Back to EveryPatent.com
United States Patent |
5,168,111
|
Canich
|
*
December 1, 1992
|
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 M. (Webster, TX)
|
Assignee:
|
Exxon Chemical Patents Inc. (Linden, NJ)
|
[*] Notice: |
The portion of the term of this patent subsequent to June 25, 2008
has been disclaimed. |
Appl. No.:
|
676690 |
Filed:
|
March 28, 1991 |
Intern'l Class: |
C08F 004/44 |
Field of Search: |
526/129,160
|
References Cited
U.S. Patent Documents
5026798 | Jun., 1991 | Canich | 526/127.
|
Foreign Patent Documents |
0416815 | Mar., 1991 | EP.
| |
WO87/03887 | Feb., 1987 | WO.
| |
Other References
"Gmelins Handbuch der Anorganischen Chemie", vol. 10; "Zirkonium-Organische
Verbindungen", vol. 11; "Hafnium-Organische Verbindungen", 1973, Verlag
Chemie, GmbH, Weinheim, DE pp. 4-25, vol. 10; pp. 3-7, vol. 11.
Chemische Berichte, vol. 123, No. 8, Aug. 1990, pp. 1649-1651, Weinheim,
DE; J. Okuda: "Synthesis and Complexation of Linked Cyclopentadienyl-Amido
Ligands" Whole document.
Organometallics, vol. 9, Sep. 1990, pp. 869-871, American Chemical Society,
Washington, DC, US; P. J. Shapiro et al.:
"[(N5-C5Me4)Me2Sl(n1-NCMe3)(PMe3)(ScH]2: A Unique Example of a
Single-Component Alpha-Olefin Polymerization Catalyst" Whole Document.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Wu; David
Attorney, Agent or Firm: Kurtzman; Myron B., Butts; Evan K.
Parent Case Text
This is a division of application Ser. No. 533,245, filed June 4, 1990, now
U.S. Pat. No. 5,055,438, which is a continuation-in-part of Ser. No.
406,945, filed Sept. 13, 1989, now abandoned.
Claims
I claim:
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 IV B transition metal component of the formula:
##STR5##
wherein M is Zr, Hf or Ti; (C.sub.5 H.sub.5-y-x R.sub.x) is a
cyclopentadienyl ring which is substituted with from zero to five 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 are 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 Period Table
of Elements and halogen radicals or (C.sub.5 H.sub.5-y-x R.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;
(JR'.sub.z-1-y) is a heteroatom ligand in which J is an element with a
coordination number of two from Group VI A of the Period 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 atoms, and "z" is the coordination number of the
element J;
each Q is, independently any univalent anionic ligand or two Q's are a
divalent anionic chelating agent;
"y" is 0 or 1 when w is greater than 0; y is 1 when w is o, when "y" is 1,
B is a covalent bridging group containing a Group IV A or V A element;
L is a Lewis base where "w" denotes a number from 0 to 3; and
(B) an alumoxane.
2. The process of claim 1 wherein the heteroatom ligand group J element is
nitrogen, phosphorous, oxygen or sulfur.
3. The process of claim 1 wherein Q is a halogen or hydrocarbyl radical.
4. The process of claim 2 wherein the heteroatom ligand group J element is
nitrogen.
5. The process of claim 1 wherein M is zirconium or hafnium.
6. The process of claim 1 wherein the mole ratio of Al:M is from 10:1 to
about 20,000:1.
7. The process of claim 1 wherein Q is independently halogen, hydride, or a
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.5 H.sub.4-x
R.sub.x) or both together are an alkylidene or a cyclometallated
hydrocarbyl.
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 1 wherein the polymerization conducted is
homopolymerization.
10. The process of claim 8 wherein the polymerization conducted is
copolymerization.
11. The process of claim 8 wherein alpha-olefin is selected from propylene,
butene, styrene, diolefins, and combinations thereof.
12. The process of claim 11 wherein 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 conducted is
selected from slurry, solution, suspension, or bulk phase polymerization.
15. The process of claim 13 or 14 wherein the process is employed in
series.
16. The process of claim 1 wherein the polymer produced has "molecular
weight distribution to a value" below about 4.
Description
FIELD OF THE INVENTION
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
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.
Traditional Ziegler-Natta catalysts systems--a transition metal compound
cocatalyzed by an aluminum alkyl--are capable of producing polyolefins
having a high molecular weight but a board molecular weight distribution.
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.
