Iron olefin copolymerization catalyst

Details Iron olefin copolymerization catalyst Iron olefin copolymerization catalyst

1999-12-17

2001-10-09

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...

C526S134000, C526S172000, C526S348600, C526S352000, C502S162000, C556S013000, C556S138000

Reexamination Certificate

active

06300435

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to late transition metal complexes, a process for their preparation and their use in the polymerization of olefins.
BACKGROUND OF THE INVENTION
The papers Organometallics, 10, 1421-1431, 1991; J. Organomet. Chem., 527(1-2), 263-276, 1997; Inorg. Chem., 35(6), 1518-28, 1996; and Inorg. Chem., 34(16), 4092-4105 (English) 1995 report the reaction of bis (iminophosphoranyl) methane (BIPM) which are typically aryl substituted on the phosphorus atom and the nitrogen with group VIII metal halides (chlorides) further comprising at two weakly coordinating ligands (L) such as nitriles or cyclooctadiene, afforded several products depending on the reaction time, type of ligand or nature of the metal. The product could be a N-C chelating type product or a N-N chelating type product.
The products contain alkyl bridges between the phosphinimine groups. Further, none of the references teach or suggest the use of such compounds for the polymerization of alpha olefins.
U.S. Pat. No. 5,557,023 issued September, 1966 teaches the use of some phosphinimines complexes to oligomerize alpha olefins. Rather, the complexes are of the structure indicated below.
wherein R, Q, etc. are as defined in the patent. The structures disclosed in the patent are not the bisphosphinimines of the present invention. While the reference does teach oligomerization, it does not suggest polymerization.
There are a number of patents and papers by Brookhart and/or Gibson disclosing the use of Group 8, 9 or 10 metals to polymerize olefins. However, such papers teach that copolymers are not produced (e.g. WO 98/27124). The present invention proved copolymers of olefins made using a catalyst of a Group 8, 9 or 10 metal other than nickel.
A poster presentation by Christopher M. Ong and Professor D. W. Stephan at the Chemical Institute of Canada's annual meeting in the summer of 1999 discloses phosphinimine complexes of aluminum. One of the complexes disclosed is similar to those of the present invention except that the metal is aluminum rather than a Group 8, 9 or 10 metal other than nickel. As far as Applicants are aware the poster did not disclose the use of such complexes for the polymerization of olefins.
Lecture 60 from the summer ACS meeting discloses a cubic cobalt complex of phosphinimines. The reference does not disclose olefin polymerization using such complexes. The paper “Phosphiniminato-Cluster von Eisen. Die Kristallstrukturen von [FeCl(NPEt
3
]
4
, [FeC|C—SiMe
3
)(NPEt
3
)]
4
and [Fe
3
Cl
4
[NP(NMe
2
)
3
]
3
]” also discloses cubic phosphinimine complexes but does not teach their use as olefin polymerization catalysts.
SUMMARY OF THE INVENTION
A process for the polymerization of one or more C
2-12
alpha olefins in the presence of an activated complex selected from the group consisting of complexes of formula I:
wherein M is a Group 8, 9 or 10 metal other than nickel; each R
1
and R
2
are independently selected from the group consisting of a hydrocarbyl radical having up to 20 carbon atoms; each X is independently selected from the group consisting of an activatable ligand and n is 1 or 2 provided that if n is 2 and R
1
and R
2
are not branched, cyclic or aromatic radicals, the complex may be cubic; and complexes of formula II:
wherein M, R
1
, R
2
and X are as defined above, and an activator.
A further aspect of the present invention provides a complex of formula II:
wherein each R
1
and R
2
are independently selected from the group consisting of a hydrocarbyl radical having up to 20 carbon atoms; each X is independently selected from the group consisting of an activatable ligand.
In a further aspect, the present invention provides a complex of formula I:
wherein M is a Group 8, 9 or 10 metal other than nickel; R
1
and R
2
are independently selected from the group consisting of a hydrocarbyl radical having up to 20 carbon atoms; each X is independently selected from the group consisting of an activatable ligand and n is 1 or 2 provided that if n is 2 and R
1
and R
2
are not branched, cyclic or aromatic radicals, the complex may be cubic and if the complex is cubic M can not be Co or Fe.
DETAILED DESCRIPTION
The term “scavenger” as used in this specification is meant to include those compounds effective for removing polar impurities from the reaction solvent. Such impurities can be inadvertently introduced with any of the polymerization reaction components, particularly with solvent, monomer and catalyst feed; and can adversely affect catalyst activity and stability. It can result in decreasing or even elimination of catalytic activity, particularly when an activator capable of ionizing the iron complex is also present.
As used herein the term “cubic” when applied to the complex means the central structure in the complex is a cube with alternating “M” and nitrogen atoms at the comers of the cube.
When the above complexes are linear M is a Group 8, 9 or 10 metal other than nickel, preferably Fe, Co, Pd or Pt and most preferably Fe. If the complexes are cubic, M may not be Fe or Co, preferably Pd or Pt.
In the above complexes R
1
and R
2
are independently selected from the group consisting of a hydrocarbyl radical having up to 20 carbon atoms; and each X is independently selected from the group consisting of an activatable ligand. In the complex of formula I, n is 1 or 2 provided that if n is 2 and R
1
and R
2
are not branched, cyclic or aromatic, the complex may be cubic. Preferably, in the above complexes R
1
and R
2
are independently selected from the group consisting of C
3-10
branched or straight chained alkyl radicals and C
6-10
cyclic alkyl radicals and C
6-10
aryl radicals. Most preferably R
1
and R
2
are independently selected from the group consisting of C
1-4
straight chained or branched alkyl radicals. In a particularly preferred embodiment of the present invention, R
1
and R
2
are the same and most preferably a t-butyl radical. In the complexes of the present invention each X is independently an activatable ligand. Generally, X may be selected from the group consisting of a halogen atom, C
1-10
alkyl or alkoxide radicals, C
6-10
cyclic alkyl radicals, cyclic alkoxide radicals, aryl radicals and aryl oxide radicals. Preferably, X is independently selected form the group consisting of a chlorine atom, a bromine atom, a C
1-4
alkyl radical and a C
1-4
alkoxy radical. Suitable alkyl and alkoxy radicals include a methyl radical, an ethyl radical and an ethoxy radical. In some cases it is advantageous if each X is the same.
The metal complexes of the present invention may be prepared by reacting the phosphinimine ligand with a compound such as butyl lithium in an inert hydrocarbyl solvent or diluent. The resulting lithiated ligand may then be reacted with a precursor compound containing M, where M is as defined above, to form the complex. Generally the above reactions may be conducted at temperatures from about −30° C. up to the degradation temperature of the phosphinimine, preferably less than 100° C., most preferably from about 20° C. to about 80° C. For the complex of formula I wherein n is 1 the molar ratio of lithiated phosphinimine ligand to M (Group 8, 9 or 10 metal other than nickel) is from about 1.90 to 2.10, preferably from about 1.92 to 2.05. For the complex of formula 1 wherein n is 2 the molar ratio of lithiated phosphinimine ligand to M, where M is defined above, is from about 3.90 to 4.10, preferably from 3.95 to 4.05. Alternately, to prepare the dimer form (e.g. formula I wherein n is 2). It should be noted that if R
1
and R
2
are straight chained alkyl groups particularly having less than four carbon atoms, the resulting complex may be cubic. However, if R
1
and R
2
are not linear, the complex will be linear (i.e. not cubic with nitrogen and M at alternating comers). It is possible to condense two moles of compound of formula I to a mole of compound of formula II. This may be done by reflux or other suitable means.
The complex of formula II

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