Phosphinimine methanide transition metal catalysts

Details Phosphinimine methanide transition metal catalysts Phosphinimine methanide transition metal catalysts

2000-07-26

2002-11-05

Shaver, Paul F. (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S012000, C556S019000

Reexamination Certificate

active

06476245

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to novel catalysts of metals preferably transition metals and to the processes for using such catalysts for olefin polymerization. The catalyst contains at least one phosphinimine center, and a carbon atom or an alkenyl radical bonded to the metal to form a metal heteroatom alkyl bond or a carbene structure, respectively.
BACKGROUND OF THE INVENTION
Currently there is increasing interest in catalysts of transition metals having novel structures.
Recently there has been significant interest in Brookhart's ligand which may complex later transition metals to form a catalyst useful in an olefin polymerization process. Such complexes are disclosed, for example in World Patent Application 96/23010 jointly in the names of the University of Carolina at Chapel Hill and E.I. DuPont published Aug. 1, 1996. The Brookhart et al patent application does not teach the complexes of the present invention.
The recent paper (Chem. Comm (1998) p. 849) by Gibson and coworkers at Imperial College UK (and BP) teach complexes having a novel structure that is dissimilar to the complexes of the present invention. It is postulated that the complexes of Gibson et al. will have utility in the polymerization of certain monomers such as alpha olefins.
There has been a great deal of work recently by both Exxon in the field of metallocene chemistry and by the Dow Chemical Company in single site constrained geometry complexes. As far as applicant has been able to determine none of the chemistry proposed by either Exxon or Dow contain a carbene structure or a constrained alkyl carbon bonded to a transition metal. There are several patents relating to amidinato complexes of transition metals which are suitable for the polymerization of various olefins. U.S. Pat. No. 5,502,128 issued Mar. 26, 1996, assigned to University of Massachusetts, teaches such complexes may be used to polymerize vinyl aromatic monomers; and U.S. Pat. No. 5,707,913 issued Jan. 13, 1998, assigned to BASF, teaches such compounds may be used to polymerize olefins. Neither of these patents disclose complexes of the structure of the present invention.
U.S. Pat. No. 5,557,023 issued September 1996 teaches the use of some complexes of transition metals to oligomerize lower alpha olefins such as ethylene to higher olefins such as hexene and the like. The complexes of the patent do not contain a carbene structure or substituted carbon bonded to the transition metal.
Copending U.S. patent application Ser. No. 09/375,943 filed Aug. 17, 1999 in the name of R. G. Cavell et al. discloses the complexes useful in the catalyst of the present invention.
U.S. Pat. No. 6,060,568 issued May 9, 2000 in the name of the Applicant discloses complexes similar to those of the present invention except that the complexes contain only one R
7
and one R
8
substituent. The present invention provides for more than one R
7
or R
8
substituents. The sum of the subscripts a and b is a whole number greater than 2 and up to the sum of the valence and co-ordination number of the metal (i.e. both the electrovalence and coordinate valence).
Applicant has been unable to identify any prior art disclosing the catalyst of the present invention for the polymerization of olefins.
SUMMARY OF THE INVENTION
The present invention provides a process for the polymerization of one or more C
2-12
alpha olefins in the presence of a complex selected from the group consisting of a complex of formula I:
wherein M is a metal atom; R
1
, R
2
, R
3
and R
4
are independently selected from the group consisting of a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom and a C
1-6
, most preferably a C
1-4
alkyl radical; R
7
and R
8
are independently selected from the group consisting of a hydrogen atom, a halogen atom, an amide of the formula —NR
1
R
2
, an imide of the formula ═NR
1
, an alkoxide or aryl oxide group of the formula —OR
1
, a siloxy group of the formula —OSi(R
1
)
3
wherein R
1
and R
2
are defined above, and a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by a halogen atom or a C
1-6
alkyl radical and a Lewis base (neutral coordinating ligands) which may contain a donor heteroatom including but not limited to ethers, tertiary amines, tertiary phosphines and cyclic amines; a and b are integers and a+b is an integer greater than 2 up to the sum of the valence and co-ordination number of M; and each R
5
is independently selected from the group consisting of radicals selected from the group consisting of saturated and unsaturated straight chained, branched and cyclic hydrocarbyl radicals, preferably C
1-15
saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals, most preferably C
1-8
straight or branched alkyl radicals, C
6-12
cyclic aliphatic or aromatic radicals, radicals of the formula Si(R
6
)
3
wherein each R
6
is independently selected from the group consisting of saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals, preferably C
1-10
saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals and radicals of the formula III:
wherein R
9
, R
10
, R
11
and R
12
are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO
2
radical, a C
1-6
alkyl radical and a C
8-12
aryl radical; E is an endocyclic nitrogen atom or a C—CN group; and R
14
is selected from the group consisting of a hydrogen atom, a sulfur atom, an oxygen atom, an amido radical which is unsubstituted or may be substituted by C
1-20
alkyl radical, preferably a C
1-6
alkyl radical or a radical of the formula —Si(R
6
)
3
wherein R
6
is as defined above, a C
1-20
hydrocarbyl radical, a C
6-12
aromatic radical and a radical of the formula III as defined above, each of which may contain one or more functional groups including a heteroatom acting as a Lewis base; and optionally R
14
taken together with the metal may form a ring; and an activator at a temperature from 20 to 250° C. and at a pressure from 15 to 15,000 psi.
The present invention also provides a complex of formula I:
wherein M, R
1
, R
2
, R
3
, R
4
, R
5
, R
7
, R
8
, R
14
, a and b are as defined above.


REFERENCES:
patent: 5502128 (1996-03-01), Flores et al.
patent: 5534474 (1996-07-01), Becker et al.
patent: 5557023 (1996-09-01), Somogyvari et al.
patent: 5589555 (1996-12-01), Zboril et al.
patent: 5707913 (1998-01-01), Schlund et al.
patent: 6060568 (2000-05-01), Cavell et al.
patent: 0668295 (1995-08-01), None
patent: WO 96/23010 (1996-08-01), None
U.S. application Ser. No. 09/375,943, Cavell et al., filed Aug. 17, 1999.*
U. Zucchini, E. Albizzati and U. Gianni, Synthesis and Properties of Some Titanium and Zirconium Benzyl Derivatives, J. Organometal. Chem., 26 (1971) 357-372.
Von R. Appel and I. Ruppert, Darstellung silylieter Alkylen-bisminophosphorane und ihre Cyclisierung mit Phosphor (V)-fluoriden, Z. anorg. allg. Chem. 406, 131-144 (1974).
Richard A. Andersen, Chloro- and Methyltris[(hexamethyldisilyl) amido]zirconium (IV) and -hafnium (IV), Inorganic Chemistry, vol. 18, No. 6, 1979.
Michael D. Fryzuk, David H. McConville and Steven J. Rettig, Synthesis, structure and hydrogenation of n3-benzyl diphosphine complexes of rhodium and iridium, Journal of Organometallic Chemistry, 445 (1993) 245-256.
Lynda K. Johnson, Christopher M. Killian, and Maurice Brookhart, New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and a-Olefins, J. Am. Chem. Soc. vol. 117, (1995), 6414.
George J.P. Britovsek, Vernon C. Gibson, Brian S. Kimberley, Peter J. Maddox, Stuart J. McTavish, Gregory A. Solan, Andrew J.P. White, and David J. Williams, Novel olefin polymerization catalysts based on iron and cobalt, Chem. Commun., (1998) 849.

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