Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-08-09
2002-09-03
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S174000, C526S189000
Reexamination Certificate
active
06444834
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel phosphinimine aluminum complexes containing additional heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur.
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 (i.e. carbene complex) 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 etal. Chem. Commun. 1998, 2523 “Novel Aluminum Ethylene Polymerization Catalysts Based on Monoanionic 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.
Applicants' co-pending U.S. patent application Ser. No. 09/375,618 filed Aug. 17, 1999 discloses precursors for the complexes of the present invention but does not disclose the complexes of the present invention.
There was a presentation at the Canadian Chemical Society National Conference, Calgary, May 27-31, 2000 entitled “Chemistry of Novel Alkyl Aluminum Bis(iminophosphorano)-Methanide and Methanediide Complexes” by Kasani Aparna and Ronald G. Cavell, Department of Chemistry, University of Alberta. The paper does disclose synthesis of some of the compounds of the present invention. The presentation does not disclose that the compounds of the present invention would be useful in the polymerization of olefins polymers.
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 complex of formula I:
wherein each R
1
is independently selected from the group consisting of a C
1-8
straight or branched alkyl radical, a C
6-12
cyclic aliphatic or aromatic radical and a radical of the formula Si(R
6
)
3
wherein each R
6
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; R
2
is selected from the group consisting of C
1-8
straight chained, branched or cyclic aliphatic radicals and C
6-12
cyclic aliphatic and aromatic radicals; c is 0 or 1; each R
3
is independently selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted by one or more substituents selected from the group consisting of halogen atoms and C
1-4
alkyl radicals; each R
4
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and b is 1 or 2; R
5
is selected from the group consisting of C
1-8
straight chained, branched or cyclic aliphatic radicals and C
6-12
cyclic aliphatic and aromatic radicals; Y is a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom and a is an integer so that the valence state of Y−2=a.
The present invention further provides a process for preparing a complex of formula I, comprising reacting a compound of formula II:
wherein each R
1
is independently selected from the group consisting of a C
1-8
straight or branched alkyl radical, a C
6-12
cyclic aliphatic or aromatic radical and a radical of the formula Si(R
6
)
3
wherein each R
6
is independently selected from the group consisting of C
1-8
alkyl and alkoxy radicals; each R
3
is independently selected from the group consisting of C
1-8
alkyl radicals and C
6-12
aromatic radicals which are unsubstituted or substituted by one or more substituents selected from the group consisting of halogen atoms and C
1-4
alkyl radicals; each R
4
is independently selected from the group consisting of C
1-8
alkyl radicals, X is a halogen atom and b is 1 or 2; with a compound selected from the group consisting of R
5
YC(YR
2
)
d
and R
2
Y═C═O wherein R
2
is selected from the group consisting of C
1-8
straight chained, branched or cyclic aliphatic radicals and C
6-12
cyclic aliphatic and aromatic radicals; d is 0 or 1; R
5
is selected from the group consisting of C
1-8
straight chained, branched or cyclic aliphatic radicals and C
6-12
cyclic aliphatic and aromatic radicals; Y is a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, provided that if a reactant of the formula R
2
Y═C═O is used in the complex of formula I, a is 0 and if a reactant of the formula R
5
YC(YR
2
)
d
is used if d is 1 c is 1 and if d is 0, c is 0.
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 according to claim 1 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.
In a further embodiment the present invention also provides a process for polymerizing one or more C
2-8
olefins at a temperature from 120° C. to 250° C. and at a pressure from 15 to 4500 psig in the presence of a complex according to claim 1 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
; wher
Cavell Ronald G.
Kasani Aparna
Wang Qinyan
Johnson Kenneth H.
Shaver Paul F.
The Governors of the University of Alberta
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