U.S. patent application number 10/968546 was filed with the patent office on 2006-01-19 for catalyst compounds, catalyst systems thereof and their use in a polymerization process.
Invention is credited to Donna J. Crowther, Phillip T. Matsunaga.
Application Number | 20060014632 10/968546 |
Document ID | / |
Family ID | 26917310 |
Filed Date | 2006-01-19 |
United States Patent
Application |
20060014632 |
Kind Code |
A9 |
Crowther; Donna J. ; et
al. |
January 19, 2006 |
Catalyst compounds, catalyst systems thereof and their use in a
polymerization process
Abstract
The present invention relates to a cyclic germanium bridged
bulky ligand metallocene-type catalyst compound, a catalyst system
thereof, and to its use in a process for polymerizing olefin(s) to
produce enhanced processability polymers.
Inventors: |
Crowther; Donna J.;
(Seabrook, TX) ; Matsunaga; Phillip T.; (Houston,
TX) |
Correspondence
Address: |
ExxonMobile Chemical Company
P.O. Box 2149
Baytown
TX
77522-2149
US
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20050054521 A1 |
March 10, 2005 |
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Family ID: |
26917310 |
Appl. No.: |
10/968546 |
Filed: |
October 19, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09955507 |
Sep 18, 2001 |
6818585 |
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10968546 |
Oct 19, 2004 |
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09451805 |
Dec 1, 1999 |
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09955507 |
Sep 18, 2001 |
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09222973 |
Dec 30, 1998 |
6034192 |
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09451805 |
Dec 1, 1999 |
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Current U.S.
Class: |
502/117 ;
502/108; 502/152 |
Current CPC
Class: |
C08F 210/16 20130101;
C08F 210/16 20130101; C08F 4/65916 20130101; C08F 110/02 20130101;
C08F 10/00 20130101; C08F 2500/03 20130101; C08F 210/16 20130101;
C08F 2500/11 20130101; C08F 2500/11 20130101; C08F 2500/10
20130101; C08F 2500/18 20130101; C08F 210/08 20130101; C08F 210/14
20130101; C08F 2500/11 20130101; C08F 2500/12 20130101; C08F
2500/11 20130101; C08F 2500/10 20130101; C08F 210/14 20130101; C08F
2500/12 20130101; C08F 210/14 20130101; C08F 4/65927 20130101; C08F
2500/18 20130101; C08F 4/65927 20130101; C08F 10/00 20130101; Y10S
526/943 20130101; C08F 4/65912 20130101; C08F 210/16 20130101; C08F
4/65908 20130101; C08F 210/16 20130101; C08F 210/16 20130101; C08F
110/02 20130101 |
Class at
Publication: |
502/117 ;
502/152; 502/108 |
International
Class: |
B01J 31/00 20060101
B01J031/00 |
Claims
1. A catalyst system for polymerizing ethylene alone or in
combination with one or more olefin(s), comprising a cyclic
germanium bridged catalyst compound and an activator, wherein the
cyclic germanium bridged catalyst compound is represented by the
formula: L.sup.A(R'GeR').sub.xL.sup.BMQ.sub.n (I) where M is a
Group 3 to 7 transition metal, each of L.sup.A and L.sup.B is an
unsubstituted or substituted ligand, wherein L.sup.A and L.sup.B
may be the same or different, wherein the ligand is selected from
the group consisting of cyclopentadienyl ligands, pentadiene
ligands, cyclooctatetraendiyl ligands, imide ligands, indenyl
ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl
ligands, azenyl ligands, azulene ligands, pentalene ligands,
phosphoryl ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl
ligands, borabenzene ligands, amide ligands, phosphide ligands
alkoxide ligands, dicarbollide ligands, borollide ligands,
porphyrin ligands, phthalocyanine ligands, corrin ligands,
polyazamacrocycle ligands, and hydrogenated versions of each, said
ligands bonded to M; (R'GeR').sub.x is a cyclic bridging group
bridging L.sup.A and L.sup.B, and the two R''s are joined to form a
cyclic ring or ring system with Ge; independently, each Q is a
monoanionic ligand, or optionally two Q's together form a divalent
anionic chelating ligand; and where n is 0, 1 or 2 depending on the
formal oxidation state of M, and x is an integer from 1 to 4 and
wherein the catalyst system is supported.
2. The catalyst system of claim 1, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of a substituted
cyclopentadienyl, a substituted indenyl, and a substituted
fluorenyl.
3. The catalyst system of claim 1, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of an unsubstituted
cyclopentadienyl, an unsubstituted indenyl, and an unsubstituted
fluorenyl.
4. The catalyst system of claim 2 or claim 3, wherein said one of
L.sup.A or L.sup.B is hydrogenated.
5. The catalyst system of claim 1, wherein x is 1.
6. The catalyst system of claim 1, wherein M is a Group 4, 5, 6
transition metal.
7. The catalyst system of claim 6, where x is 1.
8. The catalyst system of claim 6, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of a substituted
cyclopentadienyl, a substituted indenyl, and a substituted
fluorenyl.
9. The catalyst system of claim 6, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of an unsubstituted
cyclopentadienyl, an unsubstituted indenyl, and an unsubstituted
fluorenyl.
10. The catalyst system of claim 8 or claim 9, wherein said one of
L.sup.A or L.sup.B is hydrogenated.
11. A catalyst system for polymerizing ethylene alone or in
combination with one or more olefin(s), comprising a cyclic
germanium bridged catalyst compound and an activator, wherein the
cyclic germanium bridged catalyst compound is represented by the
formula: L.sup.A(R'GeR').sub.xL.sup.BMQ.sub.n (I) where M is a
Group 3 to 7 transition metal, each of L.sup.A and L.sup.B is an
unsubstituted or substituted ligand, wherein L.sup.A and L.sup.B
may be the same or different, said ligand selected from the group
consisting of, cyclopentadienyl ligands, pentadiene ligands,
cyclooctatetraendiyl ligands, imide ligands, indenyl ligands,
benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands,
azenyl ligands, azulene ligands, pentalene ligands, phosphoryl
ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands,
borabenzene ligands, amide ligands, phosphide ligands alkoxide
ligands, dicarbollide ligands, borollide ligands, porphyrin
ligands, phthalocyanine ligands, corrin ligands, polyazamacrocycle
ligands, and hydrogenated versions thereof, said ligands bonded to
M; (R'GeR').sub.x is a cyclic bridging group bridging L.sup.A and
L.sup.B, and the two R''s are joined to form a cyclic ring or ring
system with Ge; independently, each Q is a monoanionic ligand, or
optionally two Q's together form a divalent anionic chelating
ligand; and where n is 0, 1 or 2 depending on the formal oxidation
state of M, and x is an integer from 1 to 4 and wherein the
catalyst system is supported, and wherein said L.sup.A and L.sup.B
may be substituted with a combination of substituent groups R, said
R groups may be one or more of hydrogen, linear or branched alkyl
radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl
radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy
radicals, aryloxy radicals, alkylthio radicals, dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals,
carbamoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy
radicals, acylamino radicals, aroylamino radicals, straight,
branched or cyclic alkylene radicals, or combination thereof.
12. The catalyst system of claim 11, wherein said R groups are
selected from the group consisting of methyl, ethyl, propyl, butyl,
pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl and phenyl groups
and their isomers.
13. The catalyst system of claim 11, wherein said R groups are one
or more of fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl,
bromohexyl, chlorobenzyl or hydrocarbyl substituted organometalloid
radicals; or halocarbyl-substituted organometalloid radicals; or
disubstitiuted boron radicals; or disubstituted pnictogen radicals,
or chalcogen radicals.
14. The catalyst system of claim 13, wherein said hydrocarbyl
substituted organometalloid radicals comprise trimethylsilyl,
trimethylgermyl, or methyldiethylsilyl; and said
halocarbyl-substituted organometalloid radicals comprise
tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, or
bromomethyldimethylgermyl; and said disubstitiuted boron radicals
comprise dimethylboron; and said disubstituted pnictogen radicals
comprise dimethylamine, dimethylphosphine, diphenylamine, or
methylphenylphosphine; said chalcogen radicals comprise methoxy,
ethoxy, propoxy, phenoxy, methylsulfide or ethylsulfide.
