Cationic group 3 catalyst system

Details Cationic group 3 catalyst system Cationic group 3 catalyst system

2001-11-29

2004-01-13

Jones, Dameron L (Department: 1616)

Organic compounds -- part of the class 532-570 series

Organic compounds

Rare earth containing

C502S100000, C502S150000, C502S152000

Reexamination Certificate

active

06677441

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to certain transition metal compounds from Group 3 of the Periodic Table of Elements, and to a catalyst system comprising a Group 3 or Lanthanide transition metal compound and alumoxane, modified alumoxane, non-coordinating anion activator, Lewis acid, or the like to form an active cationic catalyst species for the production of polyolefins such as polyethylene, polypropylene and alpha-olefin copolymers of ethylene and propylene having a high molecular weight.
BACKGROUND OF THE INVENTION
Neutral scandium compounds having two univalent ancillary ligands or a bidentate, divalent ancillary ligand are known from Shapiro et al.,
Organometallics,
vol. 9, pp. 867-869 (1990); Piers et al.,
J. Am. Chem Soc.,
vol. 112, pp. 9406-9407 (1990); Shapiro et al.,
J. Am. Chem Soc.,
vol. 116, pp. 4623-4640 (1994); Hajela et al.,
Organometallics,
vol. 13, pp. 1147-1154 (1994); and U.S. Pat. No. 5,563,219 to Yasuda et al. Similar yttrium, lanthanum and cerium complexes are disclosed in Booij et al.,
Journal of Organometallic Chemistry,
vol. 364, pp. 79-86 (1989) and Coughlin et al.,
J. Am. Chem. Soc.,
vol. 114, pp. 7606-7607 (1992). Similar polymerizations with a metal scandium complex having a bidentate, divalent ancillary ligand using a non-ionizing cocatalyst is known from U.S. Pat. No. 5,464,906 to Patton et al.
Group 3-10 metallocyclic catalyst complexes are described in U.S. Pat. Nos. 5,312,881 and 5,455,317, both to Marks et al.; U.S. Pat. No. 5,064,802 to Stevens et al.; and EP 0 765 888 A2.
Polymerization of olefins with cationic Group 4 metal complexes is illustrated in WO 96/13529 and WO 97/42228. Boratabenzene complexes of Group 3-5 metals are disclosed in WO 97/23493.
Amidinato complexes of Group 3-6 metals are disclosed in U.S. Pat. No. 5,707,913 to Schlund et al. Group 4 bisamido catalysts are disclosed in U.S. Pat. No. 5,318,935 to Canich, et al., and related bidentate bisarylamido catalysts are disclosed by D. H. McConville, et al,
Macromolecules
1996, 29, 5241-5243.
SUMMARY OF THE INVENTION
The present invention is directed to a catalyst system for coordination polymerization comprising a cationic Group 3 or Lanthanide metal stabilized by a monoanionic bidentate ancillary ligand and two monoanionic ligands. The ancillary ligand, together with the metal, forms a metallocycle comprising a ring of at least five primary atoms, counting any &eegr;
5
-bonded cyclopentadienyl in the metallocycle as two primary metallocycle atoms. The metal is preferably scandium, yttrium or lanthanum.
In one embodiment, the monoanionic bidentate ancillary ligand, A, has the formula (C
5
H
4-x
R
x
)TE wherein x is a number from 0 to 4 denoting the degree of substitution; each R is, independently, a radical selected from C
1
-C
20
hydrocarbyl radicals, C
1
-C
20
substituted hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, amido, phosphido, alkoxy or aryloxy or any other radical containing a Lewis acidic or basic functionality, C
1
-C
20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and halogen radicals, or C
5
H
4-x
R
x
is a cyclopentadienyl ring in which two adjacent R-groups are joined to form a C
4
-C
20
ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand which may additionally be substituted with R groups, and may contain a heteroatom within the ring; T is a covalent bridging group containing a Group 14 or 15 element; and E is a &pgr; donating hydrocarbyl, &pgr; donating heterohydrocarbyl, or other &pgr;-donating ligand covalently bound to T such as, for example, allyl, phenyl, benzyl, pyridyl or the like, or E is JR′
z
