U.S. patent number RE37,400 [Application Number 09/141,478] was granted by the patent office on 2001-10-02 for monocyclopentadienyl titanium metal compounds for ethylene-.alpha.-olefin-copolymer production catalysts.
This patent grant is currently assigned to Exxon Chemical Patents Inc.. Invention is credited to Jo Ann M. Canich.
United States Patent |
RE37,400 |
Canich |
October 2, 2001 |
Monocyclopentadienyl titanium metal compounds for
ethylene-.alpha.-olefin-copolymer production catalysts
Abstract
The invention is a catalyst system including a
monocyclopentadienyl titanium compound and an alumoxane component
which is highly productive for polymerizing ethylene and
.alpha.-olefins to produce a high molecular weight
ethylene-.alpha.-olefin copolymer having a high content of
.alpha.-olefin.
Inventors: |
Canich; Jo Ann M. (Webster,
TX) |
Assignee: |
Exxon Chemical Patents Inc.
(N/A)
|
Family
ID: |
27410695 |
Appl.
No.: |
09/141,478 |
Filed: |
August 27, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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850751 |
Mar 13, 1992 |
5264405 |
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581841 |
Sep 13, 1990 |
5096867 |
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533245 |
Jun 4, 1990 |
5055438 |
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406945 |
Sep 13, 1989 |
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Reissue of: |
109194 |
Aug 19, 1993 |
05631391 |
May 20, 1997 |
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Current U.S.
Class: |
556/11; 502/103;
502/117; 526/127; 526/160; 526/943; 556/12; 556/28; 556/53;
556/56 |
Current CPC
Class: |
C07F
7/10 (20130101); C07F 17/00 (20130101); C08F
10/00 (20130101); C08F 10/06 (20130101); C08F
210/16 (20130101); C08F 10/00 (20130101); C08F
4/6592 (20130101); C08F 10/06 (20130101); C08F
4/6592 (20130101); C08F 4/65908 (20130101); C08F
4/65912 (20130101); C08F 4/6592 (20130101); C08F
110/02 (20130101); C08F 110/06 (20130101); C08F
210/06 (20130101); C08F 210/18 (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 210/14 (20130101); C08F
2500/01 (20130101); C08F 2500/03 (20130101); C08F
2500/10 (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 210/14 (20130101); C08F
2500/10 (20130101); C08F 2500/01 (20130101); C08F
2500/03 (20130101); C08F 210/16 (20130101); C08F
210/08 (20130101); C08F 2500/10 (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 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
2500/01 (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
2500/01 (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
2500/10 (20130101); C08F 2500/01 (20130101); C08F
2500/03 (20130101); Y10S 526/943 (20130101) |
Current International
Class: |
C07F
7/00 (20060101); C08F 4/00 (20060101); C07F
17/00 (20060101); C07F 7/28 (20060101); C08F
4/642 (20060101); C07F 017/00 (); C07F
007/28 () |
Field of
Search: |
;556/11,12,28,53,56
;502/103,117,152 ;526/127,160,943 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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416815 |
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Mar 1991 |
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EP |
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468651 |
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Jan 1992 |
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EP |
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514828 |
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Nov 1992 |
|
EP |
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520732 |
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Dec 1992 |
|
EP |
|
563365 |
|
Oct 1993 |
|
EP |
|
WO93/13140 |
|
Jul 1991 |
|
WO |
|
WO93/08221 |
|
Apr 1993 |
|
WO |
|
Other References
M Reetz, Organotitanium reagents in Organic Synthesis, pp. 117 and
121 (Springer-Verlay), 1986.* .
Kukenhohner, "Untersuchungen zur Darstellung Chiraler Organotian
(IV)-Verbindugen flur Enantioselektire Synthesen" (unpublished
Diplomarbeit, University of Marburg, Germany), 1983.* .
Kukenhohner, "Organotitan (IV) Agentien: Komplexe chiraler
Chelatliganden und Enantioselektic c-c-Verknufungen" (University of
Marburg, Germany), 1986.* .
Stevens et al. Motion No. 57 to Restore Jurisdiction to the ex
parte Examiner in Interference No. 102,953 (Paper No. 526) and
appended 37 C.F.R. .sctn. 1.607 Request For Interference with
patent No. 5,631,391. Identical motions have been filed in
Interference Nos. 102,954 (Paper No. 490), 102,955 (Paper No. 483),
103,067 (Paper No. 353) and 103,819 (Paper No. 103). .
Canich Opposition to Stevens Motion No. 57 (paper No. 531).
Identical oppositions have been filed in Interference Nos. 102,954
(Paper No. 495), 102,955 (Paper No. 488), 103,067 (Paper No. 358)
and 103,819 (Paper No. 116). .
Stevens Repy No. 57 (Paper No. 534). Identical replies have been
filed in Interference Nos. 102,954 (Paper No. 498), 102,955 (Paper
No. 491), 103,067 (Paper No. 361) and 103,819 (Paper No. 126).
.
Decision of APJ Downey on Stevens et al. Motion No. 57 (Paper No.
535). .
Decision of APJ Downey on Stevens Oral Request for Reconsideration
of her Decision in Paper No. 535 (Paper No. 363 [sic--536]). .
Stevens et al.'s 37 C.F.R. .sctn. 1.607 Request for Interference
with patent No. 5,631,391 and reissue application serial No.
09/141,478. .
Stevens et al.'s 37 C.F.R. .sctn. Request For Interference with
patent Nos. 5,631,391 and 5,621,126, and reissue application serial
Nos. 09/141,478 and 09/141,176..
|
Primary Examiner: Nazario-Gonzalez; Porfirio
Attorney, Agent or Firm: Fish & Neave
Parent Case Text
This is a division of application Ser. No. 07/850,751, filed Mar.
13, 1992, now U.S. Pat. No. 5,264,405, which is a
continuation-in-part of application Ser. No. 07/581,841, filed Sep.
13, 1990, now U.S. Pat. No. 5,096,867, which is a
continuation-in-part of application Ser. No. 07/533,245, filed Jun.
4, 1990, now U.S. Pat. No. 5,055,438, which is a
continuation-in-part of application Ser. No. 07/406,945, filed Sep.
13, 1989, now abandoned; all are incorporated by reference.
Claims
I claim:
1. A compound having the formula: ##STR7##
wherein R.sup.1 and R.sup.2 are each independently a C.sub.1 to
C.sub.6 a hydrocarbyl radical, each Q and Q' is independently a
halide or alkyl radical, R' is an aliphatic or alicyclic
hydrocarbyl radical having from .[.1.]. .Iadd.3 .Iaddend.to 20
carbon atoms and R' is covalently bonded to the nitrogen atom
through a 1.degree. or 2.degree. carbon atom, L is a neutral Lewis
base where "w" denotes a number from 0 to 3 and each R is,
independently a C.sub.1-4 hydrocarbyl radical or hydrogen, x is 0,
1, 2, 3 or 4, and two adjacent R groups may join to form a
C.sub.4-10 ring.
2. The compounds of claim 1, wherein R' is an alicyclic hydrocarbyl
radical.
3. The compound of claim 2, wherein R' is cyclododecyl.
4. The compound of claim 3, wherein R.sup.1 and R.sup.2 are
methyl.
5. The compound of claim 4, wherein each Q is chlorine or
methyl.
6. The compound of claim 1, having the formula: ##STR8##
wherein R.sup.1 and R.sup.2 are each independently a C.sub.1 to
C.sub.6 a hydrocarbyl radical, each Q and Q' is independently a
halide or alkyl radical, R' is an aliphatic or alicyclic
hydrocarbyl radical of from .[.1.]. .Iadd.3 .Iaddend.to 20 carbon
atoms and R' is covalently bonded to the nitrogen atom through a
1.degree. or 2.degree. carbon atom, and L is a neutral Lewis base
where "w" denotes a number from 0 to 3.
7. The compound of claim 6, wherein R' is an alicyclic hydrocarbyl
radical.
8. The compound of claim 7, wherein R' is cyclodedecyl.
9. The compound of claim 8, wherein R.sup.1 and R.sup.2 are
methyl.
10. The compound of claim 9, wherein each Q is chlorine or methyl.
Description
FIELD OF THE INVENTION
This invention relates to certain monocyclopentadienyl titanium
compounds, to a catalyst system comprising a monocyclopentadienyl
titanium compound and an alumoxane, and to a process using such
catalyst system for the production of polyolefins, particularly
ethylene-.alpha.-olefin copolymers having a high molecular weight
and high level of .alpha.-olefin incorporation. The catalyst system
is highly active at low ratios of aluminum to the titanium metal,
hence catalyzes the production of a polyolefin product containing
low levels of catalyst metal residue.
This invention relates to the discovery of various catalyst ligand
structure affects which are reflected in the activity of the
catalyst system and in the physical and chemical properties
possessed by a polymer produced with a monocyclopentadienyl
titanium metal catalyst system. Accordingly, various species within
the general class of monocyclopentadienyl titanium catalyst as
disclosed by commonly-owned U.S. patent application Ser. No.