15. The catalyst system of claim 11, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of a substituted
cyclopentadienyl, a substituted indenyl, and a substituted
fluorenyl.
16. The catalyst system of claim 11, wherein one of L.sup.A or
L.sup.B is selected from the group consisting of an unsubstituted
cyclopentadienyl, an unsubstituted indenyl, and an unsubstituted
fluorenyl.
17. The catalyst system of claim 15 or claim 16, wherein said one
of L.sup.A or L.sup.B is hydrogenated.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a divisional of and claims
priority to U.S. Ser. No. 09/451,805 filed Dec. 01, 1999, herein
incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to catalyst compounds,
catalyst systems incorporating these compounds and to their use in
a process for polymerizing olefin(s). More particularly the
catalyst compounds are cyclic germanium bridged bulky ligand
metallocene-type catalyst compounds and catalyst system thereof.
The invention is also directed to the use of this catalyst system
in the polymerization of olefin(s) to produce polymers that have a
combination of properties that make them easier to process into
various articles of manufacture.
BACKGROUND OF THE INVENTION
[0003] Processability is the ability to economically process and
shape a polymer uniformly. Processability involves such elements as
how easily the polymer flows, melt strength, and whether or not the
extrudate is distortion free. Typical bulky ligand metallocene-type
catalyzed polyethylenes (mPE) are somewhat more difficult to
process than low density polyethylenes (LDPE) made in a high
pressure polymerization process. Generally, mPE's require more
motor power and produce higher extruder pressures to match the
extrusion rate of LDPE's. This is typically evident where a polymer
exhibits a low melt index ratio. Typical mPE's also have lower melt
strength which, for example, adversely affects bubble stability
during blown film extrusion, and they are prone to melt fracture at
commercial shear rates. On the other hand, however, mPE's exhibit
superior physical properties as compared to LDPE's.
[0004] It is now common practice in the industry to add various
levels of an LDPE to an mPE to increase melt strength, to increase
shear sensitivity, i.e., to increase flow at commercial shear
rates; and to reduce the tendency to melt fracture. However, these
blends generally have poor mechanical properties as compared with
neat mPE.
[0005] Traditionally, metallocene catalysts produce polymers having
a narrow molecular weight distribution. Narrow molecular weight
distribution polymers tend to be more difficult to process. The
broader the polymer molecular weight distribution the easier the
polymer is to process. A technique to improve the processability of
mPE's is to broaden the products' molecular weight distribution
(MWD) by blending two or more mPE's with significantly different
molecular weights, or by changing to a polymerization catalyst or
mixture of catalysts that produce broad MWD polymers.
[0006] In the art specific bulky ligand metallocene-type catalyst
compound characteristics have been shown to produce polymers that
are easier to process. For example, U.S. Pat. No. 5,281,679
discusses bulky ligand metallocene-type catalyst compounds where
the bulky ligand is substituted with a substituent having a
secondary or tertiary carbon atom for the producing of broader
molecular weight distribution polymers. U.S. Pat. No. 5,470,811
describes the use of a mixture of bulky ligand metallocene-type
catalysts for producing easy processing polymers. Also, U.S. Pat.
No. 5,798,427 addresses the production of polymers having enhanced
processability using a bulky ligand metallocene-type catalyst
compound where the bulky ligands are specifically substituted
indenyl ligands.
[0007] A need exists in the industry for catalyst compounds and
catalyst systems that in a polymerization process produce polymers
having a combination of properties for use in various end-use
applications.
SUMMARY OF THE INVENTION
[0008] This invention relates to a catalyst compound, a catalysts
system thereof and to their use in a polymerization process. The
catalyst compound is a cyclic bridge, preferably a cyclic germanium
bridged bulky ligand metallocene-type compound. In one embodiment,
this cyclic germanium bridged bulky ligand metallocene-type
catalyst compound is activated or combined with an activator to
form a catalyst system. In another embodiment, the invention is
directed to a polymerization process utilizing this catalyst
system. The preferred polymerization processes are a gas phase or a
slurry phase process, most preferably a gas phase process,
especially where the catalyst system is supported.
[0009] In one preferred embodiment, the invention provides for a
process for polymerizing ethylene alone or in combination with one
or more other olefin(s) in the presence of a catalyst system of a
cyclic germanium bridged bulky ligand metallocene-type catalyst
compound, preferably a cyclic germanium bridged bulky ligand
metallocene-type catalyst compound and an activator.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
[0010] The invention relates to a catalyst compound, a catalyst
system thereof and to it use in a polymerization process for
producing polymers having a balance of properties needed for
processing the polymers into various end-use applications, such as
film. It has been surprisingly discovered that using a cyclic
germanium bridged bulky ligand metallocene-type catalyst of the
invention, particularly in a slurry or gas phase polymerization
process, polymers having a high Melt Index Ratio (MIR) and high
Melt Strength (MS) are produced. It was previously found that
cyclic bridged bulky ligand metallocene-type catalyst system
produce polymers having a high MIR, however, the melt strength
needed improvement. For example, U.S. patent application Ser. No.
09/306,142 filed May 6, 1999 illustrates a cyclic silicon bridged
bulky ligand metallocene-type catalyst system for producing
polymers having a high MIR, which is fully incorporated herein by
reference. Also, U.S. patent application Ser. No. 09/222,973 filed
Dec. 30, 1998 discusses a germanium bridged bulky ligand
metallocene-type catalyst system in a polymerization process for
producing polymers having better melt strength, which is fully
incorporated herein by reference. It is highly unusual in the art
that a combination of catalyst compound structures provide the
benefits to a particular polymer product that each bring
separately. Thus, it was surprising and totally unexpected that the
cyclic germanium bridged bulky ligand metallocene-type catalyst
compounds would produce in a polymerization process a polymer
having both a high MIR and MS.
Cyclic Ge Bridged Bulky Ligand Metallocene-Type Catalyst
Compounds
[0011] Generally, bulky ligand metallocene-type catalyst compounds
include half and full sandwich compounds having one or more bulky
ligands bonded to at least one metal atom. Typical bulky ligand
metallocene-type compounds are generally described as containing
one or more bulky ligand(s) and one or more leaving group(s) bonded
to at least one metal atom. In one preferred embodiment, at least
one bulky ligand is .eta.-bonded to a metal atom, most preferably
.eta..sup.5-bonded to the metal atom.
[0012] For purposes of this patent specification and appended
claims a cyclic germanium bridge is one in which the germanium
element(s) serves as the bridging element(s) between at least two
bulky ligands and "cyclic" refers to the atoms forming a ring or
ring system containing the germanium element(s).
[0013] The bulky ligands are generally represented by one or more
open, acyclic, or fused ring(s) or ring system(s) or a combination
thereof. These bulky ligands, preferably ring(s) or ring system(s)
are typically composed of atoms selected from Groups 13 to 16 atoms
of the Periodic Table of Elements, preferably the atoms are
selected from the group consisting of carbon, nitrogen, oxygen,
silicon, sulfur, phosphorous, boron and aluminum or a combination
thereof. Most preferably the ring(s) or ring system(s) are composed
of carbon atoms such as but not limited to those cyclopentadienyl
ligands or cyclopentadienyl-type ligand structures or other similar
functioning ligand structure such as a pentadiene, a
cyclooctatetraendiyl or an imide ligand. The metal atom is
preferably selected from Groups 3 through 15 and the lanthanide or
actinide series of the Periodic Table of Elements. Preferably the
metal is a transition metal from Groups 4 through 12, more
preferably 4, 5 and 6, and most preferably the metal is from Group
4.
