Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2002-04-24

2004-08-03

Harlan, Robert Deshon (Department: 1713)

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

Organic compounds

Heavy metal containing

C556S051000, C556S057000, C556S137000, C556S138000, C502S162000, C502S167000, C502S168000, C526S161000, C526S171000, C526S172000

Reexamination Certificate

active

06770771

ABSTRACT:

FIELD OF THE INVENTION
Various nickel and palladium complexes, for example of &agr;-diimines substituted at the carbon atoms by heteroatoms such as nitrogen or oxygen, and selected ureas and urethanes, may be used as polymerization catalysts for olefins such as ethylene. The palladium catalysts also polymerize polar comonomers.
TECHNICAL BACKGROUND
Recently polymerization catalysts containing late transition metals such as palladium and nickel have been reported. Among these compounds are complexes of &agr;-diimines (see World Patent Application 96/23010) and various other types of ligands (see U.S. Pat. No. 5,714,556). These catalysts can, under various conditions, make unique polyolefins, such as those that contain “abnormal” branching patterns when compared to polymers made by the well known Ziegler-Natta- and metallocene-type catalysts. In addition some of these catalysts can polymerize olefins which are often not polymerizable with most catalysts based on transition metal compounds, for example polar olefins such as olefinic esters. Therefore, new olefin polymerization catalysts containing late transition metals are of great interest.
The use of palladium containing catalysts to polymerize olefins is described in S. Mecking, et al., J. Am. Chem. Soc., vol. 120, p. 888-899 (1998). Nickel diimine complexes as olefin polymerization catalysts are described in L. K. Johnson, et al., J. Am. Chem. Soc., vol. 117, p. 6414-6415 (1995), and L. K. Johnson, et al., J. Am. Chem. Soc., vol. 118, p.267-268 (1996). None of the catalysts described herein are described in these papers.
Certain iron, cobalt and molybdenum complexes of &agr;-diimines having nitrogen substituted in the backbone are described in M. Doring, et al., Z. Anorg. Allg. Chem., vol. 620, p. 551-560 (1994). None of these substituted &agr;-diimines or these metal complexes are claimed herein.
The reactions of various bis(imidoyl chlorides) of oxalic acid with amines, diamines and aminoalcohols to form various nitrogen and oxygen substituted &agr;-diimines is described in D. Lauder, et al., J. Prakt. Chem., vol. 337, p. 143-152 and ibid., p. 508-515 (1995). None of the substituted &agr;-diimines enumerated in these papers is claimed herein.
SUMMARY OF THE INVENTION
This invention concerns a first process for the polymerization of one or more olefins of the formula H
2
C═CHR
1
and optionally one or more olefins of the formula H
2
C═CHR
2
, comprising, contacting said olefins with a complex containing a transition metal selected from the group consisting of palladium, nickel, titanium, zirconium, scandium, vanadium, chromium, iron, cobalt, and a rare earth metal and a ligand of the formula
which is an active polymerization catalyst, wherein:
each R
1
is independently hydrogen or alkyl;
each R
2
is independently substituted alkyl or —CO
2
R
50
;
A and E are each independently oxygen, sulfur, phosphorous or nitrogen;
R
3
and R
8
are each independently hydrocarbyl or substituted hydrocarbyl provided that the carbon atom bound to the nitrogen atom is bound to at least two other carbon atoms;
R
4
, R
5
, R
6
and R
7
are each independently hydrocarbyl or substituted hydrocarbyl;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
9
and R
10
are each independently hydrocarbyl or substituted hydrocarbyl;
R
50
is hydrocarbyl or substituted hydrocarbyl;
and provided that:
when said ligand is (II) or (III) said transition metal is nickel;
when H
2
C═CHR
2
is present a palladium complex is present;
the members of any one or more of the pairs R
4
and R
5
, R
6
and R
7
, R
4
and R
6
, and R
5
and R
7
taken together may form a ring;
when A is oxygen or sulfur, R
5
is not present; and
when E is oxygen or sulfur, R