581,841, have been discovered to be vastly superior in terms of the
ability of such species to produce ethylene-.alpha.-olefin
copolymers of high molecular weight with high levels of
.alpha.-olefin comonomer incorporation and at high levels of
catalyst productivity.
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 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.
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 a Group IV B
metal, particularly, titanocenes and zirconocenes, 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 conventional interest.
It is since become know that such metallocenes may be cocatalyzed
with an alumoxane--rather than an aluminum alkyl--to provide a
metallocene catalyst system of high activity for the production of
polyolefins.
The zirconium metallocene species, as cocatalyzed or activated with
an alumoxane, are commonly more active than their hafnium or
titanium analogs for the polymerization of ethylene alone or
together with an .alpha.-olefin comonomer. When employed in an
non-supported from--i.e., as a homogeneous or soluble catalyst
system--to obtain a satisfactory rate of productivity even with the
most active zirconium species of metallocene typically requires the
use of a quantity of alumoxane activator sufficient to provide an
aluminum atom to transition metal atom ratio (Al:TM) of at least
greater than 1000:1; often greater than 5000:1, and frequently on
the order of 10,000:1. Such quantities of alumoxane impart to a
polymer produced with such catalyst system an undesirable content
of catalyst metal residue, i.e., an undesirable "ash" content (the
nonvolatile metal content). In high pressure polymerization
procedures using soluble catalyst systems wherein the reactor
pressure exceeds about 500 bar only the zirconium or hafnium
species of metallocenes may be used. Titanium species of
metallocenes are generally unstable at such high pressures unless
deposited upon a catalyst support.
A wide variety of Group IV B transition metal compounds have been
named as possible candidates for an alumoxane cocatalyzed catalyst
system. Although bis(cyclopentadienyl) Group IV B transition metal
compounds have been the most preferred and heavily investigated for
use in alumoxane activated catalyst systems for polyolefin
production, suggestions have appeared that mono and
tris(cyclopentadienyl) transition metal compounds may also be
useful. See, for example U.S. Pat. No. 4,522,982; 4,530,914 and
4,701,431. Such mono(cyclopentadienyl) transition metal compounds
as have heretofore been suggested as candidates for an alumoxane
activated catalyst system are mono (cyclopentadienyl) transition
metal trihalides and trialkyls.
More recently, International Publication No. WO 87/03887 describes
the use of a composition comprising a transition metal coordinated
to at least one cyclopentadienyl and at least one heteroatom ligand
as a transition metal component for use in an alumoxane activated
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 transition metal coordination requirement being
satisfied with cyclopentadienyl or hydrocarbyl ligands. Catalyst
systems described by this reference are illustrated solely with
reference to transition metal compounds which are metallocenes,
i.e., bis (cyclopentadienyl) Group IV B transition metal
compounds.
Even more recently, at the Third Chemical Congress of North
American 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 was discouraging of a belief that such
monocyclopentadienyl transition metal compound could be usefully
employed for commercial polymerization processes.
Although the metallocene/alumoxane catalyst system constituted an
improvement relative to a traditional Ziegler-Natta catalyst
system, a need existed for discovering catalyst systems that permit
the production of higher molecular weight polyolefins and desirably
with a narrow molecular weight distribution. Further desired was a
catalyst which, within reasonable ranges of ethylene to
.alpha.-olefin monomer ratios, will catalyst the incorporation of
higher contents of .alpha.-olefin comonomers in the production of
ethylene-.alpha.-olefins copolymers.
SUMMARY OF THE INVENTION
Commonly owned copending U.S. application Ser. No. 581,841
disclosed the discovery of a class of monocyclopentadienyl Group IV
B translation metal compounds which, when activated with an
alumoxane, may be employed as a catalyst system 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
disclosed in application Ser. No. 581,841 is represented by the
formula: ##STR1##
wherein:
M is Zr, Hf or Ti in its highest formal oxidation state (+4,
d.sup.o 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 radical, am amido
radical, a phosphido radical, and alkoxy radical or any other
radical containing a Lewis acidic or basic functionality, 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; halogen radicals, amido radicals, phosphido radicals,
alkoxy radicals, alkylborido radicals or any other radical
containing Lewis acidic or basic functionality; or (C.sub.5
H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring in which at least
two adjacent R-groups are joined forming a 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 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 are replaced by a halogen radical, an amido radical, a
phosphido radical, an alkoxy radical or any other radical
containing a Lewis acidic or basic functionality, and "z" is the
coordination number of the element J;
each Q may be independently any univalent anionic ligand such as a
halide, 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, T 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 neutral 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 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 dimeric compounds are represented by the
formula: ##STR2##
The alumoxane component of the catalyst may be represented by the
formulas: (R.sup.3 --Al--O).sub.m ; R.sup.4 (R.sup.5 --Al--O).sub.m
--AlR.sub.2.sup.6 or mixtures thereof, wherein R.sup.3 -R.sup.6
are, independently, 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 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.
As further disclosed in U.S. application Ser. No. 581,841, that
class of the Group IV B transition metal component wherein the
metal is titanium have been found to impart beneficial properties
to a catalyst system which are unexpected in view of which is known
about the properties of bis(cyclopentadienyl) titanium compounds
which are cocatalyzed by alumoxanes. Whereas titanocenes in their
soluble form are generally unstable in the presence of aluminum
alkyls, the monocyclopentadienyl titanium metal components,
particularly those wherein the heteroatom is nitrogen, generally
exhibit greater stability in the presence of aluminum alkyls,
higher catalyst activity rates and higher .alpha.-olefin comonomer
incorporation.
Further, the titanium class of the Group IV B transition metal
component catalyst of the invention described by application Ser.
No. 581,841 generally exhibit higher catalyst activities and the
production of polymers of greater molecular weight and
.alpha.-olefin comonomer contents than catalyst systems prepared
with the zirconium or hafnium species of the Group IV B transition
metal component.
This invention comprises the discovery of a subgenus of
monocyclopentadienyl titanium compounds which, by reason of the
presence therein of ligands of a particular nature, provide a
catalyst of greatly improved performance characteristics compared
to other members of the genus of monocyclopentadienyl titanium
compounds as described in copending U.S. application Ser. No.
581,841. The subgenus of monocyclopentadienyl titanium catalyst
most preferred is that wherein the heteroatom ligand is an amido
group, the nitrogen atom of which is bridged through a bridging
group (T) to the cyclopentadienyl ring and wherein the nitrogen
atom is covalently bonded through a 1.degree. or 2.degree. carbon
atom to an alicyclic or aliphatic hydrocarbyl group. Herein a
1.degree. carbon atom is one which is methyl or a carbon atom which
is bonded to only one other carbon atom; a 2.degree. carbon atom is
one which is bonded to only two other carbon atoms, and a 3.degree.
carbon atom is bonded to three other carbon atoms. Preferably the
alicyclic or aliphatic hydrocarbyl group has three or more carbon
atoms and is bonded to the nitrogen atom through a 2.degree. carbon
atom, most preferably the hydrocarbyl group is alicyclic.
Monocyclopentadienyl titanium compounds within this subgenus have
been discovered to produce a highly productive catalyst system
which produces an ethylene-.alpha.-olefin copolymer of
significantly greater molecular weight and .alpha.-olefin comonomer
content as compared with other species of monocyclopentadienyl
titanium compounds when utilized in an otherwise identical catalyst
system under identical polymerization conditions. Further, within
this subgenus of titanium compounds it has been found that the
nature and degree of substitution groups (R) of the
cyclopentadienyl ring can be varied to produce a catalyst system
having a "catalyst reactivity ratio (r.sub.1)" which may be varied
from a high to a low value as may be most desired to best suit the
catalyst system to a particular type of polymerization process.
Particularly, it has been found that as the number of substituents
(R), which are preferably hydrocarbyl substituents, increases, the
reactivity ratio (r.sub.1) decreases, the lowest reactivity ratios
being obtained by a titanium compound having a tetrahydrocarbyl
substituted cyclopentadienyl group, preferably a
tetramethylcyclopentadienyl group.
A typical polymerization process of the invention comprises the
steps of contacting ethylene and a C.sub.3 -C.sub.20 .alpha.-olefin
alone, or with other unsaturated monomers including C.sub.3
-C.sub.20 .alpha.-olefins, C.sub.4 -C.sub.20 diolefins, and/or
acetylenically unsaturated monomers with a catalyst comprising, in
a suitable polymerization diluent, a monocyclopentadienyl titanium
compound as described above; and a methylalumoxane in an amount to
provide a molar aluminum to titanium metal ratio of from about 1:1
to about 20,000:1 or more; and reacting such monomers 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 copolymer 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
The disclosure of U.S. application Ser. No. 581,841 is hereby
incorporated by reference.
As disclosed in U.S. application Ser. No. 581,841, wherein it is
desired to produce an .alpha.-olefin copolymer which incorporates a
high content of .alpha.-olefin, the class of Group IV B transition
metal compound preferred is one of titanium. The most preferred
class of titanium metal compounds are represented by the formula:
##STR3##
wherein Q, L, R', R, "x" and "w" are as previously defined and
R.sup.1 and R.sup.2 are each independently a C.sub.1 to C.sub.20
hydrocarbyl radicals, substituted C.sub.1 to C.sub.20 hydrocarbyl
radicals wherein one or more hydrogen atom is replaced by a halogen
atom; R.sup.1 and R.sup.2 may also be joined forming a C.sub.3 to
C.sub.20 ring which incorporates the silicon bridge.