[0014] In one embodiment, cyclic germanium bridged bulky ligand
metallocene-type catalyst compounds are represented by the formula:
L.sup.A(AGe)L.sup.BMQ.sub.n (I) where M is a metal atom from the
Periodic Table of the Elements and may be a Group 3 to 12 metal or
from the lanthanide or actinide series of the Periodic Table of
Elements, preferably M is a Group 4, 5 or 6 transition metal, more
preferably M is a Group 4 transition metal, even more preferably M
is zirconium, hafnium or titanium. The bulky ligands, L.sup.A and
L.sup.B, are open, acyclic, or fused ring(s) or ring system(s) such
as unsubstituted or substituted, cyclopentadienyl ligands or
cyclopentadienyl-type ligands, heteroatom substituted and/or
heteroatom containing cyclopentadienyl-type ligands. Non-limiting
examples of bulky ligands include cyclopentadienyl ligands, indenyl
ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl
ligands, cyclooctatetraendiyl ligands, azenyl ligands, azulene
ligands, pentalene ligands, phosphoyl ligands, pyrrolyl ligands,
pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the
like, including hydrogenated versions thereof, for example
tetrahydroindenyl ligands. In one embodiment, L.sup.A and L.sup.B
may be any other ligand structure capable of .eta.-bonding to M,
preferably .eta..sup.3-bonding to M, and most preferably
.eta..sup.5-bonding to M. In another embodiment, L.sup.A and
L.sup.B may comprise one or more heteroatoms, for example,
nitrogen, silicon, boron, germanium, sulfur and phosphorous, in
combination with carbon atoms to form an open, acyclic, or
preferably a fused, ring or ring system, for example, a
heterocyclopentadienyl ancillary ligand. Other L.sup.A and L.sup.B
bulky ligands include but are not limited to bulky amides,
phosphides, alkoxides, aryloxides, imides, carbolides, borollides,
porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
Independently, each L.sup.A and L.sup.B may be the same or
different type of bulky ligand that is bonded to M.
[0015] Independently, each L.sup.A and L.sup.B may be unsubstituted
or substituted with a combination of substituent groups R.
Non-limiting examples of substituent groups R include one or more
from the group selected from hydrogen, or linear, branched alkyl
radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl
radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy
radicals, aryloxy radicals, alkylthio radicals, dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals,
carbomoyl radicals, alky- or dialkyl-carbamoyl radicals, acyloxy
radicals, acylamino radicals, aroylamino radicals, straight,
branched or cyclic, alkylene radicals, or combination thereof.
Non-limiting examples of alkyl substituents R include methyl,
ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl,
benzyl or phenyl groups and the like, including all their isomers,
for example tertiary butyl, isopropyl, and the like. Other
hydrocarbyl radicals include fluoromethyl, fluoroethyl,
difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and
halocarbyl-substituted organometalloid radicals including
tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,
bromomethyldimethylgermyl and the like; and disubstitiuted boron
radicals including dimethylboron for example; and disubstituted
pnictogen radicals including dimethylamine, dimethylphosphine,
diphenylamine, methylphenylphosphine, chalcogen radicals including
methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.
Non-hydrogen substituents R include the atoms carbon, silicon,
boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,
germanium and the like, including olefins such as but not limited
to olefinically unsaturated substituents including vinyl-terminated
ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the
like. Also, at least two R groups, preferably two adjacent R
groups, are joined to form a ring structure having from 3 to 30
atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon,
germanium, aluminum, boron or a combination thereof. Also, a
substituent group R such as 1-butanyl may form a carbon sigma bond
to the metal M.
[0016] Other ligands may be bonded to the metal M, such as at least
one leaving group Q. For the purposes of this patent specification
and appended claims the term "leaving group" is any ligand that can
be abstracted from a bulky ligand metallocene-type catalyst
compound to form a bulky ligand metallocene-type catalyst cation
capable of polymerizing one or more olefin(s). In one embodiment, Q
is a monoanionic labile ligand having a sigma-bond to M. Depending
on the oxidation state of the metal, the value for n is 0, 1 or 2
such that formula (I) above represents a neutral bulky ligand
metallocene-type catalyst compound. Non-limiting examples of Q
ligands include weak bases such as amines, phosphines, ethers,
carboxylates, dienes, hydrocarbyl radicals having from 1 to 20
carbon atoms, hydrides or halogens and the like or a combination
thereof. In another embodiment, two or more Q's form a part of a
fused ring or ring system. Other examples of Q ligands include
those substituents for R as described above and including
cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl,
tetramethylene, pentamethylene, methylidene, methoxy, ethoxy,
propoxy, phenoxy, bis(N-methylanilide), dimethylamide,
dimethylphosphide radicals and the like.
[0017] A is cyclic ring or ring system that includes the Ge atom
and preferably contains 3 or greater non-hydrogen atoms, preferably
greater than 4 carbon atoms, to form a ring or ring system about
the Ge atom. The atoms forming the ring or ring system of A may be
substituted with substituents as defined above for R. Non-limiting
examples of cyclic bridging groups A include cyclo-tri or
tetra-alkylene germyl, for example, cyclotrimethylenegermyl group
or cyclotetramethylenegermyl group.
[0018] Other examples of cyclic bridging groups are represented by
the following structures: ##STR1##
[0019] In a preferred embodiment, the cyclic germanium bridged
bulky ligand metallocene-type catalyst compounds of the invention
include cyclotrimethylenegermyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride,
cyclotetramethylenegermyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride, cyclotrimethylenegermyl
(tetramethyl cyclopentadienyl) (2-methyl indenyl) zirconium
dichloride, cyclotrimethylenegermyl (tetramethyl cyclopentadienyl)
(3-methyl cyclopentadienyl) zirconium dichloride,
cyclotrimethylenegermyl bis(2-methyl indenyl) zirconium dichloride,
cyclotrimethylenegermyl (tetramethyl cyclopentadienyl)
(2,3,5-trimethyl cyclopentadienyl) zirconium dichloride,
cyclotrimethylenegermyl bis(tetra methyl cyclopentadienyl)
zirconium dichloride, cyclotetramethylenegermyl bis(tetra methyl
cyclopentadienyl) zirconium dichloride, o-xylidenegermyl bis(tetra
methyl cyclopentadienyl) zirconium dichloride and
3,4-dimethylcyclotetramethyl-3-enegermyl(tetramethyl
cyclopentadienyl) (2,3,5-trimethyl cyclopentadienyl) zirconium
dichloride. Also, any of the above specifically named compounds or
in conjunction with any of the bulky ligand metallocene-type
catalyst compound formulas, the following cyclic germanium bridges
are included: 3,4-dimethylcyclotetramethyl-3-enegermyl,
3-methylcyclotetramethyl-3-enegermyl and o-xylidenegermyl.
[0020] In another embodiment, the bulky ligand metallocene-type
catalyst compound of the invention is represented by the formula:
(C.sub.5H.sub.4-dR.sub.d)(R'GeR').sub.x(C.sub.5H.sub.4-dR.sub.d)M
Qg-.sub.2 (II) where M is a Group 4, 5, 6 transition metal,
(C.sub.5H.sub.4-dR.sub.d) is an unsubstituted or substituted,
cyclopentadienyl ligand or cyclopentadienyl-type bulky ligand
bonded to M, each R, which can be the same or different, is
hydrogen or a substituent group containing up to 50 non-hydrogen
atoms or substituted or unsubstituted hydrocarbyl having from 1 to
30 carbon atoms or combinations thereof, or two or more carbon
atoms are joined together to form a part of a substituted or
unsubstituted ring or ring system having 4 to 30 carbon atoms,
(R'GeR').sub.x is a cyclic bridging group, where Ge is germanium,
where the one or more Ge atoms bridge the two
(C.sub.5H.sub.4-dR.sub.d) rings, and the two R''s form a cyclic
ring or ring system with Ge; more particularly, non-limiting
examples of cyclic bridging group Ge may be represented by
R'.sub.2Ge where the two R''s are joined to form a ring or ring
system. In one embodiment, R' is a hydrocarbyl containing a
heteroatom, for example boron, nitrogen, oxygen or a combination
thereof. The two R''s may be independently, hydrocarbyl,
substituted hydrocarbyl, halocarbyl, substituted halocarbyl,
hydrocarbyl-substituted organometalloid, halocarbyl-substituted
organometalloid, where the two R''s are joined to form a ring or
ring system having from 2 to 100 non-hydrogen atoms, preferably
from 3 to 50 carbon atoms; and independently, each Q can be the
same or different is a hydride, substituted or unsubstituted,
linear, cyclic or branched, hydrocarbyl having from 1 to 30 carbon
atoms, halogen, alkoxides, aryloxides, amides, phosphides, or any
other univalent anionic ligand or combination thereof; also, two
Q's together may form an alkylidene ligand or cyclometallated
hydrocarbyl ligand or other divalent anionic chelating ligand,
where g is an integer corresponding to the formal oxidation state
of M, and d is an integer selected from 0, 1, 2, 3 or 4 and
denoting the degree of substitution, x is an integer from 1 to
4.
