Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-04-24
2002-10-01
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S036000, C556S037000, C564S272000
Reexamination Certificate
active
06458979
ABSTRACT:
FIELD OF THE INVENTION
Iron and cobalt complexes of selected 1,4,7-triaza-3-oxa-1,4,6-heptatrienes or 2,5,8-triaza-1,8-nonadienes are catalysts for the polymerization of ethylene, optionally in the presence of cocatalysts such as alkylaluminum compounds.
TECHNICAL BACKGROUND
Polyethylenes are very important items of commerce, large quantities of various grades of these polymers being produced annually for a large number of uses, such as packaging films and moldings. There are many different methods for making such polymers, including many used commercially, such as free radical polymerization to make low density polyethylene, and many so-called coordination catalysts such as Ziegler-Natta-type and metallocene-type catalysts. Each of these catalyst systems has its advantages and disadvantages, including cost of the polymerization and the particular structure of the polyethylene produced. Due to the importance of polyethylenes, new catalyst systems which are economical and/or produce new types of polyethylenes are constantly being sought.
U.S. Pat. No. 5,955,555, WO98/30612, WO98/38228, WO99/02472 and WO99/12981 (incorporated by reference herein for all purposes) describe the use of iron or cobalt complexes of 2,6-diacylpyridinebisimines or 2,6-pyridinedicarboxaldehydebisimines as catalysts for the polymerization of olefins, mostly of ethylene. These publications describe the preparation of polyethylenes ranging in molecular weight from low molecular weight alpha-olefins and other oligomers to high molecular weight polyethylenes. No mention is made, however, of the use of ligands such as described herein.
R. Roy, et al.,
Transition Met. Chem
. (Weinheim, Ger.), vol. 9, p. 152-155 (1984) describes cobalt complexes of certain aminodiimines. No mention is made of ligands or metal complexes such as described herein.
SUMMARY OF THE INVENTION
This invention concerns a first process for the production of polyethylene, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., a monomer component comprising ethylene, and an Fe or Co complex of a ligand of the formula
wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, or R
1
and R
2
taken together may form a ring;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that any two of R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and R
11
that are vicinal to one another may form a ring;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl; and
Ar
3
and Ar
4
are each independently aryl or substituted aryl.
Also disclosed herein is a second process for the production of polyethylene, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., a monomer component comprising ethylene, a compound of the formula
and:
(a) a first compound W, which is a neutral Lewis acid capable of abstracting X
−
, an alkyl group or a hydride group from M to form WX
−
, (WR
20
)
−
or WH
−
, 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 second compound which is capable of transferring an alkyl or hydride group to M and a third 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;
wherein:
M is Fe or Co;
each X is an anion;
n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation state of M;
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, or R
1
and R
2
taken together may form a ring;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that any two of R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and R
11
that are vicinal to one another may form a ring;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
3
and Ar
4
are each independently aryl or substituted aryl; and
R
20
is alkyl.
This invention also concerns a third process for the production of polyethylene, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., a monomer component comprising ethylene, and a compound of the formula
wherein:
M is Fe or Co;
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, or R
1
and R
2
taken together may form a ring;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that any two of R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and R
11
that are vicinal to one another may form a ring;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
3
and Ar
4
are each independently aryl or substituted aryl;
Z
1
is hydride, alkyl or an anionic ligand into which ethylene can insert;
Y is a neutral ligand capable of being displaced by ethylene, or a vacant coordination site;
Q is a relatively non-coordinating anion;
P is a divalent polyethylene group containing one or more ethylene units; and
Z
2
is an end group.
Also disclosed herein is a compound of the formula
wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, or R
1
and R
2
taken together may form a ring;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that any two of R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and R
11
that are vicinal to one another may form a ring;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl; and
Ar
3
and Ar
4
are each independently aryl or substituted aryl.
Another compound disclosed herein is a compound of the formula
wherein:
M is Fe or Co;
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, or R
1
and R
2
taken together may form a ring;
Ar
1
and Ar
2
are each independently aryl or substituted aryl;
R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, provided that any two of R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
and R
11
that are vicinal to one another may form a ring;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
3
and Ar
4
are each independently aryl or substituted aryl;
Z
1
is hydride or alkyl or any other anionic ligand into which ethylene can insert;
Y is a neutral ligand capable of being displaced by ethylene, or a vacant coordination site;
Q is a relatively non-coordinating anion;
P is a divalent polyethylene group containing one or more ethylene units; and
Z
2
is an end group.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A structure drawn such as (II), (IV) and (V) through (X) simply means that the ligand in the square bracket is coordinated to the metal-containing moiety, as indicated by the arrow. Nothing is implied in these formulas about what atoms in the ligand are coordinated to the metal. Without wishing to be bound by any particular theory, it is believed that (I) and (III) are tridentate ligands in coordinating with Fe or Co, and that coordination is effected through the nitrogen atoms shown in formulas (I) and (III).
Herein, certain terms are used. Some of them are:
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. If n
E. I. du Pont de Nemours and Company
Nazario-Gonzalez Porfirio
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