Among this class of titanium compounds various substituent and
ligand affects have been discovered which significantly affect the
properties of a catalyst system. The nature and degree of
substitutions (R) in the cyclopentadienyl ring was found to
significantly influence the catalyst ability to incorporate
.alpha.-olefin comonomers when producing an ethylene-.alpha.-olefin
copolymer. For the greatest amount of comonomer incorporation, the
cyclopentadienyl ring should be fully substituted (x=4) with
hydrocarbyl groups (R), most preferably methyl groups. This affect
is demonstrated by a comparison between Examples 83 to 85. Next,
the nature of the R' ligand of the amido group significantly
influences the capability of a catalyst to incorporate
.alpha.-olefin comonomer. Amido group R' ligands which are
aliphatic or alicyclic hydrocarbyl ligands bonded to the nitrogen
atom through a 1.degree. or 2.degree. carbon atom provide for a
greater degree of .alpha.-olefin comonomer incorporation than do R'
groups bonded through a 3.degree. carbon atom or bearing aromatic
carbon atoms. Further, wherein the R' ligand is bonded to the
nitrogen atom through a 2 .degree. carbon atom, the activity of the
catalyst is greater when the R' substituent is alicyclic than when
R' is bonded to the nitrogen through a 1.degree. carbon atom of an
aliphatic group of identical carbon number. With regard to an
alicyclic hydrocarbyl R' ligand it has been found that as the
number of carbon atoms thereof increases the molecular weight of
the ethylene-.alpha.-olefin copolymer increases while the amount of
.alpha.-olefin comonomer incorporated remains about the same or
increases. Further, as the carbon number of the allcyclic
hydrocarbyl ligand increases the productivity of the catalyst
system increases. This is demonstrated by Examples 71-76.
Accordingly, the R' ligand most preferred is cyclododecyl (C.sub.12
H.sub.23).
The affects of the bridging group ligands R.sup.1 and R.sup.2 has
been found to be of less significance. The nature of the R.sup.1
and R.sup.2 ligands exerts a small effect upon the activity of a
catalyst. For greatest catalyst activity the R.sup.1 and R.sup.2
ligands are preferably alkyl, most preferably methyl. The Q anionic
ligands of the transition metal have not been observed to exert any
particular influence on the catalyst or polymer properties, as
demonstrated by comparison of Examples 71 and 86. Accordingly, as a
convenience in the production of the transition metal component the
Q ligands are preferably chlorine or methyl.
The compounds most preferred for reasons of their high catalyst
activity in combination with an ability to produce high molecular
weight ethylene-.alpha.-olefin copolymers of high comonomer
contents is represented by the formula: ##STR4##
wherein R.sup.1 and R.sup.2 are each independently a C.sub.1 to
C.sub.3 hydrocarbyl radical, each Q is independently a halide or
alkyl radical, R' is an aliphatic or an alicyclic hydrocarbyl
radical of the formula (C.sub.n H.sub.2n+b) wherein "n" is a number
from 3 to 20 and "b" is +1 in which case the ligand is aliphatic or
-1 in which case the ligand is alicyclic. Of these compounds, the
most preferred is that compound wherein R.sup.1 and R.sup.2 are
methyl, each Q is chlorine or methyl, n is 12, and the hydrocarbyl
radical is alicyclic (i.e., b is -1). Most preferred is that
compound wherein the (C.sub.n H.sub.2n+1 1) hydrocarbyl radical is
a cyclododecyl group. Hereafter this compound is referred to for
convenience as Me.sub.2 Si(C.sub.5 Me.sub.4) (NC.sub.12
H.sub.23)TiQ.sub.22.
The alumoxane component of the catalyst system is an oligomeric
compound which may be represented by the general formula (R.sup.3
--Al--O).sub.m which is a cyclic compound, or may be R.sup.4
(R.sub.5 --Al--O--).sup.m --AlR.sup.6.sub.2 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.3,
R.sup.4, R.sup.5 and R.sup.6 are, independently a C.sub.1 -C.sub.5
alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl
and "m" is an integer from 1 to about 50. Most preferably, R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 are each methyl and "m" is at least 4.
When an alkyl aluminum halide is employed in the preparation of the
alumoxane, one or more R.sup.3-6 groups may 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 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 a
trialkylaluminum; such as trimethylaluminum, triethylaluminum,
tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride,
diisobutylaluminumchloride, diethylaluminumchloride, and the like.
The most preferred alumoxane for use is methylalumoxane (MAO).
Methylalumoxanes having an average degree of oligomerization of
from about 4 to about 25 ("m"=4 to 25), with a range of 13 to 25,
are the most preferred.
Catalyst Systems
The catalyst systems employed in the method of the invention
comprise a complex formed upon admixture of the titanium metal
component with an alumoxane component. The catalyst system may be
prepared by addition of the requisite titanium 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 titanium 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 phase 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, oxtane 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 titanium 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.
The catalyst system ingredients--that is, the titanium metal
component, 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 -100.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.
Polymerization Process
In a preferred embodiment of the process of this invention the
catalyst system is utilized in the liquid phase (slurry, solution,
suspension or bulk phase or 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 ethylene and a
.alpha.-olefin monomer with the catalyst system in a suitable
polymerization diluent and reacting the monomers in the presence of
the catalyst system for a time and at a temperature sufficient to
produce an ethylene-.alpha.-olefin copolymer of high molecular
weight.
The monomers for such process comprise ethylene in combinations
with an .alpha.-olefin having 3 to 20 carbon atoms for the
production of an ethylene-.alpha.-olefin copolymer. It should be
appreciated that the advantages as observed in a
ethylene-.alpha.-olefin copolymer produced with a catalyst system
of this invention would also be expected to be obtained in a
copolymer of different .alpha.-olefins wherein ethylene is not used
as a monomer as viewed in comparison to a copolymer of the same or
different .alpha.-olefins produced under similar polymerization
conditions with a catalyst system which does not use a
monocyclopentadienyl titanium compound as defined herein.
Accordingly, although this invention is described with reference to
an ethylene-.alpha.-olefin copolymer and the advantages of the
defined catalyst system for the production thereof, this invention
is not to be understood to be limited to the production of an
ethylene-.alpha.-olefin copolymer, but instead the catalyst system
hereof is to be understood to be advantageous in the same respects
to the production of a copolymer composed of two or more C.sub.3 or
higher .alpha.-olefin monomers. Copolymers of higher .alpha.-olefin
such as propylene, butene, styrene or higher .alpha.-olefins and
diolefins can also be prepared. Conditions most preferred for the
homo- or copolymerization 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 titanium metal molar ratio is preferably from about 1:1
to 18,000 to 1. A more preferable range would be 1:1 to 2000:1. The
reaction time is preferably from about 10 seconds to about 1
hour.
The .alpha.-olefin to ethylene molar ratio often bears importantly
upon the production capacity of a reactor of any design--i.e.,
whether for solution or gas phase production, etc.--for production
of an ethylene based copolymer (i.e.--a copolymer the molar ratio
of which is 50% or greater ethylene). The more ethylene input to a
reactor in a given unit of time, the greater will be the amount of
ethylene based copolymer product obtained in that same unit of
time. Yet, polymers are designed for a variety of end services and
this design constraint dictates the molar percentage of
incorporated .alpha.-olefin which must be obtained in the targeted
copolymer product. The "catalyst reactive ratio (r.sub.1)" of a
catalyst system defines the property of the system of assimilating
an ethylene monomer into a polymer molecule chain in preference to
a particular .alpha.-olefin comonomer. The larger the r.sub.1
number, the greater the preference of the catalyst system for
incorporating an ethylene monomer rather than a .alpha.-olefin
monomer. Thus, to achieve a targeted .alpha.-olefin monomer
incorporation (C.sub..alpha.) in the product polymer, the higher
the r.sub.1 value of a catalyst system, the larger must be the
C.sub..alpha. /C.sub.2 molar ratio of monomers used in the reactor,
and as the C.sub..alpha. /C.sub.2 ratio increases the lower is the
production capacity of the reactor.
To achieve a desired level of .alpha.-olefin monomer incorporation
in a copolymer product, as can be seen, it is often desired to have
a catalyst system which can achieve a low molar ratio of
C.sub..alpha. /C.sub.2, i.e., a catalyst system with a low r.sub.1
is desired. For example, with reference to 1-butene, the catalyst
systems of this invention wherein the titanium metal compound has a
tetramethyl substitute cyclopentadienyl ligand generally exhibit an
r.sub.1 value of 6 or less, and typically of 5 or less. Thus, with
catalyst systems of this invention an .alpha.-olefin incorporation
of greater than 20wt. % can be achieved at a C.sub..alpha. /C.sub.2
ratio of 2.0 or less, and typically of about 1.6.