[0021] In one embodiment, the cyclic bridged bulky ligand
metallocene-type catalyst compounds are those where the R
substituents on the bulky ligands L.sup.A, L.sup.B,
(C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) are substituted
with the same or different number of substituents on each of the
bulky ligands. In another embodiment, the bulky ligands L.sup.A,
L.sup.B, (C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) are
different from each other.
[0022] In a preferred embodiment, the bulky ligands of the
metallocene-type catalyst compounds of formula (I) and (II) are
asymmetrically substituted. In another preferred embodiment, at
least one of the bulky ligands L.sup.A, L.sup.B,
(C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) is
unsubstituted.
[0023] In the most preferred embodiment, the cyclic germanium
bridged metallocene-type catalyst compounds of the invention are
achiral.
[0024] Other bulky ligand metallocene-type catalysts compounds
useful in the invention include cyclic germanium bridged
heteroatom, mono-bulky ligand metallocene-type compounds. These
types of catalysts and catalyst systems are described in, for
example, PCT publication WO 92/00333, WO 94/07928, WO 91/04257, WO
94/03506, WO96/00244 and WO 97/15602 and U.S. Pat. Nos. 5,057,475,
5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and
European publication EP-A-0 420 436, all of which are herein fully
incorporated by reference. Other bulky ligand metallocene-type
catalyst compounds and catalyst systems useful in the invention may
include those described in U.S. Pat. Nos. 5,064,802, 5,145,819,
5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106,
5,329,031, 5,304,614, 5,677,401, 5,723,398 and 5,753,578 and PCT
publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144 and
European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513
380, EP-A1-0 816 372, EP-A2-0 839 834 and EP-B1-0 632 819, all of
which are herein fully incorporated by reference.
[0025] In another embodiment, the cyclic bridged bulky ligand
metallocene-type catalyst compound is represented by the formula:
L.sup.C(Ge)JMQ.sub.n (III) where M is a Group 3 to 10 metal atom or
a metal selected from the Group of actinides and lanthanides of the
Periodic Table of Elements, preferably M is a Group 4 to 10
transition metal, and more preferably M is a Group 4, 5 or 6
transition metal, and most preferably M is a Group 4 transition
metal in any oxidation state, especially titanium; L.sup.C is a
substituted or unsubstituted bulky ligand bonded to M; J is bonded
to M; Ge is bonded to L and J; J is a heteroatom ancillary ligand;
and Ge is a cyclic bridging group; Q is a univalent anionic ligand;
and n is the integer 0,1 or 2. In formula (III) above, L.sup.C, Ge
and J form a fused or linked ring system. In an embodiment, L.sup.C
of formula (III) is as defined above for L.sup.A in formula (I), M
and Q of formula (III) are as defined above in formula (I).
[0026] In another embodiment of this invention the bulky ligand
metallocene-type catalyst compound useful in the invention is
represented by the formula:
(C.sub.5H.sub.5-y-xR.sub.x)(R''GeR'').sub.y(JR'.sub.z-1-y)M(Q).sub.n(L').-
sub.w (IV) where M is a transition metal from Group 4 in any
oxidation state, preferably, titanium, zirconium or hafnium, most
preferably titanium in either a +2, +3 or +4 oxidation state. A
combination of compounds represented by formula (IV) with the
transition metal in different oxidation states is also
contemplated. L.sup.C is represented by (C.sub.5H.sub.5-y-xR.sub.x)
and is a bulky ligand as described above. For purposes of formula
(IV) R.sub.0 means no substituent. More particularly
(C.sub.5H.sub.5-y-xR.sub.x) is a cyclopentadienyl ring or
cyclopentadienyl-type ring or ring system which is substituted with
from 0 to 4 substituent groups R, and "x" is 0, 1, 2, 3 or 4
denoting the degree of substitution. Each R is, independently, a
radical selected from a group consisting of 1 to 30 non-hydrogen
atoms. More particularly, R is a hydrocarbyl radical or a
substituted hydrocarbyl radical having from 1 to 30 carbon atoms,
or a hydrocarbyl-substituted metalloid radical where the metalloid
is a Group 14 or 15 element, preferably silicon or nitrogen or a
combination thereof, and halogen radicals and mixtures thereof.
Substituent R groups also include silyl, germyl, amine, and
hydrocarbyloxy groups and mixtures thereof. Also, in another
embodiment, (C.sub.5H.sub.5-y-xR.sub.x) is a cyclopentadienyl
ligand in which two R groups, preferably two adjacent R groups are
joined to form a ring or ring system having from 3 to 50 atoms,
preferably from 3 to 30 carbon atoms. This ring system may form a
saturated or unsaturated polycyclic cyclopentadienyl-type ligand
such as those bulky ligands described above, for example, indenyl,
tetrahydroindenyl, fluorenyl or octahydrofluorenyl.
[0027] The (JR'.sub.z-1-y) of formula (IV) is a heteroatom
containing ligand in which J is an element with a coordination
number of three from Group 15 or an element with a coordination
number of two from Group 16 of the Periodic Table of Elements.
Preferably J is a nitrogen, phosphorus, oxygen or sulfur atom with
nitrogen being most preferred. Each R' is, independently, a radical
selected from the group consisting of hydrocarbyl radicals having
from 1 to 20 carbon atoms, or as defined for R in formula (I)
above; the "y" is 1 to 4, preferably 1 to 2, most preferably y is
1, and the "z" is the coordination number of the element J. In one
embodiment, in formula (IV), the J of formula (III) is represented
by (JR'.sub.z-1-y).
[0028] In formula (IV) each Q is, independently, any univalent
anionic ligand such as halogen, hydride, or substituted or
unsubstituted hydrocarbyl having from 1 to 30 carbon atoms,
alkoxide, aryloxide, sulfide, silyl, amide or phosphide. Q may also
include hydrocarbyl groups having ethylenic unsaturation thereby
forming a .eta..sup.3 bond to M. Also, two Q's may be an
alkylidene, a cyclometallated hydrocarbyl or any other divalent
anionic chelating ligand. The integer n may be 0, 1, 2 or 3.
[0029] The (R''GeR'') y of formula (IV) is a cyclic bridging group
where Ge is a germanium and the two R'''s form a ring or ring
system about Ge, preferably, the two R''s together having from 3 to
100 non-hydrogen atoms, preferably from 3 to 50 carbon atom, and y
is preferably an integer from 1 to 4.
[0030] Optionally associated with formula (IV) is L', 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. Additionally, L' may be bonded
to any of R, R' or Q and n is 0, 1, 2 or 3.
Activator and Activation Methods for the Bulky Ligand
Metallocene-Type Catalyst Compounds
[0031] The above described cyclic germanium bridged bulky ligand
metallocene-type catalyst compounds are typically activated in
various ways to yield catalyst compounds having a vacant
coordination site that will coordinate, insert, and polymerize
olefin(s).
[0032] For the purposes of this patent specification and appended
claims, the term "activator" is defined to be any compound or
component or method which can activate any of the bulky ligand
metallocene-type catalyst compounds of the invention as described
above. Non-limiting activators, for example may include a Lewis
acid or a non-coordinating ionic activator or ionizing activator or
any other compound including Lewis bases, aluminum alkyls,
conventional-type cocatalysts and combinations thereof that can
convert a neutral bulky ligand metallocene-type catalyst compound
to a catalytically active bulky ligand metallocene cation. It is
within the scope of this invention to use alumoxane or modified
alumoxane as an activator, and/or to also use ionizing activators,
neutral or ionic, such as tri (n-butyl) ammonium tetrakis
(pentafluorophenyl) boron or a trisperfluorophenyl boron metalloid
precursor or a trisperfluoronaphthyl boron metalloid precursor that
would ionize the neutral bulky ligand metallocene-type catalyst
compound.
[0033] In one embodiment, an activation method using ionizing ionic
compounds not containing an active proton but capable of producing
both a bulky ligand metallocene-type catalyst cation and a
non-coordinating anion are also contemplated, and are described in
EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568, which
are all herein incorporated by reference.
[0034] There are a variety of methods for preparing alumoxane and
modified alumoxanes, non-limiting examples of which are described
in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,
5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,
5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,
5,391,529, 5,693,838, 5,731,253, 5,731,451 5,744,656 and European
publications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218,
and PCT publication WO 94/10180, all of which are herein fully
incorporated by reference.