7
is not present.
This invention also concerns a second process for the polymerization of one or more olefins of the formula H
2
C═CHR
1
and optionally one or more olefins of the formula H
2
C═CHR
2
, comprising, contacting said olefins, a first compound of the formula
and:
(a) a second compound W, which is a neutral Lewis acid capable of abstracting X
−
from M to form WX
−
, and which is also capable of transferring an alkyl group or a hydride to M, provided that WX
−
is a weakly coordinating anion; or
(b) a combination of a third compound which is capable of transferring an alkyl or hydride group to M and a fourth compound which is a neutral Lewis acid which is capable of abstracting X
−
, a hydride or an alkyl group from M to form a weakly coordinating anion; or
(c) when at least one of X is a hydride or alkyl group, a fifth compound which is a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; wherein:
M is Ni, Pd, Ti, Zr, Sc, V, Cr, Fe, Co or a rare earth metal;
each X is independently a monoanion;
n is equal to the oxidation number of M;
each R
1
is independently hydrogen or alkyl;
each R
2
is independently substituted alkyl or —CO
2
R
50
;
A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;
R
3
and R
8
are each independently hydrocarbyl or substituted hydrocarbyl provided that the carbon atom bound to the nitrogen atom is bound to at least two other carbon atoms;
R
4
, R
5
, R
6
and R
7
are each independently hydrocarbyl or substituted hydrocarbyl;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
9
and R
10
are each independently hydrocarbyl or substituted hydrocarbyl;
R
50
is hydrocarbyl or substituted hydrocarbyl;
and provided that
when said first compound is (II) or (III), M is Ni;
the members of any one or more of the pairs R
4
and R
5
, R
6
and R
7
, R
4
and R
6
, and R
5
and R
7
taken together may form a ring;
when H
2
C═CHR
2
is present a palladium complex is present;
when A is oxygen or sulfur, R
5
is not present; and
when E is oxygen or sulfur, R
7
is not present.
This invention also includes a compound of the formula
wherein:
M is Ni, Pd, Ti, Zr, Sc, V, Cr, Fe, Co or a rare earth metal;
each X is independently a monoanion;
n is equal to the oxidation number of M;
A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;
R
3
and R
8
are each independently hydrocarbyl or substituted hydrocarbyl provided that the carbon atom bound to the nitrogen atom is bound to at least two other carbon atoms;
R
4
, R
5
, R
6
and R
7
are each independently hydrocarbyl or substituted hydrocarbyl;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
9
and R
10
are each independently hydrocarbyl or substituted hydrocarbyl;
and provided that
when said compound is (V) or (VI), M is Ni;
the members of any one or more of the pairs R
4
and R
5
, R
6
and R
7
, R
4
and R
6
, and R
5
and R
7
taken together may form a ring;
when A is oxygen or sulfur, R
5
is not present; and
when E is oxygen or sulfur, R
7
is not present.
Also disclosed herein is a compound of the formula
wherein:
A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;
R
4
, R
5
, R
6
and R
7
are each independently hydrocarbyl or substituted hydrocarbyl;
R
11
is hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms, or a functional group;
R
12
, R
13
, R
14
, R
15
, R
16
, R
17
, R
18
, R
19
, and R
20
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
and provided that
the members of any one or more of the pairs R
4
and R
5
, R
6
and R
7
, R
4
and R
6
, and R
5
and R
7
taken together may form a ring;
any two of R
11
, R
12
, R
13
, R
14
, R
15
, R
16
, R
17
, R
18
, R
19
, and R
20
vicinal to one another taken together may form a ring with the further proviso that if R
11
and R
12
are taken together to form a ring, then R
11
and R
12
taken together contain at least 2 carbon atoms;
when A is oxygen or sulfur, R
5
is not present; and
when E is oxygen or sulfur, R
7
is not present.
DETAILS OF THE INVENTION
Herein, certain terms are used. Some of them are:
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is p

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