In addition to the benefits of increased reactor productivity
which, for a copolymer of a targeted .alpha.-olefin incorporation
level, which a catalyst system of lower r.sub.1 values allows,
other significant additional benefits ensue from a low r.sub.1
value. Recovery of unreacted monomer, particularly .alpha.-olefin
monomer for later reuse adds significantly to production cost. By
use of the catalyst systems identified by this invention, the cost
of unreacted .alpha.-olefin monomer recovery may be reduced
significantly since a smaller quantity of .alpha.-olefin monomer
can be used to achieve the same target level of .alpha.-olefin
incorporation.
Further, since it is the ratio of C.sub..alpha. /C.sub.2 in the
medium wherein polymerization occurs which is critical (i.e.,
liquid phase, gas phase, or super critical fluid phase, etc.) the
low r.sub.1 values for the catalyst systems of this invention
permit the catalyst systems to be used in a wider variety of
polymerization procedures than was heretofore believed to be
practically possible. Praticularily within this range of
possibilities is that of the gas phase polymerization of an
ethylene .alpha.-olefin copolymer of a greater than heretofore
believed possible level of .alpha.-olefin incorporation.
Without limiting in any way the scope of the invention, one means
for carrying out the process of the present invention for
production of a copolymer is as follows: in a stirred-tank reactor
liquid .alpha.-olefin monomer is introduced, such as 1-butene. 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 .alpha.-olefin comonomer, 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 .alpha.-olefin comonomer in the reactor, which
is controlled by manipulating the relative feed rates of these
components to the reactor.
As before noted, a catalyst system wherein the Group IV B
transition metal component is titanium has the ability to
incorporate high contents of .alpha.-olefin comonomers.
Accordingly, the selection of the titanium metal component to have
the cyclopentadienyl group to be tetramethyl substituted and to
have an amido group bridged through its nitrogen atom to the
cyclopentadienyl ring wherein the nitrogen of the amido group is
bonded through a 1.degree. or 2.degree. carbon atom to an aliphatic
or alicyclic hydrocarbyl group, most preferably an alicyclic
hydrocarbyl group is another parameter which may be utilized as a
control over the .alpha.-olefin content of the
ethylene-.alpha.-olefin copolymer within a reasonable ratio of
ethylene to .alpha.-olefin comonomer. For reasons already
explained, in the production of an ethylene-.alpha.-olefin
copolymer a molar ratio of .[.ethylene to .alpha.-olefin.].
.Iadd..alpha.-olefin to ethylene .Iaddend.of 2.0 or less is
preferred, and a ratio of 1.6 or less is more preferred.
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 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.
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 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.5 Me.sub.4 include C. M. Fendrick et al.
Organometallics, 3, 819 (1984) and F. H. Kohler and K. H Doll, Z.
Naturforich, 376, 144 (1982). Other lithiated substituted
cylcopentadienyl compounds are typically prepared from the
corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by
reaction of MeLi with the proper fulvene. TiCl.sub.4, ZrCl.sub.4
and HfCl.sub.4 were purchased from either Aldrich Chemical Company
or Cerac. TiCl.sub.4 was typically used in its etherate form. The
etherate, TiCl.sub.4.cndot.2Et.sub.2 O, can be prepared by gingerly
adding TiCl.sub.4 to diethylether. Amines, silanes, substituted and
unsubstituted cyclopentadienyl compounds or precursors, and lithium
reagents were purchased from Aldrich Chemical Company or Petrarch
Systems. Methylalumoxane was supplied by either Sherring or Ethyl
Corp.
Further, since the full disclosure of U.S. application Ser. No.
581,841 has been incorporated herein, the Examples hereof are
identified by designations which are consistent with the Example
designations of the incorporated application. Examples of the
incorporated application relating to the Zr or Hf metal classes of
a monocyclopentadienyl transition metal catalyst system are not
here repeated (which are Examples A to L) for sake of brevity.
Accordingly, not verbatim repeated herein (but incorporated) are
Examples A to L, and certain other double letter designated
Examples of the incorporated patent. Set forth verbatim herein as
repeats of Examples of the incorporated application are Examples
AT, FT, IT, JT, 40-47, 53-56, 58, 67 and 70.
EXAMPLE AT
Compound AT: Part 1. MePhSiCl.sub.2 (14.9 g, 0.078 mol) was diluted
with 250 ml of thf. Me.sub.4 HC.sub.5 Li (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(C.sub.5 Me.sub.4 H)Cl (15.0 g, 0.054 mol) was
added dropwise. The yellow solution was allowed to stir overnight.
The solvent was removed in vacuo. Petroleum ether was added to
precipitate the LiCl. The mixture was filtered through Celite, and
the filtrate was evaporated. MePhSi(C.sub.5 Me.sub.4 H)(NH-t-Bu)
(16.6 g, 0.053 mol) was recovered as an extremely viscous
liquid.
Part 3. MePhSi(C.sub.5 Me.sub.4 H)(NH-t-Bu) (17.2 g, 0.055 mol) was
diluted with .about.20 ml of ether. n-BuLi (60 ml in hexane, 0.096
mol, 1.6 M) was slowly added and the reaction mixture was allowed
to stir for .about.3 hours. The solvent was removed in vacuo to
yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li.sub.2
[MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)].
Part 4. Li.sub.2 [MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)] (8.75 g, 0.027
mol) was suspended in .about.125 ml of cold ether
(.about.-30.degree.). TiCl.sub.4.cndot.2Et.sub.2 O (9.1 g, 0.027
mol) was slowly added. The reaction was allowed to stir for several
hours prior to removing the ether via vacuum. A mixture of toluene
and dichloromethane was then added to solubilize the product. The
mixture was filtered through Celite to remove the LiCl. The solvent
was largely removed via vacuum and petroleum ether was added. The
mixture was cooled to maximize product precipitation. The crude
product was filtered off and redissolved in toluene. The toluene
insolubles were filtered off. The toluene was then reduced in
volume and petroleum ether was added. The mixture was cooled to
maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of
the yellow solid MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)TiCl.sub.2.
EXAMPLE FT
Compound FT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example BT for the preparation of compound BT, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (5.19 g, 0.024 mol) was
slowly added to a solution of LiHNC.sub.6 H.sub.11 (2.52 g, 0.024
mol) in .about.125 ml of thf. The solution was allowed to stir for
several hours. The thf was removed via vacuum and petroleum ether
was added to precipitate the LiCl which was filtered off. The
solvent was removed from the filtrate via vacuum yielding 6.3 g
(0.023 mol) of the yellow liquid, Me.sub.2 Si(C.sub.5 Me.sub.4
H)(HNC.sub.6 H.sub.11).
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.6 H.sub.11) (6.3 g,
0.023 mol) was diluted with .about.100 ml of ether. MeLi (33 ml,
1.4 M in ether, 0.046 mol) was slowly added and the mixture was
allowed to stir for 0.5 hours prior to filtering off the white
solid. The solid was washed with ether and vacuum dried. Li.sub.2
[Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.11)] was isolated in
a 5.4 g (0.019 mol) yield.
Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.11)]
(2.57 g, 8.90 mmol) was suspended in .about.50 ml of cold ether.
TiCl.sub.4.cndot.2Et.sub.2 O (3.0 g, 8.9 mmol) was slowly added and
the mixture was allowed to stir overnight. The solvent was removed
via vacuum and a mixture of toluene and dichloromethane was added.
The mixture was filtered through Celite to remove the LiCl
byproduct. The solvent was removed from the filtrate and a small
portion of toluene was added followed by petroleum ether. The
mixture was chilled in order to maximize precipitation. A brown
solid was filtered off which was initially dissolved in hot
toluene, filtered through Celite, and reduced in volume. Petroleum
ether was then added. After refrigeration, an olive green solid was
filtered off. This solid was recrystallized twice from
dichloromethane and petroleum ether to give a final yield of 0.94 g
(2.4 mmol) of the pale olive green solid, .[.Me.sub.2 Si(C.sub.5
Me.sub.4)(NC.sub.6 H.sub.11)TiCl.]. .Iadd.Me.sub.2 Si(C.sub.5
Me.sub.4)(NC.sub.6 H.sub.11)TiCl.sub.2.Iaddend..
EXAMPLE IT
Compound IT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example BT for the preparation of Compound BT, part
1.
Part 2. (C.sub.5 Me.sub.4 H)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 was added to precipitate out the LiCl. The mixture
was filtered through Celite. The solvent was removed from the
filtrate. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NH-t-Bu) (11.14 g, 0.044
mol) was isolated as a pale yellow liquid.
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NH-t-Bu) (11.14 g, 0.044
mol) was diluted with .about.100 ml of ether. MeLi (1.4M, 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(C.sub.5 Me.sub.4)(N-t-Bu)]Li.sub.2, was washed with several
small portions of ether, then vacuum dried.
Part 4. [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-t-Bu)Li.sub.2 (6.6 g,
0.025 mol) was suspended in cold ether. TiCl.sub.4.cndot.2Et.sub.2
O (8.4 g, 0.025 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. Methylene chloride was added to
precipitate out the LiCl. The mixture was filtered through Celite.