[0035] Ionizing compounds may contain an active proton, or some
other cation associated with but not coordinated to or only loosely
coordinated to the remaining ion of the ionizing compound. Such
compounds and the like are described in European publications
EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-500 944,
EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,
5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124
and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,
1994, all of which are herein fully incorporated by reference.
[0036] Other activators include those described in PCT publication
WO 98/07515 such as tris (2,2',2''-nonafluorobiphenyl)
fluoroaluminate, which publication is fully incorporated herein by
reference. Combinations of activators are also contemplated by the
invention, for example, alumoxanes and ionizing activators in
combinations, see for example, PCT publications WO 94/07928 and WO
95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which
are herein fully incorporated by reference. WO 98/09996
incorporated herein by reference describes activating bulky ligand
metallocene-type catalyst compounds with perchlorates, periodates
and iodates including their hydrates. WO 98/30602 and WO 98/30603
incorporated by reference describe the use of lithium
(2,2'-bisphenyl-ditrimethylsilicate).4THF as an activator for a
bulky ligand metallocene-type catalyst compound. Also, methods of
activation such as using radiation (see EP-B 1 -0 615 981 herein
incorporated by reference), electro-chemical oxidation, and the
like are also contemplated as activating methods for the purposes
of rendering the neutral bulky ligand metallocene-type catalyst
compound or precursor to a bulky ligand metallocene-type cation
capable of polymerizing olefins.
[0037] It is further contemplated by the invention that other
catalysts can be combined with the cyclic germanium bridged bulky
ligand metallocene-type catalyst compounds of the invention. For
example, see U.S. Pat. Nos. 4,937,299, 4,935,474, 5,281,679,
5,359,015, 5,470,811, and 5,719,241 all of which are herein fully
incorporated herein reference.
[0038] In another embodiment of the invention one or more cyclic
germanium bridged bulky ligand metallocene-type catalyst compounds
or catalyst systems may be used in combination with one or more
conventional-type catalyst compounds or catalyst systems.
Non-limiting examples of mixed catalysts and catalyst systems are
described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,
5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,
5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published
Aug. 1, 1996, all of which are herein fully incorporated by
reference.
Method for Supporting
[0039] The above described cyclic germanium bridged bulky ligand
metallocene-type catalyst compounds and catalyst systems may be
combined with one or more support materials or carriers using one
of the support methods well known in the art or as described below.
In the preferred embodiment, the method of the invention uses a
polymerization catalyst in a supported form. For example, in a most
preferred embodiment, a bulky ligand metallocene-type catalyst
compound or catalyst system is in a supported form, for example
deposited on, bonded to, contacted with, or incorporated within,
adsorbed or absorbed in, or on, a support or carrier.
[0040] The terms "support" or "carrier" are used interchangeably
and are any support material, preferably a porous support material,
for example, talc, inorganic oxides and inorganic chlorides. Other
carriers include resinous support materials such as polystyrene,
functionalized or crosslinked organic supports, such as polystyrene
divinyl benzene polyolefins or polymeric compounds, zeolites,
clays, or any other organic or inorganic support material and the
like, or mixtures thereof.
[0041] The preferred carriers are inorganic oxides that include
those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred
supports include silica, alumina, silica-alumina, magnesium
chloride, and mixtures thereof. Other useful supports include
magnesia, titania, zirconia, montmorillonite (EP-B1 0 511 665),
zeolites, and the like. Also, combinations of these support
materials may be used, for example, silica-chromium,
silica-alumina, silica-titania and the like.
[0042] It is preferred that the carrier, most preferably an
inorganic oxide, has a surface area in the range of from about 10
to about 700 m.sup.2/g, pore volume in the range of from about 0.1
to about 4.0 cc/g and average particle size in the range of from
about 5 to about 500 .mu.m. More preferably, the surface area of
the carrier is in the range of from about 50 to about 500
m.sup.2/g, pore volume of from about 0.5 to about 3.5 cc/g and
average particle size of from about 10 to about 200 .mu.m. Most
preferably the surface area of the carrier is in the range is from
about 100 to about 400 m.sup.2/g, pore volume from about 0.8 to
about 3.0 cc/g and average particle size is from about 5 to about
100 .mu.m. The average pore size of the carrier of the invention
typically has pore size in the range of from 10 to 1000 .ANG.,
preferably 50 to about 500 .ANG., and most preferably 75 to about
350 .ANG..
[0043] Examples of supporting the bulky ligand metallocene-type
catalyst systems of the invention are described in U.S. Pat. Nos.
4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,
5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,
5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,
5,723,402, 5,731,261, 5,759,940, 5,767,032 and 5,770,664 and U.S.
application Ser. Nos. 271,598 filed Jul. 7, 1994 and 788,736 filed
Jan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO
96/06187 and WO 97/02297 all of which are herein fully incorporated
by reference.
[0044] In one embodiment, the cyclic germanium bridged bulky ligand
metallocene-type catalyst compounds of the invention may be
deposited on the same or separate supports together with an
activator, or the activator may be used in an unsupported form, or
may be deposited on a support different from the supported bulky
ligand metallocene-type catalyst compounds of the invention, or any
combination thereof.
[0045] There are various other methods in the art for supporting a
polymerization catalyst compound or catalyst system of the
invention. For example, the cyclic germanium bridged bulky ligand
metallocene-type catalyst compound of the invention may contain a
polymer bound ligand as described in U.S. Pat. Nos. 5,473,202 and
5,770,755, which is herein fully incorporated by reference; the
bulky ligand metallocene-type catalyst system of the invention may
be spray dried as described in U.S. Pat. No. 5,648,310, which is
herein fully incorporated by reference; the support used with the
cyclic germanium bridged bulky ligand metallocene-type catalyst
system of the invention is functionalized as described in European
publication EP-A-0 802 203, which is herein fully incorporated by
reference, or at least one substituent or leaving group is selected
as described in U.S. Pat. No. 5,688,880, which is herein fully
incorporated by reference.
[0046] In a preferred embodiment, the invention provides for a
supported cyclic germanium bridged bulky ligand metallocene-type
catalyst system that includes an antistatic agent or surface
modifier that is used in the preparation of the supported catalyst
system as described in PCT publication WO 96/11960, which is herein
fully incorporated by reference. The catalyst systems of the
invention can be prepared in the presence of an olefin, for example
hexene-1.
[0047] A preferred method for producing the supported cyclic
germanium bridged bulky ligand metallocene-type catalyst system of
the invention is described below and is described in U.S.
application Ser. Nos. 265,533, filed Jun. 24, 1994 and 265,532,
filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO
96/00243 both published Jan. 4, 1996, all of which are herein fully
incorporated by reference. In this preferred method, the cyclic
bridged germanium bulky ligand metallocene-type catalyst compound
is slurried in a liquid to form a metallocene solution and a
separate solution is formed containing an activator and a liquid.
The liquid may be any compatible solvent or other liquid capable of
forming a solution or the like with the cyclic germanium bridged
bulky ligand metallocene-type catalyst compounds and/or activator
of the invention. In the most preferred embodiment the liquid is a
cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
The cyclic germanium bridged bulky ligand metallocene-type catalyst
compound and activator solutions are mixed together and added to a
porous support or the porous support is added to the solutions such
that the total volume of the bulky ligand metallocene-type catalyst
compound solution and the activator solution or the bulky ligand
metallocene-type catalyst compound and activator solution is less
than four times the pore volume of the porous support, more
preferably less than three times, even more preferably less than
two times; preferred ranges being from 1.1 times to 3.5 times range
and most preferably in the 1.2 to 3 times range.
[0048] Procedures for measuring the total pore volume of a porous
support are well known in the art. Details of one of these
procedures is discussed in Volume 1, Experimental Methods in
Catalytic Research (Academic Press, 1968) (specifically see pages
67-96). This preferred procedure involves the use of a classical
BET apparatus for nitrogen absorption. Another method well known in
the art is described in Innes, Total Porosity and Particle Density
of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical
Chemistry 332-334 (March 1956).
