a 15.9 mg in 10 ml of
toluene solution), 80.degree. C., 60 psi ethylene, 30 minutes. The
run provided 8.6 g of polyethylene (MW=321,000, MWD=2.803).
Example 31
Polymerization--Compound J
[0112] The polymerization was carried out as in Example 1 with the
following reactor conditions: 150 ml of toluene, 100 ml of.
1-butene, 7.0 ml of 1.0 M MAO, 3.18 mg of Compound J (2.0 ml of a
15.9 mg in 10 ml of toluene solution), 50.degree. C., 65 psi
ethylene, 30 minutes. The run provided 11.2 g of an ethylene-butene
copolymer (MW=224,800, MWD=2.512, 49.57 SCB/1000C by IR technique,
55.4 SCB/1000C by NMR technique).
Example 32
Polymerization--Compound K
[0113] The polymerization was carried out as in Example 1 with the
following reactor conditions: 300 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.272 mg of compound K (0.2 ml of a 13.6 mg in 10 ml of
toluene solution), 80.degree. C., 60 psi ethylene, 30 minutes. The
run provided 26.6 g of polyethylene (MW=187,300, MWD=2.401).
Example 33
Polymerization--Compound K
[0114] The polymerization was carried out as in Example 1 with the
following reactor conditions: 150 ml of toluene, 100 ml of
1-butene, 7.0 ml of 1.0 M MAO, 2.72 mg of compound K (2.0 ml of a
13.6 mg in 10 ml of toluene solution), 50.degree. C., 65 psi
ethylene, 30 minutes. The run provided 3.9 g of an ethylene-butene
copolymer (MW=207,600, MWD=2.394, 33.89 SCB/1000C by IR
technique).
Example 34
Polymerization--Compound L
[0115] The polymerization was carried out as in Example 1 with the
following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M
MAO, 0.322 mg of compound L (0.2 ml of a 16.1 mg in 10 ml of
toluene solution), 80.degree. C., 60 psi ethylene, 30 minutes. The
run provided 15.5 g of polyethylene (MW=174,300, MWD=2.193).
Example 35
Polymerization--Compound A
[0116] The polymerization was carried out as in Example 1 with the
following reactor contents: 250 ml of toluene, 150 ml of 1-hexene,
7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg
in 10 ml of toluene solution) at 50.degree. C. The reactor was
pressurized with ethylene (65 psi), and the reaction was allowed to
run for 30 minutes, followed by rapidly cooling and venting the
system. After evaporation of the solvent, 26.5 g of an
ethylene-hexene copolymer was recovered (MW=222,800, MWD=3.373,
39.1 SCB/1000C by IR technique).
Example 36
Polymerization--Compound A
[0117] The polymerization was carried out as in Example 1 with the
following reactor contents: 300 ml of toluene, 100 ml of 1-octene,
7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg
in 10 ml of toluene solution) at 50.degree. C. The reactor was
pressurized with ethylene (65 psi), and the reaction was allowed to
run for 30 minutes, followed by rapidly cooling and venting the
system. After evaporation of the solvent, 19.7 g of an
ethylene-octene copolymer was recovered (MW 548,600, MWD 3.007,
16.5 SCB/1000C by .sup.13CNMR technique).
Example 37
Polymerization--Compound A
[0118] The polymerization was carried out as in Example 1 with the
following reactor contents: 300 ml of toluene, 100 ml of
4-methyl-1-pentene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A
(2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50.degree. C.
The reactor was pressurized with ethylene (65 psi), and the
reaction was allowed to run for 30 minutes, followed by rapidly
cooling and venting the system. After evaporation of the solvent,
15.1 g of an ethylene-4-methyl-1-pentene copolymer was recovered
(MW=611,800, MWD=1.683, 1.8 mole % determined by .sup.13C NMR).