The solvent was significantly reduced in volume and petroleum ether
was added to precipitate out the product. This mixture was
refrigerated prior to filtration in order to maximize
precipitation. Me.sub.2 Si(C.sub.5 Me.sub.4)(N-t-Bu)TiCl.sub.2 was
isolated (2.1 g, 5.7 mmol).
EXAMPLE JT
Compound JT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example BT for the preparation of Compound BT, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (8.0 g, 0.037 mol) was
slowly added to a suspension of LiHNC.sub.12 H.sub.23 (C.sub.12
H.sub.23 =cyclododecyl, 7.0 g, 0.037 mol, .about.80 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 and
toluene was added to precipitate out the LiCl. The mixture was
filtered through Celite. The solvent was removed from the filtrate.
Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NHC.sub.12 H.sub.23) (11.8 g, 0.033
mol) was isolated as a pale yellow liquid.
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NHC.sub.12 H.sub.23) (11.9
g, 0.033 mol) was diluted with .about.150 ml of ether. MeLi (1.4 M,
47 ml, 0.066 mol) was slowly added. The mixture was allowed to stir
for 2 hours after the final addition of MeLi. The ether was reduced
in volume prior to filtering off the product. The product,
[Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)]Li.sub.2, was
washed with several small portions of ether, then vacuum dried to
yield 11.1 g (0.030 mol) of product.
Part 4. [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)]Li.sub.2
(3.0 g, 0.008 mol) was suspended in cold ether.
TiCl.sub.4.cndot.2Et.sub.2 O (2.7 g, 0.008 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.
Methylene chloride was added to precipitate out the LiCl. The
mixture was filtered through Celite. The solvent was significantly
reduced in volume and petroleum ether was added to precipitate out
the product. This mixture was refrigerated prior to filtration in
order to maximize precipitation. The solid collected was
recrystallized from methylene chloride and Me.sub.2 Si(C.sub.5
Me.sub.4)(NC.sub.12 H.sub.23)TiCl.sub.2 was isolated (1.0 g, 2.1
mmol).
EXAMPLE KT
Compound KT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.0279 mol) was
diluted in 200 ml of thf. LiHNC.sub.12 H.sub.25 (C.sub.12 H.sub.25
=n-dodecyl, 5.33 g, 0.0279 ml) was slowly added and the mixture was
allowed to stir for 3 hours. The thf was removed in vacuo and 200
ml ether was added.
To this solution, MeLi (1.4 M, 34 ml, 0.0476 mol) was slowly added.
Upon completion of the reaction, a small amount of
TiCl.sub.4.cndot.2Et.sub.2 O was added to scavenge the excess MeLi.
The solution was then cooled to -30.degree. C. and an additional
7.75 g (0.030 mol) of TiCl.sub.4.cndot.2Et.sub.2 O was added. The
mixture was allowed to stir overnight. The solvent was removed and
pentane was added. The resulting mixture was filtered through
Celite to remove the LiCl. The filtrate was reduced in volume and
chilled to induce crystalization of the product. Filtration yielded
4.2 g (0.0087 mol) Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12
H.sub.25)TiCl.sub.2.
EXAMPLE LT
Compound LT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (12.0 g, 0.056 mol) was
diluted with 300 ml of thf. LiHNC.sub.8 H.sub.15 (C.sub.8 H.sub.15
=cyclooctyl, .[.742.]. .Iadd.7.42 .Iaddend.g, 0.056 mol) was slowly
added and the mixture was allowed to stir overnight. The reaction
product, Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.8 H.sub.15) was
not isolated. The thf was removed and 300 ml of diethyl ether was
added. MeLi (1.12 M, 105 ml, 0.118 mol) was slowly added to form
the dilithiated salt, Li.sub.2 [Me.sub.2 Si(C.sub.5
Me.sub.4)(NC.sub.8 H.sub.15)]. This mixture was cooled to
-30.degree. C., and TiCl.sub.4.cndot.2Et.sub.2 O (19.14 g, 0.057
mol) was slowly added. The resulting mixture was allowed to stir
overnight. The ether was removed in vacuo, and pentane was added to
solubilize the product. The mixture was filtered through Celite to
remove the LiCl. The filtrate was reduced in volume and chilled to
-40.degree. C. to induce crystallization of the product. Filtration
yielded 7.9 g (0.019 mol) of Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8
H.sub.15)TiCl.sub.2.
EXAMPLE MT
Compound MT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was
diluted with 150 ml of thf. LiHNC.sub.8 H.sub.17 (C.sub.8 H.sub.17
=n-octyl, 3.7 g, 0.030 mol) was slowly added. The mixture was
allowed to stir overnight. The reaction product, Me.sub.2
Si(C.sub.5 Me.sub.4 H)(HNC.sub.8 H.sub.17) was not isolated prior
to adding MeLi (2.1 M, 35 ml, 0.074 mol) to give Li.sub.2 [Me.sub.2
Si(C.sub.5 Me.sub.4)(NC.sub.8 H.sub.17)]. The solvent was removed
via vacuum and replaced with diethyl ether, then cooled to
-30.degree. C. TiCl.sub.4.cndot.2Et.sub.2 O (8.46 g, 0.025 mol) was
slowly added and the mixture was allowed to stir overnight. The
solvent was removed in vacuo and methylene chloride was used to
solubilize the product. The solvent mixture was filtered through
Celite to remove the LiCl. The filtrate was evaporated down to
dryness and pentane was added. The pentane soluble fraction was
cooled to -40.degree. C. to induce crystallization of the product.
After filtration, Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8
H.sub.17)TiCl.sub.2 was isolated (1.8 g, 0.0042 mol).
EXAMPLE NT
Compound NT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was
diluted in 150 ml of thf. LiHNC.sub.6 H.sub.13 (C.sub.6 H.sub.13
=n-hexyl, 2.99 g, 0.028 mol) was slowly added. The mixture was
allowed to stir overnight. The thf was removed via vacuum and
replaced with diethyl ether. The reaction product Me.sub.2
Si(C.sub.5 Me.sub.4 H)(HNC.sub.6 H.sub.13) was not isolated prior
to adding MeLi (1.4 M, 45 ml, 0.063 mol) to give Li.sub.2 [Me.sub.2
Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.13)]. The resulting mixture was
then cooled to -30.degree. C. TiCl.sub.4.cndot.2Et.sub.2 O (8.6 g,
0.025 mol) was slowly added and the mixture was allowed to stir
overnight. The solvent was removed in vacuo and pentane was used to
solubilize the product. The solvent mixture was filtered through
Celite to remove the LiCl. The filtrate was reduced in volume and
cooled to -40.degree. C. to induce crystallization of the product.
While crystalline material appeared in the flask at -40.degree. C.,
upon slight warning, it dissolved back into solution and therefore
could not be isolated by filtration. Me.sub.2 Si(C.sub.5
Me.sub.4)(NC.sub.6 H.sub.13)TiCl.sub.2 was isolated in an oil form
by removing the solvent from the above solution. (4.0 g, 0.010
mol).
EXAMPLE OT
Compound OT: Part 1. MePhSi(C.sub.5 Me.sub.4 H)Cl was prepared as
described in Example At for the preparation of compound AT, Part
1.
Part 2. MePhSi(C.sub.5 Me.sub.4 H)Cl (6.0 g, 0.022 mol) was diluted
with ether. LiHN-s-Bu (1.7 g, 0.022 mol) was slowly added and the
mixture was allowed to stir overnight. The solvent was removed and
a mixture of toluene and petroleum ether was added. This mixture
was filtered through Celite to remove the LiCl. The solvent was
removed via vacuum leaving behind the viscous liquid,
MePhSi(C.sub.5 Me.sub.4 H)(HN-s-Bu). To this liquid which was
diluted with ether, 28 ml (0.039 mol 1.4 M, in ether) MeLi was
slowly added. After stirring overnight, a small portion of
TiCl.sub.4.cndot.2Et.sub.2 O (total of 5.86 g, 0.017 mol) was
slowly added and the mixture was allowed to stir overnight. The
solvent was removed via vacuum, dichloromethane was added and the
mixture was filtered through Celite. The filtrate was evaporated
down producing a brown solid. Petroleum ether was added and the
mixture was filtered. The brown solid remaining on the filter stick
was discarded and the filtrate was reduced in volume and
refrigerated to maximize precipitation. After filtration and
washing with cold aliquots of petroleum ether, a dark mustard
yellow solid was isolated and identified as MePhSi(C.sub.5
Me.sub.4)(N-s-Bu)TiCl.sub.2 (2.1 g, 4.9 mmol).
EXAMPLE PT
Compound PT: Part 1. MePhSi(C.sub.5 Me.sub.4 H)Cl was prepared as
described in Example AT for the preparation of compound AT, Part
1.
