Metallocene catalyst systems

Details Metallocene catalyst systems Metallocene catalyst systems

2000-05-05

2001-02-06

Wu, David W. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C502S108000, C502S152000, C502S158000, C526S128000, C526S160000, C526S162000, C526S943000

Reexamination Certificate

active

06184170

ABSTRACT:

FIELD OF THE INVENTION
This invention relates generally to metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to a method for preparing metallocene catalyst systems using olefin additives which promote catalyst activity.
BACKGROUND
Metallocene catalyst systems are well known in the art. While the prior art discloses the use of olefins to prepare prepolymer and the use of polyolefins as supports, the prior art does not disclose the use of olefins as a reactant with the metallocene active site to promote catalyst system activity. For example, U.S. Pat. No. 5,346,925 describes supporting catalyst components on porous polymer supports such as polystyrenes. Canadian Patent Application No. 2,093,056 also describes using polymeric supports such as polystyrenes. WO 96/34020 describes a catalyst system prepared with an inert hydrocarbon and WO 95/25129 describes a method for preparing catalyst systems using a spray drying technique which can include polystyrene microparticles. EP 748823 A1 describes the use of styrene and styrenic compounds combined with certain transition metal compounds and modified alumoxanes to prepare catalyst systems.
The present inventor has discovered that the activity of metallocene catalyst systems is substantially increased when certain olefin promoters are used to prepare the catalyst systems.
SUMMARY
This invention relates to metallocene catalyst systems comprising the reaction product of a mixture comprising a metallocene, an activator, and promoter wherein the promoter comprises a styrene, a substituted styrene or a compound represented by the formula:
(1.) R—CH═CH
2
wherein R may be a C
6
-C
10
aryl group which may be halogenated, or a C
7
-C
40
alkylaryl group; or
(2) R
1
R
2
R
3
MCH═CH
2
wherein R
1
may be a C
6
-C
10
aryl group which may be halogenated, or a C
7
-C
40
alkylaryl group, R
2
and R
3
are identical or different and may be a C
6
-C
10
aryl group which may be halogenated, a C
7
-C
40
alkylaryl group or a C
1
-C
10
alkyl group which may be halogenated, preferably a C
1
-C
3
alkyl group; M is carbon, silicon, germanium or tin; wherein the molar ratio of the metallocene to promoter in the mixture is in the range of from about 1:1 to about 1:1000.
This invention also relates to metallocene catalyst systems comprising the reaction product of a mixture comprising a metallocene, an activator, and a styrene or substituted styrene wherein the catalyst system is essentially free of polystyrene.
In another embodiment this invention relates to a method for forming, a metallocene catalyst system comprising: combining at least one metallocene, at least one activator, and promoter wherein the promoter comprises a styrene or substituted styrene, a compound represented by the formula Ph—SiR
1
R
2
—CH═CH
2
wherein R
1
and R
2
are independently an alkyl group, an arylalkyl, or an alkylaryl; and wherein the amount of promoter is such that the molar ratio of metallocene to promoter is in the range of from about 1:1 to about 1:1000.
In another embodiment this invention relates to a method for forming a supported metallocene catalyst system comprising: (a) combining at least one metallocene and at least one activator to form an activated metallocene; then (b) adding a promoter; then (c) combining the mixture with support material; wherein the promoter comprises a styrene, a substituted styrene or a compound represented by the formula Ph—SiR
1
R
2
—CH═CH
2
wherein R
1
and R
2
are independently an alkyl group, an arylalkyl, or an alkylaryl; and wherein the amount of promoter added in step (b) is such that the molar ratio of metallocene to promoter is in the range of from about 1:1 to about 1:1000.