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 is generally too low to be of any commercial interest.
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.
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.
More recently International Publication No. WO 87/03887 has appeared which
describeds 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 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 soley with reference to transition metal compounds which
are bis(cyclopentadienyl) Group IV B transition metal compounds.
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 catalystic 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.
A need still exists for discovering catalysts systems that permit the
production of higher molecular weight polyolefins and desirably with a
narrow molecular weight distribution.
SUMMARY OF THE INVENTION
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.
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);
(C.sub.5 H.sub.5-y-x R.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.5 .sub.5-y-x R.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;
(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;
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.5
H.sub.5-y-x R.sub.x), or both Q together may be an alkylidene or a
cyclometallated hydrocarbyl or any other divalent anionic chelating
ligand.
"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;
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##
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.
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.
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
Catayst Component
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);
(C.sub.5 H.sub.5-y-x R.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.5 .sub.5-y-x R.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;
(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 J;
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.5
H.sub.5-y-x R.sub.x), or both Q together may be be an alkylidene or a
cyclometallated hydrocarbyl or any other divalent anionic chelating
ligand;
"y+ is 0 or 1 when w is greater than 0, and y is 1 when w=0; when "y" is 1B
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".
Examplary 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-methylphenoixde.
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 alkyldience
radicals for both Q together are methlidene, 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".
Suitable hydrocarbyl and substituded 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.5
H.sub.5-y-x R.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.5 H.sub.5-y-x
R.sub.x).
Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be
substituted as an R' group for at least one hydrogen atom in the
heteroatomj 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).
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 dichoride,
dimethylsily-tertk-butylcyclopentadienyl-tert-butylamido zirconium
dichloride, dimethylsilyl-tert-butylcyclopentadienyl hafnium dichloride,
dimethylsilyltrimethylsilylcyclopentadienyl-tert-butylamido zirconium
dichloride, dimethylsilyltetramethylcyclopentadienylphenylamido zirconium
dichloride, dimethylsilyltetramethylcyclopentadienylphenylamido hafnium
chloride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido
zirconium dichloride,
methylphenylsilytetranethylcyclopentadienyl-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 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.2 Si(Me.sub.4 C.sub.5)(N-t-Bu)ZrCl.sub.2 has greater steric
requirements than the phenyl group in Me.sub.2 Si(Me.sub.4
C.sub.5)(NPh)ZrCl.sub.2.ET.sub.2 O thereby not permitting ether
coordination in the former compound. Similarly, due to the decreased
steric bulk of the trimethylsilylcyclopentadienyl group in [Me.sub.2
Si(Me.sub.3 SiC.sub.5 H.sub.3)(N-t-Bu)ZrCl.sub.2 ].sub.2 versus that of
the tetramethylcyclopentadienyl group in Me.sub.2 Si(Me.sub.4
C.sub.5)(N-t-Bu)ZrCl.sub.2, the former compound is dimeric and the latter
is not.
TABLE 1
__________________________________________________________________________
##STR4##
B (when y = 1) (C.sub.5 H.sub.5-y-x R.sub.x)
(JR'.sub.x-1-y)
Q M
__________________________________________________________________________
dimethylsilyl cyclopentadienyl .sub.-t-butylamido
hydride zirconium
diethylsilyl methylcyclopentadienyl
phenylamido chloro hafnium
di- -n-propylsilyl
1,2-dimethylcyclopentadienyl
p- -n-butylphenylamido
methyl titanium
diisopropylsilyl 1,3-dimethylcyclopentadienyl
cyclohexylamido
ethyl
di- -n-butylsilyl
imdenyl perflurophenylamido
phenyl
di- .sub.-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- .sub.-t-butylphenethylsilyl)
-n-octylcyclopentadienyl
benzylamido -n-butyl
-n-hexylmethylsilyl
.beta.-phenylpropylcyclopentadienyl
.sub.-t-butylphosphido
amyl
cyclopentamethylenesilyl
tetrahydroimdenyl
ethylphosphido
isoamyl
cyclotetramethylenesilyl
propylcyclopentadienyl
phenylphosphido
hexyl
cyclotrimethylenesilyl
.sub.-t-butylcyclopentadienyl
cyclohexylphosphido
isobutyl
dimethylgermanyl benzylcyclopentadienyl
exo (when y = 1)
heptyl
diethylgermanyl diphenylmethylcyclopentadienyl