Part 2. MePhSi(C.sub.5 Me.sub.4 H)Cl (6.0 g, 0.022 mol) was diluted
with either. LiHN-n-Bu (1.7 g, 0.022 mol) was slowly added and the
mixture was allowed to stir overnight. The solvent was removed via
vacuum and a mixture of toluene and petroleum ether was added. This
was filtered through Celite to remove the LiCl. The solvent was
removed from the filtrate leaving behind a viscous yellow liquid
which was diluted with ether. To this, 28 ml of MeLi (1.4 M in
ether, 0.038 mol) was added and the mixture was allowed to stir
overnight. A small portion of TiCl.sub.4.cndot.2Et.sub.2 O (total
of 5.7 g, 0.017 mol) was slowly added. In spite of the slow
addition, the highly exothermic reaction bumped, thus some product
loss occurred at this point in the reaction. The remaining mixture
was stirred overnight. The solvent was then removed via vacuum.
Dichloromethane was added and the mixture was filtered through
Celite to remove the LiCl. The solvent was removed and petroleum
ether was added. The mixture was refrigerated to maximize
precipitation. Filtration produced a yellow-brown solid which was
recrystallized from petroleum ether. The final filtration produced
2.0 g (4.6 mmol) of MePhSi(Me.sub.4 C.sub.5)(N-n-Bu)TiCl.sub.2.
EXAMPLE QT
Compound QT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (9.0 g, 0.042 mol) was
diluted in ether. LiHN-s-Bu (3.31 g, 0.042 mol) was slowly added
and the mixture was allowed to stir overnight. The solvent was
removed via vacuum and petroleum ether was added. This mixture was
filtered through Celite to remove the LiCl. The solvent was removed
from the filtrate leaving behind the pale yellow liquid, Me.sub.2
Si(C.sub.5 Me.sub.4 H)(HN-s-Bu) (10.0 g, 0.040 mol).
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HN-s-Bu) (10.0 g, 0.040
mol) was diluted with ether. MeLi (58 ml, 1.4 M in ether, 0.081
mol) was added and the mixture was allowed to stir overnight. The
solvent was reduced in volume and the white solid was filtered off
and washed with small portions of ether. Li.sub.2 [Me.sub.2
Si(C.sub.5 Me.sub.4)(N-s-Bu)] (10.1 g, 0.038 mol) was isolated
after vacuum drying.
Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-s-Bu)] (7.0 g,
0.027 mol) was suspended in cold ether. TiCl.sub.4.cndot.2Et.sub.2
O (8.98 g, 0.027 mol) was slowly added and the mixture was allowed
to stir overnight. The solvent was removed via vacuum and
dichloromethane was added. The mixture was filtered through Celite
to remove the LiCl. The filtrate was reduced in volume and
petroleum ether was added. This mixture was refrigerated to
maximize precipitation prior to filtering off the olive green
solid. The solid was recrystallized from dichloromethane and
petroleum ether yielding 2.4 g (6.5 mmol) of the yellow solid,
Me.sub.2 Si(C.sub.5 Me.sub.4)(N-s-Bu)TiCl.sub.2.
EXAMPLE RT
Compound RT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared
as described in Example A for the preparation of compound A, Part
1.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (8.0 g, 0.037 mol) was
diluted with ether. LiHN-n-Bu (2.95 g, 0.037 mol) was slowly added
and the mixture was allowed to stir overnight. The solvent was
removed via vacuum and petroleum ether was added. The mixture was
filtered through Celite to remove the LiCl. The solvent was removed
from the filtrate leaving behind the yellow liquid, Me.sub.2
Si(C.sub.5 Me.sub.4 H)(HN-n-Bu) (8.6 g, 0.034 mol).
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HN-n-Bu) (8.6 g, 0.034 mol)
was diluted with ether. MeLi (50 ml, 1.4 M in ether, 0.070 mol) was
slowly added and the mixture was allowed to stir for two hours. The
solvent was removed leaving behind 10.2 g (0.035 mol) of the yellow
solid, Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4
(N-n-Bu)].cndot.1/3Et.sub.2 O.
Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5
Me.sub.4)(N-n-Bu)].cndot.1/3Et.sub.2 O (6.0 g, 0.021 mol) was
suspended in cold ether. TiCl.sub.4.cndot.2Et.sub.2 O (7.04 g,
0.0212 mol) was slowly added and the mixture was allowed to stir
overnight. The solvent was removed and dichloromethane was added.
The mixture was filtered through Celite to remove the LiCl. The
filtrate was reduced in volume and petroleum ether was added. The
mixture was refrigerated to maximize precipitation prior to
filtering off a mixture of dark powder and yellow crystals. The
material was redissolved in a mixture of dichloromethane and
toluene. A small portion of petroleum ether was added and the brown
precipitate was filtered off and discarded. The filtrate was
reduced in volume, additional petroleum ether was added and the
mixture was placed back in the refrigerator. Later, 3.65 g of the
maize yellow solid, Me.sub.2 Si(C.sub.5 Me.sub.4)(N-n-Bu)TiCl.sub.2
was filtered off.
EXAMPLE ST
Compound ST: Part 1. Me.sub.2 SiCl.sub.2 (210 ml, 1.25 mol) was
diluted with a mixture of ether and thf. LiMeC.sub.5 H.sub.4 (25 g,
0.29 mol) was slowly added, and the resulting mixture was allowed
to stir for a few hours, after which time the solvent was removed
in vacuo. Pentane was added to precipitate 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(Me.sub.5 H.sub.4)Cl.
Part 2. Me.sub.2 Si(MeC.sub.5 H.sub.4)Cl (10.0 g, 0.058 mol) was
diluted with a mixture of ether and thf. To this, LiHNC.sub.12
H.sub.23 (11.0 g, 0.058 mol) was slowly added. The mixture was
allowed to stir overnight. The solvent was removed via vacuum and
toluene and pentane were added to precipitate the LiCl. The solvent
was removed from the filtrate leaving behind a pale yellow liquid,
Me.sub.2 Si(MeC.sub.5 H.sub.4)(HNC.sub.12 H.sub.23) (18.4 g, 0.058
mol).
Part 3. Me.sub.2 Si(MeC.sub.5 H.sub.4)(HNC.sub.12 H.sub.23) (18.4
g, 0.058 mol) was diluted in ether. MeLi (1.4 M in ether, 82 ml,
0.115 mol) was slowly added, the reaction was allowed to stir for
several hours before reducing the mixture in volume and then
filtering off the white solid, Li.sub.2 [Me.sub.2 Si(MeC.sub.5
H.sub.3) (NC.sub.12 H.sub.23)] (14.3 g, 0.043 mol).
Part 4. Li.sub.2 [Me.sub.2 Si(MeC.sub.5 H.sub.3)(NC.sub.12
H.sub.23)] (7.7 g, 0.023 mol) was suspended in cold ether.
TiCl.sub.4.cndot.2Et.sub.2 (7.8 g, 0.023 mol) was slowly added and
the mixture was allowed to stir overnight. The solvent was removed
via vacuum. Dichloromethane was added and the mixture was filtered
through Celite. The dichloromethane was reduced in volume and
petroleum ether was added to maximize precipitation. This mixture
was then refrigerated for a short period of time prior to filtering
off a yellow/green solid identified as Me.sub.2 Si (MeC.sub.5
H.sub.3)(NC.sub.12 H.sub.23)TiCl.sub.2 (5.87 g, 0.013 mol).
EXAMPLE TT
Compound TT: Part 1. Me.sub.2 SiCl.sub.2 (7.5 ml, 0.062 mol) was
diluted with .about.30 ml of thf. A t-BuH.sub.4 C.sub.5 Li solution
(7.29 g, 0.057 mol .about.100 ml of thf) was slowly added, and the
resulting mixture was allowed to stir overnight. The thf was
removed in vacuo. Pentane was add to precipitate 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-BuC.sub.5 H.sub.4)Cl (10.4 g, 0.048 mol).
Part 2. Me.sub.2 Si(t-BuC.sub.5 H.sub.4)Cl (8.0 g, 0.037 mol) was
diluted with thf. To this, LiHNC.sub.12 H.sub.23 (7.0 g, 0.037 mol)
was slowly added. The mixture was allowed to stir overnight. The
solvent was removed via vacuum and toluene was added to precipitate
the LiCl. The toluene was removed from the filtrate leaving behind
a pale yellow liquid, Me.sub.2 Si(t-BuC.sub.5 H.sub.4)(HNC.sub.12
H.sub.23) (12.7 g, 0.035 mol).
Part 3. Me.sub.2 Si(t-BuC.sub.5 H.sub.4)(HCN.sub.12 H.sub.23) (12.7
g, 0.035 mol) was diluted with ether. To this, MeLi (1.4 M in
ether, 50 ml, 0.070 mol) was slowly added. This was allowed to stir
for two hours prior to removing the solvent via vacuum. The
product, Li.sub.2 [Me.sub.2 Si(t-Bu-C.sub.5 H.sub.3)(NC.sub.12
H.sub.23)] (11.1 g, 0.030 mol) was isolated.
Part 4. Li.sub.2 [Me.sub.2 Si(t-BuC.sub.5 H.sub.3)(NC.sub.12
H.sub.23)] (10.9 g, 0.029 mol) was suspended in cold ether.