wherein J is an element from Group 15 or 16, z is 2 when J is a Group 15 element and 1 when J is a Group 16 element, each R′ is independently a radical selected from C
1
-C
20
hydrocarbyl radicals, substituted C
1
-C
20
hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and C
1
-C
20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements.
Heterocyclic pi donating ligands wherein one to three ring carbons of the C
5
H
4-x
R
x
ligand is replaced by a Group 15 or 16 heteroatom; substituted or unsubstituted boratabenzene ligands; substituted or unsubstituted allyl ligands; substituted or unsubstituted pentadienyl ligands; or other delocalized pi-bonded ligands may also be used in place of the C
5
H
4-x
R
x
ligand.
In another embodiment, as represented by structure (I), the monoanionic bidentate ancillary ligand, A, has the formula —NR′=T′—NR′-wherein N is nitrogen and T′ is a covalent bridging group selected from ═C(R)-[C(R)═C(R)]
&eegr;
- and
wherein each R′ is independently as defined above, each R is independently as defined above, except that R independently may also be hydrogen except for R groups attached to the carbon atoms directly bonded to the nitrogen atoms.
In a further embodiment, a typical polymerization process according to the present invention, such as the polymerization or copolymerization of olefins, comprises the steps of activating the transition metal component to a cationic form and contacting ethylene or C
3
-C
20
alpha-olefins alone or with other unsaturated monomers including C
3
-C
20
alpha-olefins, C
5
-C
20
diolefins, and/or acetylenically unsaturated monomers, either alone or in combination with other olefins and/or other unsaturated monomers, with a catalyst comprising, in a suitable polymerization diluent, the activated cationic transition metal component of the invention. The catalyst is activated with an alumoxane, modified alumoxane, non-coordinating anion activator, Lewis acid or the like, or combinations, in an amount to provide a molar ratio of aluminum, non-coordinating anion, or Lewis acid to transition metal of from about 1:10 to about 20,000:1 or more; and reacts with the monomer(s) at a temperature from about −100° C. to about 300° C. for a time from about one second to about 10 hours to produce a polyolefin having a weight average molecular weight of from about 1000 or less to about 5,000,000 or more and a molecular weight distribution of from about 1.5 to about 15.0 or greater.
DETAILED DESCRIPTION OF THE INVENTION
The Group 3 transition metal component of the catalyst system of the invention can be defined broadly by the formula:
wherein M is a Group 3 or Lanthanide metal;
A is a monoanionic, bidentate ancillary ligand which forms a metallocycle with M comprising at least 5 primary atoms, provided that any cyclopentadienyl group or other delocalized pi-bonded ligand in the metallocycle is counted as two primary metallocycle atoms; each Q is independently a monoanionic ligand such as a radical selected from halide, hydride, substituted or unsubstituted C
1
-C
20
hydrocarbyl, hydrocarbylsilyl, alkoxide, aryloxide, amide or phosphide or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand, or a diene, with the proviso that where any Q is a hydrocarbyl radical, such Q is not a substituted or unsubstituted cyclopentadienyl radical;
L is a neutral Lewis base such as, for example, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylphosphine, lithium chloride or the like, and can also be optionally covalently bound to one or both Q, provided Q is not hydride or halide. L can also be a second transition metal of the same type, i.e. the transition metal component can be dimeric; and
w is a number from 0 to 3.
In cationic form as activated for olefin polymerization, the transition metal complex has the formula:
wherein M, A, Q, L and w are as defined above and A′ is a weakly or noncoordinating anion which counterbalances the cationic complex.
In a preferred embodiment, the transition metal component of the catalyst system has the formula:
wherein C
5
H
4-x
R
x
is typically a c

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