Polymerization of ethylene

Details Polymerization of ethylene Polymerization of ethylene

2001-11-27

2002-07-09

Wu, David W. (Department: 1713)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S257000, C546S258000, C526S161000, C526S171000, C526S172000, C502S155000, C502S157000

Reexamination Certificate

active

06417364

ABSTRACT:

FIELD OF THE INVENTION
Ethylene is polymerized using selected iron or nickel complexes of 2,2′-bipyridine-6-imines, optionally in the presence of certain activators such alkylaluminum compounds. Also disclosed herein are novel 2,2′-bipyridine-6-imines and their iron and nickel complexes.
TECHNICAL BACKGROUND
Polyethylene is a very important item of commerce, large quantities of various grades of this polymer being produced annually for a large number of uses, such as packaging films and moldings. There are many different methods for making such polyethylenes, 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 polyethylene, new catalyst systems which are economical and/or produce new types of polyethylenes are constantly being sought.
U.S. Pat. No. 5,866,663 describes the polymerization of ethylene and other olefins using nickel and other transition metal complexes of various imines and similar compounds. This publication is incorporated by reference herein for all purposes.
U.S. Pat. No. 5,955,555, WO98/30612, WO98/38228, WO99/02472 and WO99/12981 (all 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.
EP-A-0454231 (also incorporated by reference herein for all purposes) describes the use of various complexes of transition metals with selected ligands such as “bipyridine” to polymerize ethylene or other olefins.
In all of the publications cited above, the ligands described herein are not mentioned.
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., ethylene and a Ni or Fe complex of a ligand of the formula
wherein:
R
1
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R
2
bound to an imino nitrogen atom has at least two carbon atoms bound to it; and
each of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
R
6
, R
7
, R
8
and R
9
vicinal to one another, or R
6
and R
7
taken together, may form a ring.
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., 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 Ni;
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
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R
2
bound to an imino nitrogen atom has at least two carbon atoms bound to it; and
each of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
vicinal to one another, or R
6
and R
7
taken together, may form a ring.
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., ethylene and a compound of the formula
wherein:
M is Ni or Fe;
each X is an anion;
R
1
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R
2
bound to an imino nitrogen atom has at least two carbon atoms bound to it;
each of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
vicinal to one another, or R
6
and R
7
taken together, may form a ring;
Z
1
is hydride or 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 described herein is a compound of the formula
wherein:
R
1
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R
2
bound to an imino nitrogen atom has at least two carbon atoms bound to it; and
each of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
vicinal to one another or, R
6
and R
7
taken together, may form a ring.
Described herein is a compound of the formula
wherein:
M is Fe or Ni;
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
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R
2
bound to an imino nitrogen atom has at least two carbon atoms bound to it;
each of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
vicinal to one another, or R
6
and R
7
taken together, may form a ring;
Z
1
is hydride or 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.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
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 preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heteroaromatic rings.
By “(inert) functional group ” herein is meant a group, other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein

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