TiCl.sub.4.cndot.2Et.sub.2 O (9.9 g, 0.029 mol) was slowly added
and the mixture was allowed to stir overnight. The solvent was
removed via vacuum. Dichloromethane was added and the mixture was
filtered through Celite. The solvent was removed and pentane was
added. The product is completely soluble in pentane. This solution
was passed through a column containing a top layer of silica and a
bottom layer of Celite. The filtrate was then evaporated down to an
olive green colored solid identified as Me.sub.2 Si(t-BuC.sub.5
H.sub.3)(NC.sub.12 H.sub.23)TiCl.sub.2 (5.27 g, 0.011 mol).
EXAMPLE UT
Compound UT
Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiMe.sub.2 was
prepared by adding a stoichiometric amount of MeLi (1.4 M in ether)
to Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiCl.sub.2
(Compound JT from Example JT) suspended in ether. The white solid
recrystallized from toluene and petroleum ether was isolated in a
57% yield.
EXAMPLE 40
Polymerization--Compound AT
The polymerization run was performed in a .[.12.].
.Iadd.1.Iaddend.-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 or
comonomers, 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, 5 ml of 1.0 M MAO,
0.206 mg compound AT (0.2 ml of a 10.3 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 (11.8 g, MW=279,700, MWD=2.676).
EXAMPLE 41
Polymerization--Compound AT
Using the same reactor design and general procedure as described in
Example 40, 400 ml of toluene, 5.0 ml of 1.0 M MAO, and 0.2 ml of a
preactivated compound AT solution (10.3 mg of compound AT dissolved
in 9.5 ml of toluene and 0.5 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, 14.5 g of polyethylene was recovered
(MW=406,100, MWD=2.486).
EXAMPLE 42
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1.0 M
MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 80.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
48.6 g of an ethylene-1-hexene copolymer was recovered (MW 98,500,
MWD=1.745, 117 SCB/1000C by .sup.13 C NMR).
EXAMPLE 43
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M
MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 80.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
29.2 g of an ethylene-1-hexene copolymer was recovered (MW=129,800,
MWD=2.557, 53.0 SCB/1000C by .sup.13 C NMR).
EXAMPLE 44
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M
MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 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 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
15.0 g of an ethylene-1-hexene copolymer was recovered (MW=310,000,
MWD=2.579, 47.2 SCB/1000C by .sup.13 C NMR).
EXAMPLE 45
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 300 ml of toluene, 100 ml of propylene, 7.0 ml of 1.0 M
MAO, and 2.06 mg of compound AT (2.0 ml of a 10.3 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 80.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
46.0 g of an ethylene-propylene copolymer was recovered
(MW=110,200, MWD=5.489, 20 wt % ethylene by IR).
EXAMPLE 46
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M
MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 80.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
35.1 g of an ethylene-1-butene copolymer was recovered (MW=94,400,
MWD=2.405, 165 SCB/1000C by .sup.13 C NMR).
EXAMPLE 47
Polymerization--Compound AT
Using the same reactor design and general procedure described in
Example 40, 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0 M
MAO, and 1.04 mg of compound AT (1.0 ml of a 10.4 mg in 10 ml of
toluene solution) were added to the reactor. The reactor was heated
at 80.degree. C., the ethylene was introduced (65 psi), and the
reaction was allowed to run for 10 minutes, followed by rapidly
cooling and venting the system. After evaporation of the toluene,
30.6 g of an ethylene-1-octene copolymer was recovered (MW=73,100,
MWD=2.552, 77.7 SCB/1000C by .sup.13 C NMR).
EXAMPLE 53
Polymerization--Compound AT
The polymerization was performed in a stirred 100 ml stainless
steel autoclave which was equipped to perform polymerizations at
temperatures up to 300.degree. C. and pressures up to 2500 bar. The
reactor was evacuated, purged with nitrogen, purged with ethylene
and heated to 200.degree. C. 1-hexene (75 ml) was added to the
reactor under ethylene pressure. A stock solution of compound AT
was prepared by dissolving 6.5 mg of compound AT in 12.5 ml of
toluene. The test solution was prepared by adding 1.0 ml of the
compound AT stock solution to 1.9 ml of 1.0 M MAO solution,
followed by 7.1 ml of toluene. The test solution (0.43 ml) was
transferred by nitrogen pressure into a constant-volume injection
tube. The autoclave was pressurized with ethylene to 1748 bar and
was stirred at 1800 rpm. The test solution was injected into the
autoclave with excess pressure, at which time a temperature rise of
16.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 polymer remaining
within. These washings were combined with the polymer released when
the reactor was vented. Precipitation of the polymer from the
mixture by addition of acetone yielded 2.7 g of polymer (MW=64,000,
MWD=3.16, 14.7 SCB/1000C by IR).
EXAMPLE 54
Polymerization--Compound AT
For this Example a stirred 1 L steel autoclave reaction vessel
which was equipped to perform continuous Ziegler polymerization
reactions at pressures to 2500 bar and temperatures up to
300.degree. C. was used. The reaction system was supplied with a
thermocouple and pressure transducer to measure temperature and
pressure continuously, and with means to supply continuously
purified compressed ethylene and 1-butene (or propylene). Equipment
for continuously introducing a measured flow of catalysts solution,
and equipment for rapidly venting and quenching the reaction, and
of collecting the polymer product were also a part of the reaction
system. The polymerization was performed with a molar ratio of
.[.ethylene to 1-butene.]. .Iadd.1-butene to ethylene .Iaddend.of
1.6 without the addition of a solvent. The temperature of the
cleaned reactor containing ethylene and 1-butene was equilibrated
at the desired reaction temperature of 180.degree. C. The catalyst
solution was prepared by mixing 0.888 g of solid compound AT with
0.67 L of a 30 wt % methylalumoxane solution in 4.3 L of toluene in
an inert atmosphere. This catalyst solution was continuously fed by
a high pressure pump into the reactor at a rate of 0.56 L/hr which
resulted in a temperature of 180.degree. C. in the reactor. During
this run, ethylene and 1-butene were pressured into the autoclave
at a total pressure of 1300 bar. The reactor contents were stirred
at 1000 rpm. The yield of polymer products was 3.9 kg/hr of an
ethylene-1-butene copolymer which had a weight average molecular
weight of 50,200, a molecular weight distribution of 2.36 and 60.1
SCB/1000C as measured by .sup.13 C NMR.
EXAMPLE 55
Polymerization--Compound AT
Using the same reactor design as described in Example 54, and using
a molar ratio of .[.ethylene to propylene.]. .Iadd.propylene to
ethylene .Iaddend.of 2.6 without the addition of a solvent. The
temperature of a cleaned reactor containing ethylene and propylene
was equilibrated at the desired reaction temperature of 140.degree.
C. The catalyst solution was prepared by mixing 0.779 g of solid
compound AT with 0.5 L of a 30 wt % methylalumoxane solution in
24.5 L of toluene in an inert atmosphere. This catalyst solution
was continuously fed by a high pressure pump into the reactor at a
rate of 0.9 L/hr which resulted in a temperature of 140.degree. C.
in the reactor. During this run, ethylene and propylene were
pressured into the autoclave at a total pressure of 2200 bar. The
reactor contents were stirred at 1000 rpm. The yield of polymer
product was 2.3 kg/hr of an ethylene-propylene copolymer which had
a weight average molecular weight of 102,700, a molecular weight
distribution of 2.208 and a density of 0.863 g/cc.
EXAMPLE 56
Polymerization--Compound FT
Using the same reactor design as described in Example 54, and using
a molar ratio of .[.ethylene to 1-butene.]. .Iadd.1-butene to
ethylene .Iaddend.of 1.6 without the addition of a solvent. The
temperature of the cleaned reactor containing ethylene and 1-butene
was equilibrated at the desired reaction temperature of 180.degree.
C. The catalyst solution was prepared by mixing 0.859 g of solid FT
with 30 wt % methylalumoxane solution and toluene such that the
catalyst concentration was 0.162 g/L with an Al/M molar ratio of
1200. The preparation was done under an inert atmosphere. This
catalyst solution was continuously fed by a high pressure pump into
the reactor at a rate of 1.15 L/hr which resulted in a temperature
of 180.degree. C. in the reactor. During this run, ethylene and
1-butene were pressured into the autoclave at a total pressure of
1300. The reactor contents were stirred at 1000 rpm. The yield of
polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer
which had a weight average molecular weight of 61,400, a molecular
weight distribution of 2.607 and 104.8 SCB/1000C by .sup.13 C
NMR.
EXAMPLE 58
Polymerization--Compound AT
Using the same reactor design as described in Example 54, and using
a molar ratio of .[.ethylene to 1-butene.]. .Iadd.1-butene to
ethylene .Iaddend.of 1.6 without the addition of a solvent, the
temperature of the cleaned reactor containing ethylene and 1-butene
was equilibrated at the desired reaction temperature of 170.degree.
C. The catalyst solution was prepared by mixing 0.925 g of solid
compound AT with 2 L of a 10 wt % methylalumoxane solution in 8 L
of toluene in an inert atmosphere. This catalyst solution was
continuously fed by a high pressure pump into the reactor at a rate
of 0.28 L/hr which resulted in a temperature of 170.degree. C. in
the reactor. During this run, ethylene and 1-butene were pressured
into the autoclave at a total pressure of 1300 bar. The reactor
contents were stirred at 1000 rpm. The yield of polymer product was
3.7 kg/hr of an ethylene-1-butene copolymer which had a weight
average molecular weight of 69,500, a molecular weight distribution
of 2.049 and 35.7 SCB/1000C by .sup.13 C NMR.