sulfido (when y = 1)
octyl
phenylamido trimethylgermylcyclopentadienyl
methoxide (when y = 0)
nonyl
.sub.-t-butylamido
trimethylstannylcyclopentadienyl
ethoxide (when y = 0)
decyl
methylamido triethylplumbylcyclopentadienyl
methylthio cetyl
.sub.-t-butylphosphido
trifluromethylcyclopentadienyl
(when y = 0)
methoxy
ethylphosphido trimethylsilylcyclopentadienyl
ethylthio (when y = 0)
ethoxy
phenylphosphido pentamethylcyclcopentadienyl propoxy
methylene (when y = 0) butoxy
dimethylmethylene
fluorenyl phenoxy
diethylmethylene octahydrofluorenyl dimethylamido
ethylene diethylamido
dimethylethylene methylethylamido
diethylethylene di- .sub.-t-butylamido
dipropylethylene diphenylamido
propylene diphenylphosphido
dimethylpropylene dicyclohexylphosphido
diethylpropylene dimethylphosphido
1,1-dimethyl-3,3-dimethylpropylene methylidene (both Q)
tetramethyldisiloxane ethylidene (both Q)
1,1,4,4-tetramethyldisilylethylene propylidene (both Q)
ethyleneglycol
__________________________________________________________________________
dianion
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 product is then reacted with an alkyl lithium reagent
whereupon the labile hydrogen atoms, at the carbon atom of the
cyclopentadienyl compound at the nitrogen atom of the amine moiety
convalently bound to the substitutent 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.
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, ethylphenylsily,
diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of
the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl
bridged compounds.
Suitable Group IV B transition metal compounds which are illustrative o 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-butylphosphinomethyletyl hafnium;
cyclopentadienyl-2-methylbutoxide dimethyl titanium.
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.
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. As 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 moreof
R.sup.2-5 could be halide.
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.
Suitable alumoxanes which may be utilized in the catalyst systems of this
invention are those prepared by the hydrolysis of the alkylaluminum
reagnet; such as trimethylaluminum, triethyaluminum, tripropylaluminum;
triisobutylaluminum, dimethylaluminumchloride, diisobutyaluminumchloride,
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
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.
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.
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 bout 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.
The catalyst system ingredients--that is, the Group IV B transition metal,
the alumoxane, and polymerization diluent can be added to the reaction
vessel rapdicly or slowly. The temperature maintained during the contact
of the catalyst components can vary widely, such as, for example, from
-10.degree. C. 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. C. to
100.degree. C., most preferably about 25.degree. C.
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
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.
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 high .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 nozzle 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 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 rate of these
components to the reactor.
EXAMPLES
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 measrued using a Waters 150 gel permeation
chromatograph equipped with a differential refractive index (DRI) detector
and a Chromatic 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, 304
and 805 were used. This technique is discussed in "Liquid Chromatography
of Polymers and Related Materials III", J. Cazes edit, 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
ethyle-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 100 computer.
The following examples are intended to illustrate specific embodiments of
the invention and are not intended to limit the scope of the invention.
All procedures were preformed 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.5 Me.sub.4 include C. M.
Fendrick et al. Organometallics, 3, 180 (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 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 VI B Transition Metal Components
Example A
Compound A: Part 1. Me.sub.4 HC.sub.5 Li (10.0 g. 0.078 mol) was slowly
added to a Me.sub.2 SiCl.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.4 HC.sub.5 SiMe.sub.2 Cl (15.34 g, 0.071 mol)
was recovered as a pale yellow liquid.
Part 2. Me.sub.4 HC.sub.5 SiMe.sub.2 Cl (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 (.about.100 ml) was
added to precipitate out the LiCl. The mixture was filtered through
Celite. The solvent was removed from the filtrate. Me.sub.2 Si(Me.sub.4
HC.sub.5)(HN-t-Bu) (11.14 g, 0.004 mol) was isolated as a pale yellow
liquid.
Part 3. Me.sub.2 Si(Me.sub.4 HC.sub.5)(HN-t-Bu) (11.14 g, 0.044 mol) was
diluted with .about.100 ml Et.sub.2 O. 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.2 Si(Me.sub.4 C.sub.5)(N-t-Bu)]Li.sub.2,
was washed with several small portions of ether, than vacuum dried.