[0049] The mole ratio of the metal or metalloid of the activator
component to the metal of the supported cyclic germanium bridged
bulky ligand metallocene-type catalyst compounds are in the range
of between 0.3:1 to 1000:1, preferably 20:1 to 800:1, and most
preferably 50:1 to 500:1. Where the activator is an ionizing
activator such as those based on the anion
tetrakis(pentafluorophenyl)boron, the mole ratio of the metal or
metalloid of the activator component to the metal component of the
cyclic germanium bridged bulky ligand metallocene-type catalyst is
preferably in the range of between 0.3:1 to 3:1. Where an
unsupported cyclic germanium bridged bulky ligand metallocene-type
catalyst system is utilized, the mole ratio of the metal or
metalloid of the activator component to the metal of the cyclic
germanium bridged bulky ligand metallocene-type catalyst compound
is in the range of between 0.3:1 to 10,000:1, preferably 100:1 to
5000:1, and most preferably 500:1 to 2000:1.
[0050] In one embodiment of the invention, olefin(s), preferably
C.sub.2 to C.sub.30 olefin(s) or alpha-olefin(s), preferably
ethylene or propylene or combinations thereof are prepolymerized in
the presence of the cyclic germanium bridged bulky ligand
metallocene-type catalyst system of the invention prior to the main
polymerization. The prepolymerization can be carried out batchwise
or continuously in gas, solution or slurry phase including at
elevated pressures. The prepolymerization can take place with any
olefin monomer or combination and/or in the presence of any
molecular weight controlling agent such as hydrogen. For examples
of prepolymerization procedures, see U.S. Pat. Nos. 4,748,221,
4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and
European publication EP-B-0279 863 and PCT Publication WO 97/44371
all of which are herein fully incorporated by reference.
[0051] In one embodiment the polymerization catalyst is used in an
unsupported form, preferably in a liquid form such as described in
U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication
EP-A-0 593 083, all of which are herein incorporated by reference.
The polymerization catalyst in liquid form can be fed to a reactor
as described in PCT publication WO 97/46599, which is fully
incorporated herein by reference.
[0052] In one embodiment, the cyclic germanium bridged
metallocene-type catalysts of the invention can be combined with a
carboxylic acid salt of a metal ester, for example aluminum
carboxylates such as aluminum mono, di- and tri-stearates, aluminum
octoates, oleates and cyclohexylbutyrates, as described in U.S.
application Ser. No. 09/113,216, filed Jul. 10, 1998.
Polymerization Process
[0053] The catalysts and catalyst systems of the invention
described above are suitable for use in any polymerization process
over a wide range of temperatures and pressures. The temperatures
may be in the range of from -60.degree. C. to about 280.degree. C.,
preferably from 50.degree. C. to about 200.degree. C., and the
pressures employed may be in the range from 1 atmosphere to about
500 atmospheres or higher.
[0054] Polymerization processes include solution, gas phase, slurry
phase and a high pressure process or a combination thereof.
Particularly preferred is a gas phase or slurry phase
polymerization of one or more olefins at least one of which is
ethylene or propylene.
[0055] In one embodiment, the process of this invention is directed
toward a solution, high pressure, slurry or gas phase
polymerization process of one or more olefin monomers having from 2
to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more
preferably 2 to 8 carbon atoms. The invention is particularly well
suited to the polymerization of two or more olefin monomers of
ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,
hexene-1, octene-1 and decene-1.
[0056] Other monomers useful in the process of the invention
include ethylenically unsaturated monomers, diolefins having 4 to
18 carbon atoms, conjugated or nonconjugated dienes, polyenes,
vinyl monomers and cyclic olefins. Non-limiting monomers useful in
the invention may include norbornene, norbornadiene, isobutylene,
isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted
styrene, ethylidene norbornene, dicyclopentadiene and
cyclopentene.
[0057] In the most preferred embodiment of the process of the
invention, a copolymer of ethylene is produced, where with
ethylene, a comonomer having at least one alpha-olefin having from
4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and
most preferably from 4 to 8 carbon atoms, is polymerized in a gas
phase process.
[0058] In another embodiment of the process of the invention,
ethylene or propylene is polymerized with at least two different
comonomers, optionally one of which may be a diene, to form a
terpolymer.
[0059] In one embodiment, the invention is directed to a
polymerization process, particularly a gas phase or slurry phase
process, for polymerizing propylene alone or with one or more other
monomers including ethylene, and/or other olefins having from 4 to
12 carbon atoms. Polypropylene polymers may be produced using the
particularly bridged bulky ligand metallocene-type catalysts as
described in U.S. Pat. Nos. 5,296,434 and 5,278,264, both of which
are herein incorporated by reference.
[0060] Typically in a gas phase polymerization process a continuous
cycle is employed where in one part of the cycle of a reactor
system, a cycling gas stream, otherwise known as a recycle stream
or fluidizing medium, is heated in the reactor by the heat of
polymerization. This heat is removed from the recycle composition
in another part of the cycle by a cooling system external to the
reactor. Generally, in a gas fluidized bed process for producing
polymers, a gaseous stream containing one or more monomers is
continuously cycled through a fluidized bed in the presence of a
catalyst under reactive conditions. The gaseous stream is withdrawn
from the fluidized bed and recycled back into the reactor.
Simultaneously, polymer product is withdrawn from the reactor and
fresh monomer is added to replace the polymerized monomer. (See for
example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,
5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661
and 5,668,228, all of which are fully incorporated herein by
reference.)
[0061] The reactor pressure in a gas phase process may vary from
about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably
in the range of from about 200 psig (1379 kPa) to about 400 psig
(2759 kPa), more preferably in the range of from about 250 psig
(1724 kPa) to about 350 psig (2414 kPa).
[0062] The reactor temperature in a gas phase process may vary from
about 30.degree. C. to about 120.degree. C., preferably from about
60.degree. C. to about 115.degree. C., more preferably in the range
of from about 70.degree. C. to 110.degree. C., and most preferably
in the range of from about 70.degree. C. to about 95.degree. C.
[0063] Other gas phase processes contemplated by the process of the
invention include those described in U.S. Pat. Nos. 5,627,242,
5,665,818 and 5,677,375, and European publications EP-A-0 794 200,
EP-A-0 802 202 and EP-B-634 421 all of which are herein fully
incorporated by reference.
[0064] In a preferred embodiment, the reactor utilized in the
present invention is capable and the process of the invention is
producing greater than 500 lbs of polymer per hour (227 Kg/hr) to
about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer,
preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably
greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably
greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably
greater than 35,000 lbs/hr (15,900 Kg/hr), still even more
preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most
preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater
than 100,000 lbs/hr (45,500 Kg/hr).
[0065] A slurry polymerization process generally uses pressures in
the range of from about 1 to about 50 atmospheres and even greater
and temperatures in the range of 0.degree. C. to about 120.degree.
C. In a slurry polymerization, a suspension of solid, particulate
polymer is formed in a liquid polymerization diluent medium to
which ethylene and comonomers and often hydrogen along with
catalyst are added. The suspension including diluent is
intermittently or continuously removed from the reactor where the
volatile components are separated from the polymer and recycled,
optionally after a distillation, to the reactor. The liquid diluent
employed in the polymerization medium is typically an alkane having
from 3 to 7 carbon atoms, preferably a branched alkane. The medium
employed should be liquid under the conditions of polymerization
and relatively inert. When a propane medium is used the process
must be operated above the reaction diluent critical temperature
and pressure. Preferably, a hexane or an isobutane medium is
employed.
[0066] A preferred polymerization technique of the invention is
referred to as a particle form polymerization, or a slurry process
where the temperature is kept below the temperature at which the
polymer goes into solution. Such technique is well known in the
art, and described in for instance U.S. Pat. No. 3,248,179 which is
fully incorporated herein by reference. Other slurry processes
include those employing a loop reactor and those utilizing a
plurality of stirred reactors in series, parallel, or combinations
thereof. Non-limiting examples of slurry processes include
continuous loop or stirred tank processes. Also, other examples of
slurry processes are described in U.S. Pat. No. 4,613,484, which is
herein fully incorporated by reference.
[0067] In an embodiment the reactor used in the slurry process of
the invention is capable of and the process of the invention is
producing greater than 2000 lbs of polymer per hour (907 Kg/hr),
more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most
preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another
embodiment the slurry reactor used in the process of the invention
is producing greater than 15,000 lbs of polymer per hour (6804
Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to
about 100,000 lbs/hr (45,500 Kg/hr).