EXAMPLE 67
Polymerization--Compound IT
Using the same reactor design as described in Example 54, and using
a molar ratio of .[.ethylene to 1-butene.]. .Iadd.1-butene to
ethylene .Iaddend.of 1.6 without the addition of a solvent, the
temperature of the cleaned reactor containing ethylene and 1-butene
was equilibrated at the desired reaction temperature of 180.degree.
C. The catalyst solution was prepared by mixing 1.94 g of solid
compound IT with 30 wt % methylalumoxane solution and toluene such
that the catalyst concentration was 0.388 g/L and the Al/M molar
ratio was 600. The preparation was done under an inert atmosphere.
This catalyst solution was continuously fed by a high pressure pump
into the reactor at a rate of 0.42 L/hr which resulted in a
temperature of 180.degree. C. in the reactor. During this run,
ethylene and 1-butene were pressured into the autoclave at a total
pressure of 1300 bar. The reactor contents were stirred at 1000
rpm. The yield of polymer product was 3.9 kg/hr of an
ethylene-1-butene copolymer which had a weight average molecular
weight of 50,800, a molecular weight distribution of 2.467 and 69
SCB/1000C as measured by .sup.1 H NMR.
EXAMPLE 70
Polymerization--Compound JT
Using the same reactor design as described in Example 54, and using
a molar ratio of .[.ethylene to 1-butene.]. .Iadd.1-butene to
ethylene .Iaddend.of 1.6 without the addition of a solvent, the
temperature of the cleaned reactor containing ethylene and 1-butene
was equilibrated at the desired reaction temperature of 180.degree.
C. The catalyst solution was prepared by mixing 1.78 g of solid
compound JT with 30 wt % methylalumoxane solution and toluene such
that the catalyst concentration was 0.318 g/L and the Al/M molar
ratio was 1400. The preparation was done under an inert atmosphere.
This catalyst solution was continuously fed by a high pressure pump
into the reactor at a rate of 0.55 L/hr which resulted in a
temperature of 180.degree. C. in the reactor. During this run,
ethylene and 1-butene were pressured into the autoclave at a total
pressure of 1300 bar. The reactor contents were stirred at 1000
rpm. The yield of polymer product was 3.9 kg/hr of an
ethylene-1-butene copolymer which had a weight average molecular
weight of 72,600, a molecular weight distribution of 2.385 and 110
SCB/1000C as measured by .sup.1 H NMR.
EXAMPLES 71-86
Each of the compounds of Examples KT through TT were used to
prepare an ethylene-1-butene copolymer. The polymerization
reactions were carried out in the same reactor design as described
in Example 54. .[.With the sole exception of Example 83 all.].
.Iadd.All .Iaddend.polymerizations were carried out using a molar
ratio of 1-butene to ethylene of 1.6 without the addition of a
solvent. .[.In Example 83 a 1-butene to ethylene ratio of 2.0 was
used..]. The temperature of the cleaned reactor containing ethylene
and 1-butene was equilibrated at the desired reaction temperature
of 180.degree. C.
The catalyst solution was prepared by mixing a specified amount of
solid transition metal component with a 30 weight percent
methylalumoxane solution and this catalyst solution was then
further diluted in toluene under an inert atmosphere. This catalyst
solution was continuously fed by a high pressure pump into the
reactor at a rate which resulted in the desired reactor temperature
of 180.degree. C. which was the polymerization temperature for all
examples. The reactor contents were stirred at 1000 rpm and a
reactor mass flow rate of 40 .[.kg/g.]. .Iadd.kg/hr .Iaddend.was
used for all examples. The reactor pressure was maintained at 1300
bar and no hydrogen was supplied to the reactor. Exact run
conditions including catalyst preparation [transition metal
component (TMC) and amount (g), methylalumoxane (MAO) volume used
(L), total volume of catalyst solution (L) and concentration (g
TMC/L) and (g MAO/L)], catalyst feed rate (L/hr), polymer
production rate (kg polymer/hr), molar Al/M ratio, productivity (kg
polymer/g catalyst) and polymer characteristics including weight
average MW (Daltons), molecular weight distribution (MW/MN), melt
index (.[.10 g/minute.]. .Iadd.g/10 minutes .Iaddend.at 190.degree.
C.), weight percent comonomer (determined by .sup.1 H NMR or
.sup.13 C NMR), and catalyst reactivity ratios (r.sub.1) are
collected in Table 1.
TABLE 1 Feed Pro- TMC Catalyst Total TMC MAO Rate duction Produc-
Produc- Wt Ex. TMC MAO Vol (g/ (g/ (L/ Rate Al/ tivity tivity % #
(g) (L) (L) (L) (L) hr) (kg/hr) M (kg/g) (kg/g) MW MWD MI C4 Method
I.sub.1 JT 71 0.540 0.4 10 0.0540 10.4 1.75 5.1 1595 54 0.28 63.600
2.363 11.3 42.0 1HMMR 4.4 KT 72 2.259 1.8 6 0.3765 78.3 0.51 3.9
1723 20 0.10 84.100 4.775 3.3 40.8 1HMMR 4.7 LT 73 1.480 1.2 8
0.1850 39.2 0.46 4.0 1541 48 0.22 72.700 3.610 7.9 42.0 1HMMR 4.4
MT 74 1.366 1.0 6 0.2277 43.5 0.58 4.0 1398 31 0.16 78.300 4.601
5.0 40.8 1HMMR 4.7 FT 75 0.859 0.6 5.3 0.1620 29.5 1.14 4.2 1239 23
0.12 61.400 2.607 13.2 41.9 13CMMR 4.4 NT 76 1.441 1.2 8 0.1801
39.2 1.51 4.4 1485 16 0.07 85.400 3.971 3.6 44.0 1HMMR 4.1 AT 77
0.888 0.7 5 0.1776 35.0 0.56 4.35 1461 44 0.22 50.200 2.360 19 24.0
13CMMR 10 OT 78 1.934 1.3 6 0.3223 54.4 0.62 4.3 1252 22 0.13
64.600 2.494 8.1 43.6 13CMMR 4.1 PT 79 1.500 1.3 6 0.3167 54.4 0.96
3.75 1274 12 0.07 71.200 2.259 3.8 41.1 13CMMR 4.6 IT 80 0.878 0.8
10 0.0878 19.6 0.84 4.3 1416 59 0.26 63.600 2.751 6.6 32.4 1HMMR
6.7 QT 81 0.953 0.9 10 0.0953 23.5 1.32 4.9 1565 39 0.16 64.500
2.342 10 42.8 1HMMR 4.3 RT 82 0.885 0.9 10 0.0885 23.5 1.68 4.65
1685 31 0.12 71.100 2.262 8.8 40.0 1HMMR 4.8 JT 83 1.494 0.5 10
0.1494 13.1 1.02 3.9 721 26 0.29 78.200 2.617 5.2 40.8 1HMMR 4.6 ST
84 3.053 1.0 12 0.2540 21.8 0.51 2.9 643 22 0.26 60.500 2.183 8.5
17.62 13CMMR 15.0 TT 85 3.043 1.0 18 0.1690 14.5 1.11 2.6 708 14
0.16 53.900 2.308 13.8 17.38 13CMMR 15.2 UT 86 1.566 1.0 5 0.3132
52.2 0.35 5.0 1258 46 0.27 70.200 2.441 4.6 46.4 13CMMR 3.7
By appropriate selection of (1) 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;
(4) reaction temperature; and (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.
From the above examples, particularly as collected in Table 1, it
appears that for a catalyst system wherein the group IV B
transition metal component is a titanium species of the following
structure: ##STR5##
the nature of the R' group dramatically influence the catalytic
properties of the system. For production of ethylene-.alpha.-olefin
copolymers of greatest comonomer content, at a selected ethylene to
.alpha.-olefin monomer ratio, R' is preferably a non-aromatic
substituent, such as an alkyl or cycloalkyl substituent preferably
bearing a primary or secondary carbon atom attached to the nitrogen
atom.
Further, from the above data, the nature of the Cp ligand structure
of a Ti metal component may be seen to influence the properties of
the catalyst system. Those Cp ligands which are not too sterically
hindered and which contain good electron donor groups, for example
the Me.sub.4 C.sub.5 ligand, are preferred.
From the standpoint of having a catalyst system of high
productivity which is capable of producing an
ethylene-.alpha.-olefin copolymer of high molecular weight and high
comonomer incorporation, the most preferred transition metal
compound for the catalyst system is of the following structure:
##STR6##
wherein R.sup.1 and R.sup.2 are alkyl radicals having 1 to 6 carbon
atoms, each Q is chlorine or methyl, and R' is an aliphatic or
alicyclic hydrocarbyl having from 1 to 20 carbon atoms, preferably
3 to 20 carbon atoms.
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.
* * * * *