Aluminum complexes for olefin polymerization

Details Aluminum complexes for olefin polymerization Aluminum complexes for olefin polymerization

2001-03-15

2002-12-10

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C502S103000, C526S131000, C526S134000, C526S154000, C526S352000, C556S174000, C556S176000, C556S178000

Reexamination Certificate

active

06492474

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to novel aluminum complexes. The complexes are of aluminum and a bridged phosphinimine compound. The complexes may have one aluminum atom or may be a “dimer” having two aluminum atoms.
BACKGROUND OF THE INVENTION
Over the last fifteen years or so there has been an increasing interest in complexes other than the Ziegler-Natta complexes which have the potential to polymerize olefins. The work of EXXON and Dow have lead to the commercialization of metallocene and constrained geometry catalysts which produce polymers tending to have a single active catalyst site. This type of research has lead to more complex ligand structures such as those of Brookhart which also show activity as polymerization catalysts. These systems are used with transition metals as the active catalyst center. There is a desire to find new species which may be capable of olefin polymerization with metals other than the transition metals.
There was a poster presentation by Christopher M. Ong and Professor Douglas W. Stephan of the University of Windsor at the summer meeting of the Chemical Institute of Canada in Toronto which disclosed aluminum phosphinimine complexes. The complex disclosed is a mono aluminum complex having phenyl substituents on the phosphorus atom and trimethyl silyl substituents on the nitrogen atom. The presentation does not disclose the dimer of the present invention.
Jordan et al. JACS 1997, 119, 8125 “Cationic Aluminum Alkyl Complexes Incorporating Amidinate Ligands”, teaches amine, imine and aluminum complexes. The paper does not teach complexes of aluminum phosphinimine. The polymerization activity of the complexes of Jordan is very low.
Gibson et al. Chem. Commun. 1998, 2523 “Novel Aluminum Ethylene Polymerization Catalysts Based on Monoaonic N,N,N,-Pyridyliminoamide Ligands” teaches the polymerization of ethylene using a complex with a “Brookhart” tridentate ligand and aluminum. Gibson's catalyst does not teach the complexes of aluminum phosphinimine of the present invention. Further, the polymerization activity of the complexes of Gibson is very low.
The present invention seeks to provide novel aluminum complexes and processes for polymerizing olefins using such complexes.
SUMMARY OF THE INVENTION
The present invention provides a process for preparing a complex of aluminum and a bridged phosphinimine comprising reacting moles of a bridged phosphinimine compound of the formula I:
wherein each R
1
is independently selected from the group consisting of C
1-8
straight or branched alkyl radical or a C
6-12
cyclic aliphatic or aromatic radical; radicals of the formula Si(R
4
)
3
wherein each R
4
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; and R
3
is selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted with one or more halogen atoms or a C
1-4
alkyl radical with an aluminum compound of the formula III (Al(R
2
)
3−n
X
n
) wherein each R
2
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and n is 0, 1, or 2 under an inert atmosphere, in an inert hydrocarbyl solvent or diluent at a temperature from 50° C. to 200° C. provided that if the molar ratio of compound of formula I to aluminum compound is from 0.8 to 1.20, R
3
can not be phenyl if R
1
is trimethyl silyl, X is chlorine and n is 2.
The present invention also provides a complex of formula IV:
wherein each R
1
is independently selected from the group consisting of C
1-8
straight or branched alkyl radical or a C
6-12
cyclic aliphatic or aromatic radical; radicals of the formula Si(R
4
)
3
wherein each R
4
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; R
2
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and a is 1 or 2; and R
3
is selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted with one or more halogen atoms or a C
1-4
alkyl radical.
The present invention further provides a complex of the formula V:
wherein each R
1
is independently selected from the group consisting of C
1-8
straight or branched alkyl radical or a C
6-12
cyclic aliphatic or aromatic radical; radicals of the formula Si(R
4
)
3
wherein each R
4
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; R
2
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and a is 1 or 2; and R
3
is selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted with one or more halogen atoms or a C
1-4
alkyl radical provided that R
3
can not be phenyl if R
1
is trimethyl silyl, X is chlorine and n is 2.
The present invention further provides a process for the polymerization of alpha olefins at a temperature from 20° C. to 250° C. and at a pressure from 15 to 4500 psig in the presence of the complexes of formula IV and an activator selected from the group consisting of:
(i) aluminoxane compounds R
20
2
AlO(R
20
AlO)
m
AlR
20
2
wherein each R
20
is independently selected from the group consisting of C
1-20
hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum in the activator to aluminum in the complex from 20:1 to 1000:1;
(ii) anions of the formula [B(R
18
)
4
]
—
wherein each R
18
is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C
1-4
alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula —Si(R
19
)
3
; wherein each R
19
is independently selected from the group consisting of a hydrogen atom and a C
1-4
alkyl radical; and an activator of the formula [B(R
18
)
3
] wherein R
18
is as defined above, to provide a molar ratio of B:Al from 0.4 to 1.2; and
(iii) a mixture of (i) and (ii) above.
The present invention further provides a process for polymerizing one or more C
2-8
olefins at a temperature from 20° C. to 120° C. and at a pressure from 15 to 4500 psig in the presence of a complex of the formula V:
wherein each R
1
is independently selected from the group consisting of C
1-8
straight or branched alkyl radical or a C
6-12
cyclic aliphatic or aromatic radical; radicals of the formula Si(R
4
)
3
wherein each R
4
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; R
2
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and a is 1 or 2; and R
3
is selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted with one or more halogen atoms or a C
1-4
alkyl radical and an activator selected from the group consisting of:
(i) aluminoxane compounds R
20
2
AlO(R
20
AlO)
m
AlR
20
2
wherein each R
20
is independently selected from the group consisting of C
1-20
hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum in the activator to aluminum in the complex from 20:1 to 1000:1;
(ii) anions of the formula [B(R
18
)
4
]
—
wherein each R
18
is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C
1-4
alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula —Si(R
19
)
3
; wherein each R
19
is independently selected from the group consisting of a hydrogen atom and a C
1-4
alkyl radical; and an activator of the formula [B(R
18
)
3
] wherein R
18
is as defined above, to provide a molar ratio of B:Al from 0.8 to 1.2; and
(iii) a mixture of (i) and (ii) above.
DETAILED DESCRIPTION OF T

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