Part 4. [Me.sub.2 Si(Me.sub.4 C.sub.5)(N-t-Bu)]Li.sub.2 (3.0 g, 0.011 mol)
was suspended in .about.150 ml Et.sub.2 O. 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. Me.sub.2
Si(Me.sub.4 C.sub.5)(N-t-Bu)ZrCl.sub.2 (1.07 g, 0.0026 mole) was
recovered. Additional Me.sub.2 Si(Me.sub.4 C.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
Compound B: The same procedure of Example A for prepareing 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.2 Si(Me.sub.4
C.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.2 Si(Me.sub.4 C.sub.5)(N-t-Bu)HfCl.sub.2
(0.98 g, 0.0020 mol was produced.
Example C
Compund C: Part 1. Me.sub.2 SiCl.sub.2 (7.5 ml, 0.062 mol) was diluted with
.about.30 ml thf. A t-BuH.sub.4 C.sub.5 Li 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.4 C.sub.5
SiMe.sub.2 Cl (10.5 g. 0.048 mol).
Part 2. To a thf solution of LiHN-t-Bu (3.83 g, 0.048 mol, .about.125 ml),
t-BuH.sub.4 C.sub.5 SiMe.sub.2 Cl (10.4 g, 0.048) 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.2 Si(t-BuH.sub.4 C.sub.5)(MH-t-Bu) (11.4 g, 0.045 mol).
Part 3. Me.sub.2 Si(t-BuH.sub.4 C.sub.5%)(NH-t-Bu) (11.4 g, 0.045 mol) was
diluted with .about.100 ml Et.sub.2 O. 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 -196.degree. C., leaving behind a
pale yellow solid, [Me.sub.2 Si(t-BuH.sub.3 C.sub.5)(N-t-Bu)]Li.sub.2
(11.9 g, 0.045 mol).
Part 4. [Me.sub.2 Si(t-BuH.sub.3 C.sub.5)(N-t-Bu)]Li.sub.2 (3.39 g, 0.013
mol) was suspended in .about.100 ml Et.sub.2 O. 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.2 Si(t-BuH.sub.3 C.sub.5)(N-t-Bu)ZrCl.sub.2 (2.43 g, 0.0059 mol)
was isolated.
Example D
Compound D: The same procedure of Example C for preparing compound C was
followed with the exeception of the use of HfCl.sub.4 in Part 4. Thus,
when [Me.sub.2 Si(t-BuH.sub.3 C.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.2 Si(t-BuH.sub.3 C.sub.5)(N-t-Bu)HfCl.sub.2 (1.86
g, 0.0037 mol) was produced.
Example E
Compound E: Part 1. Me.sub.2 SiCl.sub.2 (7.0 g, 0.054 mol) was diluted with
.about.100 ml of ether. Me.sub.3 SiC.sub.5 H.sub.4 Li (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.2 Si(Me.sub.3 SiC.sub.5 H.sub.4)Cl (8.1 g,
0.035 mol) as a pale yellow liquid.
Part 2. Me.sub.2 Si(Me.sub.3 SiC.sub.5 H.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.2 Si(Me.sub.3 SiC.sub.5
H.sub.3)(N-t-Bu)].about.3/4ET.sub.2 O and unreacted MeLi which was not
removed from the solid.
Part 4. Li.sub.2 [Me.sub.2 Si(Me.sub.3 SiC.sub.5
H.sub.3)(N-t-Bu)].multidot.3/4Et.sub.2 O (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.2 Si(Me.sub.3
SiC.sub.5 H.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
Compound F: Part 1. Me.sub.4 HC.sub.5 SiMe.sub.2 Cl was prepared as
described in Example A for the preparation of compound A, Part 1.
Part 2. LiHNPh (4.6 g, 0.0462 mol) was dissolved in .about.100 ml of thf.
Me.sub.4 HC.sub.5 SiMeCl (10.0 g, 0.0466 mol) was slowly added. The
mixture was allowed to stir overnight. The thf was removed via a vacuum.
Petroleium 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.2 Si(Me.sub.4 HC.sub.5)(NHPh) (10.5g,
0.0387 mol).
Part 3. Me.sub.2 Si(Me.sub.4 HC.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.2 Si(Me.sub.4
C.sub.5)(NPh).multidot.3/4Et.sub.2 O (11.0 g), was filtered off and was
washed with ether.
Part 4. Li.sub.2 [Me.sub.2 Si(Me.sub.2 Si(Me.sub.4
C.sub.5)(NPh).multidot.3/4Et.sub.2 O (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
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 pentane. Me.sub.2
Si(Me.sub.4 C.sub.5)(NPh)ZrCl.sub.2 .multidot.Et.sub.2 O was recovered as
a pale yellow solid (1.89 g).