Example 38
Polymerization--Compound A
[0119] The polymerization was carried out as in Example 1 with the
following reactor contents: 300 ml of toluene, 100 ml of a 2.2 M
norbornene in toluene solution, 7.0 ml of 1.0 M MAO and 2.3 mg of
compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at
50.degree. C. The reactor was pressurized with ethylene (65 psi),
and the reaction was allowed to run for 30 minutes, followed by
rapidly cooling and venting the system. After evaporation of the
solvent, 12.3 g of an ethylene-norbornene copolymer was recovered
(MW=812,600, MWD=1.711, 0.3 mole % determined by .sup.13C NMR).
Example 39
Polymerization--Compound A
[0120] The polymerization was carried out as in Example 1 with the
following reactor contents: 300 ml of toluene, 100 ml of
cis-1,4-hexadiene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A
(2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50.degree. C.
The reactor was pressurized with ethylene (65 psi), and the
reaction was allowed to run for 30 minutes, followed by rapidly
cooling and venting the system. After evaporation of the solvent,
13.6 g of an ethylene-cis-1,4-hexadiene copolymer was recovered
(MW=163,400, MWD=2.388, 2.2 mole % determined by .sup.13C NMR).
[0121] Table 2 summarizes the polymerization conditions employed
and the properties obtained in the product polymers as set forth in
Examples 1-34 above. TABLE-US-00002 TABLE 2 TRANSITION METAL
COMPOUND mmole EXP. DILUENT (TMC) ALUMOXANE MAO:TMC CO- NO. Type ml
Type mmole Type mmole (.times.10.sup.3) MONOMER MONOMER 4 Hexane
300 A 5.588 .times. 10.sup.-4 MAO 9 16.11 ethylene- 60 psi 1
Toluene 400 A 5.588 .times. 10.sup.-4 MAO 9 16.11 ethylene- 60 psi
2 Toluene 300 A 2.794 .times. 10.sup.-4 MAO 4.5 16.11 ethylene- 60
psi 3 Toluene 300 A 2.794 .times. 10.sup.-4 MAO 4.5 16.11 ethylene-
60 psi 16 Toluene 400 A 5.588 .times. 10.sup.-4 MAO 5 8.95
ethylene- 400 psi 12 Toluene 400 A.sup.a 5.588 .times. 10.sup.-4
MAO 5.02 8.98 ethylene- 60 psi 13 Toluene 400 A.sup.a,b 5.588
.times. 10.sup.-4 MAO 5.02 8.98 ethylene- 60 psi 14 Toluene 400
A.sup.a 5.588 .times. 10.sup.-4 MAO 0.2 0.47 ethylene- 60 psi 15
Toluene 400 A.sup.a 5.588 .times. 10.sup.-4 MAO 0.1 0.018 ethylene-
60 psi 18 Toluene 400 B 5.573 .times. 10.sup.-4 MAO 5 8.97
ethylene- 60 psi 19 Toluene 300 C 1.118 .times. 10.sup.-3 MAO 4
3.58 ethylene- 60 psi 20 Toluene 400 D 5.573 .times. 10.sup.-4 MAO
5 8.97 ethylene- 60 psi 21 Hexane 300 E 5.61 .times. 10.sup.-4 MAO
9 16.04 ethylene- 60 psi 23 Toluene 400 F 4.79 .times. 10.sup.-4
MAO 5 10.44 ethylene- 60 psi 25 Toluene 400 G 5.22 .times.
10.sup.-4 MAO 5 9.58 ethylene- 60 psi 27 Toluene 400 H 5.62 .times.
10.sup.-4 MAO 5 8.90 ethylene- 60 psi 29 Toluene 400 I 5.57 .times.
10.sup.-4 MAO 5 8.98 ethylene- 60 psi 30 Toluene 400 J 5.59 .times.
10.sup.-4 MAO 5 8.94 ethylene- 60 psi 32 Toluene 300 K 5.06 .times.
10.sup.-4 MAO 5 9.87 ethylene- 60 psi 34 Toluene 400 L 5.60 .times.