[0068] Examples of solution processes are described in U.S. Pat.
Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fully
incorporated herein by reference
[0069] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated in the
presence of a bulky ligand metallocene-type catalyst system of the
invention and in the absence of or essentially free of any
scavengers, such as triethylaluminum, trimethylaluminum,
tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum
chloride, dibutyl zinc and the like. This preferred process is
described in PCT publication WO 96/08520 and U.S. Pat. No.
5,712,352 and 5,763,543, which are herein fully incorporated by
reference.
Polymer Product of the Invention
[0070] The polymers produced by the process of the invention can be
used in a wide variety of products and end-use applications. The
polymers produced by the process of the invention include linear
low density polyethylene, elastomers, plastomers, high density
polyethylenes, low density polyethylenes, polypropylene and
polypropylene copolymers.
[0071] The polymers, typically ethylene based polymers, have a
density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in
the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the
range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the
range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in
the range from 0.910 g/cc to 0.940 g/cc, and most preferably
greater than 0.915 g/cc to about 0.930 g/cc.
[0072] The melt strength of the polymers produced using the
catalyst of the invention are greater than 6 cN, preferably greater
than 7 cN, and most preferably 8 cN or higher. For purposes of this
patent application and appended claims melt strength is measured
with an Instron capillary rheometer in conjunction with the
Goettfert Rheotens melt strength apparatus. A polymer melt strand
extruded from the capillary die is gripped between two
counter-rotating wheels on the apparatus. The take-up speed is
increased at a constant acceleration of 24 mm/sec.sup.2, which is
controlled by the Acceleration Programmer (Model 45917, at a
setting of 12). The maximum pulling force (in the unit of cN)
achieved before the strand breaks or starts to show draw-resonance
is determined as the melt strength. The temperature of the
rheometer is set at 190.degree. C. The capillary die has a length
of one inch (2.54 cm) and a diameter of 0.06'' (0.1 5 cm). The
polymer melt is extruded from the die at a speed of 3 inch/min
(7.62 cm/min). The distance between the die exit and the wheel
contact point should be 3.94 inches (100 mm).
[0073] The polymers produced by the process of the invention
typically have a molecular weight distribution, a weight average
molecular weight to number average molecular weight
(M.sub.w/M.sub.n) of greater than 1.5 to about 15, particularly
greater than 2 to about 10, more preferably greater than about 2.5
to less than about 8, and most preferably from 3.0 to 8.
[0074] In one preferred embodiment, the polymers of the present
invention have a M.sub.z/M.sub.w of greater than or equal to 3,
preferably greater than 3. M.sub.z is the z-average molecular
weight. In another preferred embodiment, the polymers of the
invention have a M.sub.z/M.sub.w of greater than or equal to 3.0 to
about 4. In yet another preferred embodiment, the M.sub.z/M.sub.w
is in the range greater than 3 to less than 4.
[0075] Also, the polymers of the invention typically have a narrow
composition distribution as measured by Composition Distribution
Breadth Index (CDBI). Further details of determining the CDBI of a
copolymer are known to those skilled in the art. See, for example,
PCT Patent Application WO 93/03093, published Feb. 18, 1993, which
is fully incorporated herein by reference.
[0076] The bulky ligand metallocene-type catalyzed polymers of the
invention in one embodiment have CDBI's generally in the range of
greater than 50% to 100%, preferably 99%, preferably in the range
of 55% to 85%, and more preferably 60% to 80%, even more preferably
greater than 60%, still even more preferably greater than 65%. In
another embodiment, polymers produced using a bulky ligand
metallocene-type catalyst system of the invention have a CDBI less
than 50%, more preferably less than 40%, and most preferably less
than 30%.
[0077] The polymers of the present invention in one embodiment have
a melt index (MI) or (I.sub.2) as measured by ASTM-D-1238-E in the
range from 0.01 dg/min to 1000 dg/min, more preferably from about
0.01 dg/min to about 100 dg/min, even more preferably from about
0.1 dg/min to about 50 dg/min, and most preferably from about 0.1
dg/min to about 10 dg/min.
[0078] The polymers of the invention in an embodiment have a melt
index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from 30 to less than 200, more preferably from
about 35 to less than 100, and most preferably from 40 to 95.
[0079] The polymers of the invention in a preferred embodiment have
a melt index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from preferably greater than 30, more preferably
greater than 35, even more preferably greater that 40, still even
more preferably greater than 50 and most preferably greater than
65.
[0080] The polymers of the invention may be blended and/or
coextruded with any other polymer. Non-limiting examples of other
polymers include linear low density polyethylenes produced via
conventional Ziegler-Natta and/or bulky ligand metallocene-type
catalysis, elastomers, plastomers, high pressure low density
polyethylene, high density polyethylenes, polypropylenes and the
like.
[0081] Polymers produced by the process of the invention and blends
thereof are useful in such forming operations as film, sheet, and
fiber extrusion and co-extrusion as well as blow molding, injection
molding and rotary molding. Films include blown or cast films
formed by coextrusion or by lamination useful as shrink film, cling
film, stretch film, sealing films, oriented films, snack packaging,
heavy duty bags, grocery sacks, baked and frozen food packaging,
medical packaging, industrial liners, membranes, etc. in
food-contact and non-food contact applications. Fibers include melt
spinning, solution spinning and melt blown fiber operations for use
in woven or non-woven form to make filters, diaper fabrics, medical
garments, geotextiles, etc. Extruded articles include medical
tubing, wire and cable coatings, geomembranes, and pond liners.
Molded articles include single and multi-layered constructions in
the form of bottles, tanks, large hollow articles, rigid food
containers and toys, etc.
EXAMPLES
[0082] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered.
Example 1
Synthesis of
C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4C.sub.5).sub.2]ZrCl.sub.2
[0083] A solution of C.sub.6H.sub.4(CH.sub.2).sub.2Mg(THF).sub.1.9
(3.99 g, 15.0 mmol) in THF (300 mL) was added dropwise to a
solution of (Me.sub.4C.sub.5H).sub.2GeCl.sub.2 (5.77 g, 15.0 mmol)
in THF (250 mL) at room temperature. After stirring for 18 h, the
volatiles were removed under reduced pressure and the residue was
extracted with pentane (300 mL). The mixture was filtered and the
solution was concentrated and cooled to -25.degree. C. A mass of
faint yellow crystals was collected and dried in vacuo. A second
crop was obtained for a total yield of 3.32 g (7.92 mmol, 53%) of
C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4C.sub.5H).sub.2.
[0084] The C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4CSH).sub.2 was
dissolved in Et.sub.2O (300 mL) and a 1.7 M solution of t-BuLi in
pentane (9.29 mL, 15.8 mmol) was added dropwise by syringe. After
addition, the cloudy mixture was stirred at room temperature for 4
h, and then solid ZrCl.sub.4 (1.85 g, 7.94 mmol) was added in
portions. After stirring for 18 h, the volatiles were removed under
reduced pressure and the residue was extracted with
CH.sub.2Cl.sub.2 (200 mL). The mixture was filtered and the
solution was concentrated and cooled to -25.degree. C. A
microcrystalline solid was collected and dried in vacuo. A second
crop was collected for a total yield of 0.91 g (1.6 mmol, 20%) of
[C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4C.sub.5).sub.2]ZrCl.sub.2,
a cyclic germanium bridged metallocene-type catalyst compound.
[0085] The compound produced is represented by the following
chemical structure: ##STR2##
Example 2
Catalyst Preparation for
C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4C.sub.5).sub.2]ZrCl.sub.2
[0086] To a solution of 31.86 g of 30 wt. % methylalumoxane (MAO)
(available from Albemarle Corporation, Baton Rouge, La.) diluted in
toluene (32.7 g, Aldrich anhydrous grade stored over molecular
sieves) was added 0.78 g (1.35 mmol)
[C.sub.6H.sub.4(CH.sub.2).sub.2Ge(Me.sub.4C.sub.5).sub.2]ZrCl.sub.2.