Example G
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
NrCl.sub.4 in Part 4. Thus, when Li.sub.2 [Me.sub.2 Si(Me.sub.4
C.sub.5)(Nph)].multidot.3/4Et.sub.2 O (2.0 g, 0.0059 mol) and HfCl.sub.4
(1.89 g, 0.0059 mol) were used, Me.sub.2 Si(Me.sub.4
C.sub.5)(NPh)HfCl.sub.2 .multidot.1/2Et.sub.2 O (1.70 g) was produced.
Example H
Compound H: Part 1. MePhSiCl.sub.2 (14.9 g, 0.078 mol) was diluted with
.about.250 ml of thf. Me.sub.4 C.sub.5 MLi (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.4 C.sub.5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow
viscous liquid.
Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in .about.100 ml of
thf. MePhSi(Me.sub.4 C.sub.5 H)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.4 C.sub.5 H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as
an extremely viscous liquid.
Part 3. MePhSi(Me.sub.4 C.sub.5 H)(NH-t-Bu) (16.6 g, 0.053 mol) was diluted
with 18 100 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.4 C.sub.5)(N-t-Bu)].multidot.3/4Et.sub.2 O.
Part 4. Li.sub.2 [MePhSi(Me.sub.4 C.sub.5)(N-t-Bu)].multidot.3/4Et.sub.2 O
(5.0 g, 0.0131 mol) was suspended in .about.100 ml of Et.sub.2 O.
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 reactiojn 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.4
C.sub.5)(N-t-Bu)ZrCl.sub.2, was 3.82 g (0.0081 mol).
Example I
Compound I: Li.sub.2 [MePhSi(Me.sub.4
C.sub.5)(N-t-Bu)].multidot.3/4Et.sub.2 O was prepared as described in
Example H for the preparation of compound H, Part 3.
Part 4. Li.sub.2 [MePhSi(Me.sub.4 C.sub.5)(N-t-Bu)].multidot.3/4Et.sub.2 O
(5.00 g, 0.0131 mol) was suspended in .about.100 ml of Et.sub.2 O.
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.4 C.sub.5)(N-t-Bu)HfCl.sub.2 was recovered (3.54 g, 0.0058
mole).
Example J
Compound J: MePhSi(Me.sub.4 C.sub.5)(N-t-Bu)NfMe.sub.2 was prepared by
adding a stoichiometric amount of MeLi (1.4 M in ether) to MePhSi(Me.sub.4
C.sub.5)(N-t-Bu)HfCl.sub.2 suspended in ether. The white solid could be
isolated in near quantitative yield.
Example K
Compound K: Part 1. Me.sub.4 C.sub.5 SiMe.sub.2 Cl was prepared as
described in Example A for the preparation of compound A, Part 1.
Part 2. Me.sub.4 C.sub.5 SiMe.sub.2 Cl (10.0 g, 0.047 mol) was diluted with
.about.25 ml Et.sub.2 O. LiHNC.sub.5 H.sub.4 p-n-Bu.multidot.1/10Et.sub.2
O (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.2 Si(Me.sub.4 C.sub.5 H)(NHC.sub.6 H.sub.4 p-n-Bu) (12.7 g,
0.039 mol).
Part 3. Me.sub.2 Si(Me.sub.4 C.sub.5 H)(HNC.sub.6 H.sub.4 p-n-Bu) (12.7 g,
0.039 mol) was diluted with .about.50 ml of Et.sub.2 O. 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.2 O
producing Li.sub.2 [Me.sub.2 Si(Me.sub.4 C.sub.5)(NH.sub.6 H.sub.4
p-n-Bu)].multidot.3/4Et.sub.2 O as a white solid (13.1 g, 0.033 mol).
Part 4. Li.sub.2 [Me.sub.2 Si(Me.sub.2 Si(Me.sub.4 C.sub.5)(NC.sub.6
H.sub.4 p-n-Bu)].multidot.3/4Et.sub.2 O (3.45 g, 0.0087 mol) was suspended
in .about.50 ml of Et.sub.2 O. 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.2 Si(me.sub.4 C.sub.5)(NC.sub.6 H.sub.4
-p-n-Bu)ZrCl.sub.2 .multidot.2/3Et.sub.2 O (4.2 g).