10.sup.-4 MAO 5 8.93 ethylene- 60 psi 5 Toluene 300 A 1.118 .times.
10.sup.-3 MAO 9 8.05 ethylene- propylene- 60 psi 200 ml 6 Toluene
200 A 2.235 .times. 10.sup.-3 MAO 9 4.03 ethylene- propylene- 60
psi 200 ml 7 Toluene 150 A 5.588 .times. 10.sup.-3 MAO 9 1.61
ethylene- 1-butene- 65 psi 100 ml 8 Toluene 100 A 5.588 .times.
10.sup.-3 MAO 9 1.61 ethylene- 1-butene- 65 psi 150 ml 9 Toluene
200 A 5.588 .times. 10.sup.-3 MAO 8 1.43 ethylene- 1-butene- 65 psi
50 ml 10 Hexane 200 A 5.588 .times. 10.sup.-3 MAO 8 1.43 ethylene-
1-butene- 65 psi 50 ml 11 Hexane 150 A 5.588 .times. 10.sup.-3 MAO
8 1.43 ethylene- 1-butene- 65 psi 100 ml 22 Toluene 200 E 5.61
.times. 10.sup.-3 MAO 9 1.60 ethylene- 1-butene- 65 psi 100 ml 24
Toluene 150 F 4.79 .times. 10.sup.-3 MAO 9 1.88 ethylene- 1-butene-
65 psi 100 ml 26 Toluene 150 G 5.22 .times. 10.sup.-3 MAO 7 1.34
ethylene- 1-butene- 65 psi 100 ml 28 Toluene 150 H 5.62 .times.
10.sup.-3 MAO 1.25 ethylene- 1-butene- 65 psi 100 ml 30 Toluene 150
J 5.59 .times. 10.sup.-3 MAO 7 1.25 ethylene- 1-butene- 65 psi 100
ml 32 Toluene 150 K 5.06 .times. 10.sup.-3 MAO 7 1.38 ethylene-
1-butene- 65 psi 100 ml 35 Toluene 250 A 5.588 .times. 10.sup.-3
MAO 7 1.25 ethylene- 1-hexene- 65 psi 100 ml 36 Toluene 300 A 5.588
.times. 10.sup.-3 MAO 7 1.25 ethylene- 1-octene- 65 psi 150 ml 37
Toluene 300 A 5.588 .times. 10.sup.-3 MAO 7 1.25 ethylene-
4-methyl- 65 psi 1-pentene- 100 ml 38 Toluene 300 A 5.588 .times.
10.sup.-3 MAO 7 1.25 ethylene- norbornene- 65 psi 100 ml 2.2 M 39
Toluene 300 A 5.588 .times. 10.sup.-3 MAO 7 1.25 ethylene- cis-1,4-
65 psi hexadiene 100 ml RXN RXN SCB/ CAT. ACTIVITY EXP. TEMP. TIME
YIELD 1000 C. G. POLYMER/MMOLE NO. .degree. C. HR. g. MW MWD NMR IR
TMC-MOLE 4 80 0.5 5.4 212,600 2.849 1.933 .times. 10.sup.4 1 80 0.5
9.2 257,200 2.275 3.293 .times. 10.sup.4 2 80 0.5 3.8 359,800 2.425
2.720 .times. 10.sup.4 3 40 0.5 2.4 635,000 3.445 1.718 .times.
10.sup.4 16 80 0.5 19.4 343,700 3.674 6.943 .times. 10.sup.4 12 80
0.5 3.4 285,000 2.806 1.217 .times. 10.sup.4 13 80 0.5 2.0 260,700
2.738 7.158 .times. 10.sup.3 14 80 0.5 1.1 479,600 3.130 3.937
.times. 10.sup.3 15 80 0.5 1.6 458,800 2.037 5.727 .times. 10.sup.2
18 80 0.17 9.6 241,200 2.628 1.034 .times. 10.sup.5 19 80 0.5 1.1
278,400 2.142 3.041 .times. 10.sup.3 20 80 0.5 1.9 229,700 2.618
6.819 .times. 10.sup.3 21 80 0.5 2.2 258,200 2.348 7.843 .times.
