Polymerization catalyst activator complexes and their use in...

Details Polymerization catalyst activator complexes and their use in... Polymerization catalyst activator complexes and their use in...

2002-12-05

2004-10-19

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C502S103000, C502S203000, C502S231000

Reexamination Certificate

active

06806328

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to polymerization catalyst activator compounds, to methods of making these activator compounds, to polymerization catalyst systems containing these activator compounds, and to polymerization processes utilizing the same. More particularly, the invention relates to activator complexes including at least two Group 13 metals comprising one or more halogenated aryl groups, the metals bound to the oxygen atoms of a diol.
BACKGROUND OF THE INVENTION
Polymerization catalyst compounds are typically combined with an activator (or co-catalyst) to yield compositions having a vacant coordination site that will coordinate, insert, and polymerize olefins. Typically, methylaluminoxane (MAO) is utilized to activate metallocene catalysts. Alternative activators for metallocenes and other single-site polymerization catalysts have been discovered in recent years.
Group 13 based Lewis acids having three fluorinated aryl substituents are known to be capable of activating transition metal compounds into olefin polymerization catalysts. Trisperfluorophenylborane is demonstrated in EP 0 425 697 and EP 0 520 732 to be capable of abstracting a ligand for cyclopentadienyl derivatives of transition metals while providing a stabilizing, compatible noncoordinating anion. The noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for cationic metallocene complexes which are active for olefin polymerization. The term noncoordinating anion as used herein applies both to truly noncoordinating anions and coordinating anions that are at most weakly coordinated to the cationic complex so as to be labile to replacement by olefinically or acetylenically unsaturated monomers at the insertion site.
The synthesis of Group 13-based compounds derived from trisperfluorophenylborane are described in EP 0 694 548. These Group 13-based compounds are said to be represented by the formula M
1
(C
6
F
5
)
3
(where M
i
is a Group 13 metalloid such as aluminum or boron) and are prepared by reacting the trisperfluorophenylborane with dialkyl or trialkyl Group 13-based compounds at a molar ratio of “basically 1:1” so as to avoid mixed products, those including the type represented by the formula M
i
(C
6
F
5
)
n
R
3−n
, where n=1 or 2. Utility for the tris-aryl aluminum compounds in Ziegler-Natta olefin polymerization is suggested.
U.S. Pat. No. 6,147,174 discloses an olefin polymerization process utilizing activator compounds of the formula R
n
Al(ArHal)
3−n
, where ArHal represents a halogenated aryl group and R represents a monoanionic group other than a halogenated aryl group.
V. C. Williams et al. 121 J. AM. CHEM. SOC. 3244-3245 (1999) disclose the synthesis of diborane activators (bis-pentafluorophenyl)boryl groups tethered via organic linkers. The problem with some of these Group 13-based activators in polyolefin polymerization is low activity, among other problems. What is need is an improved Group 13-based activator and method of polymerizing olefins that can utilize these metalloid-type activators.
SUMMARY OF THE INVENTION
The present invention solves these and other problems by providing a catalyst system and a method of polymerizing olefins, the catalyst system comprising a catalyst compound and an activator compound, wherein the activator compound is represented in one aspect by:
wherein each M
1
is a Group 13 atom;
each R
3
, R
3′
, R
3″
, and R
3′″
group is independently selected from: C
1
to C
30
alkyls, C
1
to C
30
heteroatom containing alkyls, C
1
to C
30
alkoxys, halogenated C
1
to C
30
alkoxys, C
2
to C
30
alkenyls, C
6
to C
60
aryls, C
6
to C
60
aryloxys, halogenated C
6
to C
60
aryloxys, and C
6
to C
60
halogenated aryls; with the proviso that at least one of R
3
, R
3′
, R
3″
, and R
3′″
is a fluorinated C
6
to C
60
aryl group
R
1
and R
2
are independently selected from substituted or unsubstituted C
1
to C
100
hydrocarbylenes, aliphatic or aromatic;
R, when present, is a substituted or unsubstituted C
30
hydrocarbylene aliphatic or aromatic group; wherein when R is absent, R
1
and R
2
are bound together; and
x is 0 or an integer from 1 to 100.


REFERENCES:
patent: 6031145 (2000-02-01), Commereuc et al.
patent: 6124231 (2000-09-01), Fritze et al.
patent: 6147174 (2000-11-01), Holtcamp et al.
patent: 6211111 (2001-04-01), Chen et al.
patent: 6214760 (2001-04-01), Chen et al.
patent: 6248445 (2001-06-01), Yamakawa et al.
patent: 6291614 (2001-09-01), Chen et al.
patent: WO 99/42467 (1999-08-01), None
patent: WO 99/42467 (1999-08-01), None
Mulford et al., J. Am. Chem. Soc. 2000, 19, 35-42.*
V. Clifford Williams, et al., J. Am. Chem. Soc. 1999, 121, 3244-3245.
Mulord, Douglas R. et al., “Group 4 and 5 metal derivatives of 2,2'-methylene-bis(6-phenylphenoxide),” vol. 19, 35-42 (2000).
Chen, Eugene et al., “Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships, ” vol. 100, 1391-1434 (2000).

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