Example L
Compound L: Li.sub.2 [Me.sub.2 Si(Me.sub.4 C.sub.5)(NH.sub.6 H.sub.4
-p-n-Bu)].multidot.3/4Et.sub.2 O was prepared as described in Example K
for the preparation of compound K, Part. 3.
Part 4. Li.sub.2 [Me.sub.2 Si(Me.sub.4 C.sub.5)(NC.sub.6 H.sub.4
-p-n-Bu)].multidot.3/4Et.sub.2 O (3.77 g, 0.0095 mol) was suspended in
.about.50 ml of Et.sub.2 O. 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.2 Si(Me.sub.4
C.sub.5)(NC.sub.6 H.sub.4 p-n-Bu)HfCl.sub.2 (1.54 g, 0.0027 mol).
EXAMPLES 1-34 OF POLYMERIZATION
EXAMPLE 1
Polymerization--Compound A
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,
transitions 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, MW=257,200, MWD=2.275).
EXAMPLE 2
Polymerization--Compound A
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, MW=359,800, MWD=2.425).
Example 3
Polymerization-Compound A
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
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
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
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 at 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
Using the same reactor design and general procedures 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.13 C NMR and 21.5 SCB/1000C
by IR).
Example 8
Polymerization--Compound A
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.13 C NMR and 26.5 SCB/1000C by IR).
Example 9
Polymerization--Compound A
The polymerization was carried out as in Example 7 except with the
following changes: 200 ml of toluene, 8.0 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.13 C NMR and 18.9 SCB/1000C by IR).
Example 10
Polymerization--Compound A
The polymerization was carried out as in Example 9 except for the
replacement of 200 ml of hexane. Anm ethylene-butene copolymer was
recovered (19.5 g, MW=150,600, MWD =3.510, 12.1 SCB/1000 C by .sup.13 C
NMR and 12.7 SCB/1000C by IR).
Example 11
Polymerization--Compound A
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.13 C NMR and 10.4 SCB/1000C by IR).
Example 12
Polymerization--Compound A
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
The 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
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 reator. The reactor was heated to
80.degree. C., the ethylene waas introduced (60 psi), and the reaction was
allowed to run for 30 minutes, followed 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
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
evporation of the solvent, 1.6 g of polyethylene was recovered
(MW=458,800, MWD=2.037).
Example 16
Polymerization--Compound A
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
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 continously 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
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, MW=241,200, MWD=2.628).
Example 19
Polymerization--Compound C
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
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
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
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
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
The polymerization was carried out as in Example 1 with the following
reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 9.0 ml of 1.0 M
MAO, 2.42 mg of compounds 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
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
The polymerization was carried out as in Example 1 with the following
reactor conditions: 150 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
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
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 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
The polymerization was carried out as in Example 1 with the following
reactor conditions: 400 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
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
The polymerization was carried out as in Example b 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
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
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 234
Polymerization--Compound L
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=174,300MWD=2.193).
Example 35
Polymerization--Compound A
The polymerization was carried out as in Example 1 with the following
reactor contents: 250 ml of toluene, 150 ml of 1-hexane, 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=222,8000,
MWD=3.373, 39.1 SCB/1000C by IR technique).
Example 36
Polymerization--Compound A
The polymerization was carried out as in Example b 1 with the following
reactor conditions: 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 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, HWD=3.007, 16.5
SCB/1000C by .sup.13 C NMR technique).
Example 37
Polymerization--Compound A
The polymerization was carried out as in Example 1 with the following
reactor conditions: 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 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.13 C NMR).
Example 38
Polymerization--Compound A
The polymerization was carried out as in Example 1 with the following
reactor conditions: 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.13 C NMR).
Example 239
Polymerization--Compound A
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.13 C NMR).
Table 2 summarizes the polymerization conditions employed and the
properties obtained in the product polymers as set forth in Examples 1-34
above.
TABLE 2
TRANSITION METAL COMPOUND mmole RXN. RXN. SCB/
CAT. ACTIVITY EXP. DILUENT (TMC) ALUMOXANE MAO:TMC TEMP. TIME YIELD
1000 C G. POLYMER/ NO. Type ml Type mmole Type mmole (.times. 10.sup.3)
MONOMER COMONOMER .degree.C. HR. g. MW MWO NMR IR MMOLE TMC-HOUR
4 Hexane 300 A 5.588 .times. 10.sup.-4 MAO 9 16.11 ethylene- 80 0.5
5.4 212,600 2.849 1.933 .times. 10.sup.4 60 psi 1 Toluene 400
A 5.588 .times. 10.sup.-4 MAO 9 16.11 ethylene- 80 0.5 9.2 257,200
2.275 3.293 .times. 10.sup.4 60 psi 2 Toluene 300 A 2.794
.times. 10.sup.-4 MAO 4.5 16.11 ethylene- 80 0.5 3.8 359,800 2.425
2.720 .times. 10.sup.4 60 psi 3 Toluene 300 A 2.794 .times.