10.sup.3 23 80 0.5 5.3 319,900 2.477 2.213 .times. 10.sup.4 25 80
0.5 3.5 237,300 2.549 1.341 .times. 10.sup.4 27 80 0.5 11.1 299,800
2.569 3.950 .times. 10.sup.4 29 80 0.5 0.9 377,000 1.996 3.232
.times. 10.sup.3 30 80 0.5 8.6 321,000 2.803 3.077 .times. 10.sup.4
32 80 0.5 26.6 187,300 2.401 1.051 .times. 10.sup.5 34 80 0.5 15.5
174,300 2.193 5.536 .times. 10.sup.4 5 80 0.5 13.3 24,900 2.027
73.5 2.379 .times. 10.sup.4 6 50 0.5 6.0 83,100 2.370 75.7 5.369
.times. 10.sup.3 7 50 0.5 25.4 184,500 3.424 23.5 21.5 9.091
.times. 10.sup.3 8 50 0.5 30.2 143,400 3.097 30.8 26.5 1.081
.times. 10.sup.4 9 50 0.5 24.9 163,200 3.290 23.3 18.9 8.912
.times. 10.sup.3 10 50 0.5 19.5 150,600 3.510 12.1 12.7 6.979
.times. 10.sup.3 11 50 0.5 16.0 116,200 3.158 19.2 19.4 5.727
.times. 10.sup.3 22 50 0.5 1.8 323,600 2.463 33.5 6.417 .times.
10.sup.2 24 50 0.5 3.5 251,300 3.341 33.3 1.461 .times. 10.sup.3 26
50 0.5 7.0 425,000 2.816 27.1 2.682 .times. 10.sup.3 28 50 0.5 15.4
286,600 2.980 45.4 5.480 .times. 10.sup.3 30 50 0.5 11.2 224,800
2.512 49.6 4.007 .times. 10.sup.3 32 50 0.5 3.9 207,600 2.394 33.9
1.542 .times. 10.sup.3 35 50 0.5 26.5 222,800 3.373 39.1 9.485
.times. 10.sup.3 36 50 0.5 19.7 548,600 3.007 16.5 6.979 .times.
10.sup.3 37 50 0.5 15.1 611,800 1.683 1.8.sup.c 5.404 .times.
10.sup.3 38 50 0.5 12.3 812,600 1.711 0.3.sup.c 4.402 .times.
10.sup.3 39 50 0.5 13.6 163,400 2.388 2.2.sup.c 4.868 .times.
10.sup.3 .sup.aCompound A was preactivated by dissolving the
compound in solvent containing MAO. .sup.bPreincubation of
activated compound A was for one day. .sup.cMole % comonomer.
[0122] It may be seen that the requirement for the alumoxane
component can be greatly diminished by premixing the catalyst with
the alumoxane prior to initiation of the polymerization (see
Examples 12 through 15).
[0123] By appropriate selection of (1) the Group IV B transition
metal component for use in the catalyst system; (2) the type and
amount of alumoxane used; (3) the polymerization diluent type and
volume; and (4) reaction temperature; (5) reaction pressure, one
may tailor the product polymer to the weight average molecular
weight value desired while still maintaining the molecular weight
distribution to a value below about 4.0.
[0124] The preferred polymerization diluents for practice of the
process of the invention are aromatic diluents, such as toluene, or
alkanes, such as hexane.
[0125] The resins that are prepared in accordance with this
invention can be used to make a variety of products including films
and fibers.
[0126] The invention has been described with reference to its
preferred embodiments. Those of ordinary skill in the art may, upon
reading this disclosure, appreciate changes or modifications which
do not depart from the scope and spirit of the invention as
described above or claimed hereafter.
* * * * *