The resulting orange solution was stirred for 10 min. and then 25.0
g of silica (MS948, 1.6 cc/g P.V. (P.V.=pore volume), available
from W. R. Grace, Davison Chemical Division, Baltimore, Md.
previously heated to 600.degree. C. under N.sub.2 for 3 hours) was
added with swirling. When the mixture was no longer mobile, it was
thoroughly homogenized with a spatula. The volatiles were removed
in vacuo over 18 h at room temperature. The free flowing catalyst
was mixed with 3 wt. % of Aluminum Stearate #22 in a dry box, (AlSt
#22 is (CH.sub.3(CH.sub.2).sub.16COO).sub.2Al--OH and is available
from Witco Corporation, Memphis, Tenn.), then transferred to a
catalyst bomb for testing.
Example 3
Synthesis of [--CH.sub.2CMe.dbd.CMeCH.sub.2--]Ge(CpMe.sub.4H).sub.2
(Compound 1)
[0087] GeCl.sub.2 (dioxane) (See JACS, 120 (27), 1998, 6743) (3.6
g, 16.1 mmol) was dissolved in 40 ml THF and reacted with 2.0 g
butadiene. After the reaction was stirred at room temperature for 1
h., CpMe.sub.4HLi (4.1 g, 32.2 mmol) was added, and the reaction
allowed to proceed for 18 h. The volatiles are then removed in
vacuo and the crude reaction mixture extracted with Et.sub.2O. The
Et.sub.2O filtrate is cooled to -35.degree. C. to yield pure
Compound 1 as a white solid.
Example 4
Synthesis of
[--CH.sub.2CMe.dbd.CMeCH.sub.2--]Ge(CpMe.sub.4).sub.2ZrCl.sub.2
(Compound 2)
[0088] A sample of 5.6 g of the above Compound 1 made in Example 3
was dissolved in Et.sub.2O and deprotonated with nBuLi. The dianion
was isolated, reslurried in Et.sub.2O and reacted with ZrC.sub.4
(3.0 g). The crude reaction was filtered over a glass frit. The
crude solid collected was extracted with CH.sub.2Cl.sub.2
(3.times.20 ml), the filtrates reduced and cooled to -35.degree. C.
Compound 2 was isolated as a very pale-yellow to white solid (2.1
g). The compound produced is represented by the following chemical
structure: ##STR3##
Example 5
Catalyst Preparation
[0089] 0.60 g of the cyclic germanium bridged metallocene-type
catalyst Compound 2 prepared above in Example 4 was slurried in 26
g toluene and reacted with 26 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.). To this was added 25 g
SiO.sub.2 (Davison 948, 600.degree. C., available from W. R. Grace,
Davison Chemical Division, Baltimore, Md.). The catalyst system was
dried at ambient temperature in vacuo for 18 hr. and loaded in a
metal bomb for testing in a gas phase pilot plant.
Comparative Example 6
[0090] The compound [CpMe.sub.4--GeMe.sub.2--CpMe.sub.4]ZrCl.sub.2
(0.52 g) was slurried in 34.5 g toluene and reacted with 34.5 g 30%
MAO (available from Albemarle Corporation, Baton Rouge, La.).
Silica gel (25 g) (Davison 948, 600.degree. C., available from W.
R. Grace, Davison Chemical Division, Baltimore, Md.) was added in
increments and mixed with a spatula. The catalyst system was dried
at ambient temperature in vacuo for 18 hr. and loaded in a metal
bomb for testing in a gas phase pilot plant.
Comparative Example 7
[0091] The compound [CpMe.sub.4--SiMe.sub.2--CpMe.sub.4]ZrCl.sub.2
(0.74 g) was slurried in 53.5 g toluene and reacted with 53.5 g 30%
MAO (available from Albemarle Corporation, Baton Rouge, La.).
Silica gel (40 g) (Davison 948, 600.degree. C., available from W.
R. Grace, Davison Chemical Division, Baltimore, Md.) was added in
increments and mixed with a spatula. The catalyst system was dried
at ambient temperature in vacuo for 18 hr. and loaded in a metal
bomb for testing in a gas phase pilot plant.
Comparative Example 8
[0092] A sample of (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4).sub.2 (0.63
g, 1.33 mmol) was weighed into a beaker and reacted with 32.0 g 30%
MAO (available from Albemarle Corporation, Baton Rouge, La.) and
32.0 g toluene and stirred until dissolution (10 min). To the
reaction mixture was added 24.0 g silica gel (Davison 948,
600.degree. C., available from W. R. Grace, Davison Chemical
Division, Baltimore, Md.) and mixed with a spatula. The resulting
mud was dried in vacuo at room temperature for 15 h and transferred
into a bomb for screening in a continuous gas phase pilot
plant.
Example 9
Polymerization for Examples 2, 5 and Comparative Examples 6 to
8
[0093] A continuous cycle fluidized bed gas phase polymerization
reactor was used for the polymerization studies for Examples 2, 5
and Comparative Examples 6 to 8 and the results are summarized in
Tables 1 and 2. The reactor consists of a 6 inch (15.24 cm)
diameter bed section increasing to 10 inches (25.4 cm) at the
reactor top. Gas comes in through a perforated distributor plate
allowing fluidization of the bed contents and polymer sample is
discharged at the reactor top. Gas enters through a perforated
distributor plate allowing fluidization of the bed contents and
polymer is discharged at the reactor top. Polymer samples were
collected after several bed turnovers once the reactor and product
were stabilized.
[0094] It can be seen from Table 2 below that the polymers produced
by the catalyst systems of the invention have both a high melt
strength and a high melt index ratio.
[0095] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For
example, it is contemplated that the cyclic germanium bridged
metallocene-type catalyst compound of the invention can be combined
with one or more non-cyclic bridged metallocene-type catalyst
compounds. It is also contemplated that the process of the
invention may be used in a series reactor polymerization process.
For example, a supported cyclic germanium bridged bulky ligand
metallocene-type catalyst compound is used in one reactor and a
non-cyclic bridged or unbridged, bulky ligand metallocene-type
catalyst compound being used in another or vice-versa. For this
reason, then, reference should be made solely to the appended
claims for purposes of determining the true scope of the present
invention. TABLE-US-00001 TABLE 1 Example 2 5 CEx 6 CEx 7 CEx 8
Temperature (.degree. F.) (.degree. C.) 175 (79.4) 175 175 175 168
Pressure (psi) (kPa) 300 (2067) 300 300 300 300 Ethylene (mole %)
35.0 35.1 35.0 35.0 30.1 Hydrogen (mole ppm) 129 384 88 106 342
Hydrogen/Ethylene 3.7 10.9 2.5 3.0 11.4 Concentration Ratio Hexene
(mole %) 0.62 0.99 1.00 0.87 0.46 Hexene/Ethylene 0.018 0.028 0.099
0.025 0.015 Concentration Ratio Bed Weight (g) 1903 1947 1951 1930
1626 Residence Time (hrs) 3.6 5.0 7.0 4.8 3.0 Productivity.sup.1
(g/g) 1697 750 373 3458 633 Gas Velocity 1.57 (47.9) 1.58 1.59 1.57
0.553 (ft/sec) (cm/sec) Production Rate (g/hr) 533 391 278 400 209
Bulk Density (g/cc) 0.3630 NM 0.2988 0.3880 0.4438
.sup.1Productivity is number of grams of product per gram of
catalyst. NM = not measured.
[0096] TABLE-US-00002 TABLE 2 Example 2 5 CEx 6 CEx 7 CEx 8 Density
(g/cc) 0.923 0.9187 0.9186 0.9193 0.9256 Melt Index 1.2 0.96 1.1
1.72 0.78 (g/10 min) Melt Index Ratio 37 60.0 30.0 31.7 86.3
(I.sub.21/I.sub.2) Melt Strength 9.5 8.8 10.4 7.4 4.7 (cN) 1.sup.st
M.P. (.degree. C.) 120.7 120.3 -- -- -- 2.sup.nd M.P. (.degree. C.)
113.5 103.6 -- -- -- Mn 30,900 NM -- -- -- Mw 113,200 NM -- -- --
Mz 342,500 NM -- -- -- Mw/Mn 3.67 NM -- -- -- Mz/Mw 3.03 NM -- --
-- CDBI NM NM -- -- -- SCB.sup.1 12.8 16.6 -- -- -- .sup.1Short
chain branches per 1000 carbon atoms. NM is not measured.
* * * * *