10.sup.-4 MAO 4.5 16.11 ethylene- 40 0.5 2.4 635,000 3.445 1.718
.times. 10.sup.4 60 psi 16 Toluene 400 A 5.588 .times. 10.sup.-4
MAO 5 8.95 ethylene- 80 0.5 19.4 343,700 3.674 6.943 .times. 10.sup.4
400 psi 12 Toluene 400 A.sup.a 5.588 .times. 10.sup.-4 MAO 5.02
8.98 ethylene- 80 0.5 3.4 285,000 2.808 1.217 .times. 10.sup.4
60 psi 13 Toluene 400 A.sup.a,b 5.588 .times. 10.sup.-4 MAO 5.02 8.98
ethylene- 80 0.5 2.0 260,700 2.738 7.158 .times. 10.sup.3 60
psi 14 Toluene 400 A.sup.a 5.588 .times. 10.sup.-4 MAO 0.26 0.47
ethylene- 80 0.5 1.1 479,600 3.130 3.937 .times. 10.sup.3 60
psi 15 Toluene 400 A.sup.a 5.588 .times. 10.sup.-4 MAO 0.1 0.018
ethylene- 80 0.5 1.6 458,800 2.037 5.727 .times. 10.sup.2 60
psi 18 Toluene 400 B 5.573 .times. 10.sup.-4 MAO 5 8.97 ethylene- 80
0.17 9.6 241,200 2.628 1.034 .times. 10.sup.5 60 psi 19
Toluene 300 C 1.118 .times. 10.sup.-3 MAO 4 3.58 ethylene- 80 0.5 1.7
278,400 2.142 3.041 .times. 10.sup.3 60 psi 20 Toluene 400 D
5.573 .times. 10.sup.-4 MAO 5 8.97 ethylene- 80 0.5 1.9 229,700 2.618
6.819 .times. 10.sup.3 60 psi 21 Hexane 300 E 5.61 .times.
10.sup.-4 MAO 9 16.04 ethylene- 80 0.5 2.2 258,200 2.348 7.843
.times. 10.sup.3 60 psi 23 Toluene 400 F 4.79 .times. 10.sup.-4
MAO 5 10.44 ethylene- 80 0.5 5.3 319,900 2.477 2.213 .times. 10.sup.4
60 psi 25 Toluene 400 G 5.22 .times. 10.sup.-4 MAO 5 9.58
ethylene- 80 0.5 3.5 237,300 2.549 1.341 .times. 10.sup.4 60
psi 27 Toluene 400 H 5.62 .times. 10.sup.-4 MAO 5 8.90 ethylene- 80 0.5
11.1 299,800 2.569 2.950 .times. 10.sup.4 60 psi 29 Toluene
400 I 5.57 .times. 10.sup.-4 MAO 5 8.98 ethylene- 80 0.5 0.9 377,000
1.996 3.232 .times. 10.sup.3 60 psi 30 Toluene 400 J 5.59
.times. 10.sup.-4 MAO 5 8.94 ethylene- 80 0.5 8.6 321,000 2.803 3.077
.times. 10.sup.4 60 psi 32 Toluene 300 K 5.06 .times. 10.sup.-4
MAO 5 9.87 ethylene- 80 0.5 26.6 187,300 2.401 1.051 .times. 10.sup.5
60 psi 34 Toluene 400 L 5.60 .times. 10.sup.-4 MAO 5 8.93
ethylene- 80 0.5 15.5 174,300 2.193 5.536 .times. 10.sup.4 60
psi 5 Toluene 300 A 1.118 .times. 10.sup.-3 MAO 9 8.05 ethylene-
propylene- 80 0.5 13.3 24,900 2.027 73.5 2.379 .times. 10.sup.4
60 psi 200 ml 6 Toluene 200 A 2.235 .times. 10.sup.-3 MAO 9 4.03
ethylene- propylene- 50 0.5 6.0 83,100 2.370 75.7 5.369 .times.