In another embodiment this invention relates to a method for forming a supported metallocene catalyst system comprising: (a) combining at least one metallocene and at least one activator to form an activated metallocene; (b) mixing the activated metallocene with support material; and then (c) adding a promoter to the mixture wherein the promoter comprises styrene or a substituted styrene or is represented by the formula: Ph—SiR
1
R
2
—CH═CH
2
wherein R
1
and R
2
are independently an alkyl group, an arylalkyl, or an alkylaryl; and wherein the amount of promoter added in step (c) is such that the molar ratio of metallocene to promoter is in the range of from about 1:1 to about 1:1000.
In another embodiment this invention relates to a method for forming a metallocene catalyst system comprising: (a) combining at least one metallocene with at least one promoter; then (b) adding at least one activator; then (c) combining the mixture with support material wherein the promoter comprises styrene, substituted styrene or is represented by the formula Ph—SiR
1
R
2
—CH═CH
2
wherein R
1
and R
2
are independently an alkyl group, an arylalkyl, or an alkylaryl; wherein the amount of promoter added is such that the molar ratio of metallocene to promoter is in the range of from about 1:1 to about 1:1000.
DETAILED DESCRIPTION
Examples of substituted sytrenes include but are not limited to: 4-methylstyrene, 3-methylstyrene, 3(4)-methylstyrene, 4-t-butylstyrene, 4-fluorostyrene, 2-fluorostyrene, and 3-fluorostyrene.
As used herein, the term “essentially free of polystyrene” means that the catalyst system when completely dry contains less than about 5 weight percent polystyrene. “Polystyrene” refers to a polymer of styrene or substituted styrene.
As used herein, the term “essentially no polymerization of styrene” means that the catalyst system when completely dry is essentially free of polystyrene.
Catalyst System Components
Metallocenes
As used herein “metallocene” refers generally to compounds represented by the formula Cp
m
MR
n
X
q
wherein Cp is a cyclopentadienyl ring which may be substituted, or derivative thereof which may be substituted, M is a Group 4, 5, or 6 transition metal, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X is a halogen, and m=1−3, n=0−3, q=0−3, and the sum of m+n+q is equal to the oxidation state of the transition metal.
Methods for making and using metallocenes are very well known in the art. For example, metallocenes are detailed in U.S. Pat. Nos. 4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403; 4,937,299; 5,017,714; 5,026,798; 5,057,475; 5,120,867; 5,278,119; 5,304,614; 5,324,800; 5,350,723; 5,391,790; and 5,510,502 each fully incorporated herein by reference.
Preferred metallocenes are those represented by the formula:
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, hafnium and titanium, most preferably zirconium;
R
1
and R
2
are identical or different, preferably identical, and are one of a hydrogen atom, a C
1
-C
10
alkyl group, preferably a C
1
-C
3
alkyl group, a C
1
-C
10
alkoxy group, preferably a C
1
-C
3
alkoxy group, a C
6
-C
10
aryl group, preferably a C
6
-C
8
aryl group, a C
6
-C
10
aryloxy group, preferably a C
6
-C
8
aryloxy group, a C
2
-C
10
alkenyl group, preferably a C
2
-C
4
alkenyl group, a C
7
-C
40
arylalkyl group, preferably a C
7
-C
10
arylalkyl group, a C
7
-C
40
alkylaryl group, preferably a C
7
-C
12
alkylaryl group, a C
8
-C
40
arylalkenyl group, preferably a C
8
-C
12
arylalkenyl group, or a halogen atom, preferably chlorine;
R
3
and R
4
are hydrogen atoms;
R
5
and R
6
are identical or different, preferably identical, are one of a halogen atom, preferably a fluorine, chlorine or bromine atom, a C
1
-C
10
alkyl group, preferably a C
1
-C
4
alkyl group, which may be halogenated, a C
6
-C
10
aryl group, which may be halogenated, preferably a C
6
-C
8
aryl group, a C
2
-C
10
alkenyl group, preferably a C
2
-C
4
alkenyl group, a C
7
-C
40
arylalkyl group, preferably a C
7
-C
10
arylalkyl group, a C
7
-C
40
alkylaryl group, preferably a C
7
-C
12
alky

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