Group 8, 9 or 10 olefin copolymerization catalyst

Details Group 8, 9 or 10 olefin copolymerization catalyst Group 8, 9 or 10 olefin copolymerization catalyst

2000-08-10

2002-04-30

Rotman, Alan L. (Department: 1625)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C526S348600, C526S352000, C556S013000, C556S138000, C546S021000

Reexamination Certificate

active

06380333

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 in Organometallics, 10, 1421-1431, 1991; Inorg. Chem., 34, 4092-4105, 1995; J. Organomet. Chem., 527(1-2), 263-276,1997; and Inorg. Chem., 35(6), 1518-28, 1996, report the reaction of bis (iminophosphoranyl) methane (BIPM) which are typically aryl substituted on the phosphorus atom and the nitrogen with Group 8, 9 or 10 metal halides (chlorides) further comprising at two weakly coordinating ligands (L) such as nitrites 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 product (similar to those of the present invention).
The products contain alkyl bridges between the phosphinimine groups and the references do not disclose the pyridyl bridged compounds of the present invention. 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, 1996 teaches the use of some phosphinimines complexes to oligomerize alpha olefins. However, the complexes disclosed are not bisphosphinimine complexes. 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.
WO 98/30609 patent application published Jul. 16, 1998 assigned to E. I. du Pont de Nemours teaches the use of various complexes of nickel to polymerize alpha olefins. The most structurally similar complex in the disclosure is compound XXXXI at the middle of page 9 and the associated description of the various substituents. However, the compound does not contain a pyridyl bridge. Rather, the nickel atom completes the cyclic structure in the middle of the compound. The reference does not contemplate or disclose compounds of the present invention which have a pyridyl bridge between the bisphosphinimine functionality. The reference fails to disclose the subject matter of the present invention.
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 did not teach the copolymerizations (e.g. WO 98/27124). The present invention provides olefin copolymerization using an iron based catalyst.
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 an activatable complex of a Group 8, 9 or 10 metal and ligand of formula I:
wherein R
2
, R
3
, R
4
and R
5
are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted, further substituted or an inert functional group; R
6
and R
7
are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted, trialkyl silyl radical and an inert functional group; and R
8
, R
9
and R
10
are independently selected from the group consisting of a hydrogen atom, a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group.
A further aspect of the present invention provides a process for the polymerization of one or more C
2-12
alpha olefins in the presence of:
(a) a complex comprising a Group 8, 9 or 10 metal and ligand of formula I:
wherein R
2
, R
3
, R
4
and R
5
are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional group; R
6
and R
7
are each independently selected from hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl; and R
8
, R
9
and R
10
are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group; and
(b) an activator at a temperature from 20 to 250° C. and at a pressure from 15 to 15000 psi.
In a further aspect, the present invention provides a process for reacting one or more C
2-12
alpha olefins in the presence of a catalyst of formula III:
wherein R
2
to R
10
and M are defined above; L
1
is a neutral monodenate ligand which is displaced by one or more of an activator, a scavenger or a monomer; x is from 0 to 12; L
2
is an activatable ligand; and y is the oxidation state of the metal; with an activator at a temperature from 20 to 250° C. and at a pressure from 15 to 15000 psi.
The present invention further comprises reacting a compound of formula II:
wherein R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and M are as defined above, X is a halogen and n is an integer from 1 to 3 with an alkylating agent at a temperature from −50 to 250° C. to produce a compound of formula III as defined above.
The present invention also provides an olefin co- or homopolymer having a weight average molecular weight (Mw) from 5×10
4
to 10
7
and a degree of short chain branching from 1-30 per 1000 carbon atoms prepared in the presence of an iron (or cobalt) containing catalyst.
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 Group 8, 9 or 10 metal complex is also present.
The term “an inert functional group” means a functional group on a ligand or substituent which does not participate or react in the polymerization reaction. For example, in the polymerization aspect of the present invention an inert functional group would not react with any of the monomers, the activator or the scavenger of the present invention. Similarly for the alkylation of the metal complex or the formation of the metal complex the inert functional group would not interfere with the alkylation reaction or the formation of the metal complex respectively.
The phrase “a neutral monodenate ligand” means a ligand which is only loosely bound to the metal by a coordinative bond. These may include water (H
2
O) or tetrahydrofuran (THF).
As used in this specification, an activatable ligand is a ligand removed or transformed by an activator. These include anionic substituents and/or bound ligands. Exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C
1-10
hydrocarbyl radical, a C
1-10
alkoxy radical, a C
5-10
aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C
1-8
alkyl radical, a C
1-8
alkoxy radical, a C
6-10
aryl or aryl oxy radical, an amido radical which is unsubstituted or substituted by up to two C
1-8
alkyl radicals, and a phosphido radical which is unsubstituted or substituted by up to two C
1-8
alkyl radicals.
In the above compounds formula I-III, R
2
, R
3
, R
4
and R
5
are independently selected from the group consisting of a hydrocarbyl radical and an inert functional group. Preferably R
2
, R
3
, R
4
and R
5
are selected from the group consisting of C
1-10
alkyl or aryl radicals, most preferably C
1-4
radicals such as a bulky t-butyl radical and phenyl radicals. In the above compounds, R
8
, R
9
and R
10
are independently selected from the group consisting of a hydrogen atom, a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group, preferably a hydrogen atom and a C
1-10
, most preferably a C
1-4
alkyl radical. In the above formula, R
6
and R
7
are independently selected from the group consisti

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