10.sup.3 60 psi 200 ml 7 Toluene 150 A 5.588 .times. 10.sup.-3
MAO 9 1.61 ethylene- 1-butene- 50 0.5 25.4 184,500 3.424 23.5 21.5 9.091
.times. 10.sup.3 65 psi 100 ml 8 Toluene 100 A 5.588 .times.
10.sup.-3 MAO 9 1.61 ethylene- 1-butene- 50 0.5 30.2 143,400 3.097 30.8
26.5 1.081 .times. 10.sup.4 65 psi 150 ml 9 Toluene 200 A 5.588
.times. 10.sup.-3 MAO 8 1.43 ethylene- 1-butene- 50 0.5 24.9 163,200
3.290 23.3 18.9 8.912 .times. 10.sup.3 65 psi 50 ml 10 Hexane
200 A 5.588 .times. 10.sup.-3 MAO 8 1.43 ethylene- 1-butene- 50 0.5 19.5
150,600 3.510 12.1 12.7 6.979 .times. 10.sup.3 65 psi 50 ml 11
Hexane 150 A 5.588 .times. 10.sup.-3 MAO 8 1.43 ethylene- 1-butene- 50
0.5 16.0 116,200 3.158 19.2 19.4 5.727 .times. 10.sup.3 65 psi
100 ml 22 Toluene 200 E 5.61 .times. 10.sup.-3 MAO 9 1.60 ethylene-
1-butene- 50 0.5 1.8 323,600 2.463 33.5 6.417 .times. 10.sup.2
65 psi 100 ml 24 Toluene 150 F 4.79 .times. 10.sup.-3 MAO 9 1.88
ethylene- 1-butene- 50 0.5 3.5 251,300 3.341 33.3 1.461 .times.
10.sup.3 65 psi 100 ml 26 Toluene 150 G 5.22 .times. 10.sup.-3
MAO 7 1.34 ethylene- 1-butene- 50 0.5 7.0 425,000 2.816 27.1 2.682
.times. 10.sup.3 65 psi 100 ml 28 Toluene 150 H 5.62 .times.
10.sup.-3 MAO 7 1.25 ethylene- 1-butene- 50 0.5 15.4 286,600 2.980 45.4
5.480 .times. 10.sup.3 65 psi 100 ml 30 Toluene 150 J 5.59
.times. 10.sup.-3 MAO 7 1.25 ethylene- 1-butene- 50 0.5 11.2 224,800
2.512 49.6 4.007 .times. 10.sup.3 65 psi100 ml 32 Toluene 150 K
5.06 .times. 10.sup.-3 MAO 7 1.38 ethylene- 1-butene- 50 0.5 3.9 207,600
2.394 33.9 1.542 .times. 10.sup.3 65 psi 100 ml 35 Toluene 250
A 5.588 .times. 10.sup.- 3 MAO 7 1.25 ethylene- 1-butene- 50 0.5 26.5
222,800 3.373 39.1 9.485 .times. 10.sup.3 65 psi 150 ml 36
Toluene 300 A 5.588 .times. 10.sup.-3 MAO 7 1.25 ethylene- 1-octene- 50
0.5 19.7 548,600 3.007 16.5 6.979 .times. 10.sup.3 65 psi 100
ml 37 Toluene 300 A 5.588 .times. 10.sup.-3 MAO 7 1.25 ethylene-
4-methyl- 50 0.5 15.1 611,800 1.683 1.8.sup.c 5.404 .times. 10.sup.3
65 psi 1-pentene- 100 ml 38 Toluene 300 A 5.588 .times.
10.sup.-3 MAO 7 1.25 ethylene- norbornene- 50 0.5 12.3 812,600 1.711
0.3.sup.c 4.402 .times. 10.sup.3 65 psi 100 ml 2.2M 39 Toluene
300 A 5.588 .times. 10.sup.-3 MAO 7 1.25 ethylene- cis-1,4- 50 0.5 13.6
163,400 2.388 2.2.sup.c 4.868 .times. 10.sup.3 65 psi hexadiene
100 ml
.sup.a Compound A was preactivated by dissolving the compound in solvent
containing MAO.
.sup.b Preincubation of activated compound A was for one day.
.sup.c Mole % comonomer.
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).
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.
The preferred polymerization diluents for practice of the process of the
invention are aromatic diluents, such as toluene, or alkanes, such as
hexane.
The resins that are prepared in accordance with this invention can be used
to make a variety of products including films and fibers.
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.
Top