Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-12-13
2003-03-11
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S167000, C526S161000, C526S171000, C526S172000, C556S032000, C556S035000, C564S270000, C564S271000
Reexamination Certificate
active
06531424
ABSTRACT:
FIELD OF THE INVENTION
Olefins, such as ethylene, are polymerized using as a polymerization catalyst a complex of a selected transition metal with a monoanionic ligand that has three donor atoms which may coordinate to the transition metal.
TECHNICAL BACKGROUND
Polymers of olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc.
Olefins may be polymerized by a variety of transition metal containing catalysts, for example metallocene and Ziegler-Natta type catalysts. More recently, late transition metal containing polymerization catalysts have also been discovered, and among them are nickel and other transition metal containing catalysts in which the nickel atom is complexed to a neutral or monoanionic ligand, see for instance U.S. Pat. No. 5,714,556, U.S. Pat. No. 5,880,241, U.S. Pat. No. 6,060,569, WO9842664, WO9842665 and WO9830609, all of which are incorporated by reference herein for all purposes as if fully set forth. None of these references describes the complexes disclosed herein. Since polyolefins are important commercial materials, new catalysts for their manufacture are constantly being sought.
SUMMARY OF THE INVENTION
One aspect of the present invention concerns a first process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more monomers selected from the group consisting of ethylene and an olefin of the formula H
2
C═CH(CH
2
)
n
G (XVII), with an active catalyst comprising a Group 3 to Group 10 transition metal complex of an anion of the formula (I)
wherein:
R
1
is hydrocarbyl or substituted hydrocarbyl, and R
2
is hydrogen, hydrocarbyl or substituted hydrocarbyl, and provided that R
1
and R
2
taken together may be ortho-arylene or substituted ortho-arylene;
R
3
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that when R
1
and R
2
taken together are ortho-arylene or substituted ortho-arylene, R
3
may form a fused ring system therewith;
Q is nitrogen, oxygen, phosphorous or sulfur;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that R
4
and R
5
taken together may form a ring, and further provided that when Q is oxygen or sulfur R
5
is not present;
Z is a bridging group of the formula (II) or (III)
R
6
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
3
and R
6
together may form a ring;
R
7
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
3
, R
6
and R
7
together may form an aromatic ring or R
6
and R
7
taken together may form a ring;
R
8
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
9
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
4
and R
9
taken together may be part of a double bond to an imino nitrogen atom, or R
8
and R
9
taken together may form a ring, or R
4
, R
5
, R
8
and R
9
taken together may form an aromatic ring, or R
4
and R
9
taken together may form a ring, or R
4
, R
8
and R
9
taken together may form a ring, or R
4
, R
5
, R
6
, R
7
, R
8
, and R
9
taken together may form a fused aromatic ring system;
R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl or R
10
, R
11
, R
12
and R
13
taken together are ortho-arylene;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
4
and R
15
together are part of a double bond to an imino nitrogen atom;
n is an integer of 1 or more;
G is hydrogen, —CO
2
R
16
or —C(O)NR
16
2
; and
each R
16
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl.
Another aspect of the present invention conerns a second process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more monomers selected from the group consisting of ethylene and H
2
C═CH(CH
2
)
n
G (XVII), with a compound of the formula (IV)
wherein:
R
1
is hydrocarbyl or substituted hydrocarbyl, and R
2
is hydrogen, hydrocarbyl or substituted hydrocarbyl, and provided that R
1
and R
2
taken together may be ortho-arylene or substituted ortho-arylene;
R
3
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that when R
1
and R
2
taken together are ortho-arylene or substituted ortho-arylene, R
3
may form a fused ring system therewith;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that R
4
and R
5
taken together may form a ring, and further provided that when Q is oxygen or sulfur R
5
is not present;
Q is nitrogen, oxygen, phosphorous or sulfur;
Z is a bridging group of the formula (II) or (III)
R
6
is hydrogen, hydrocarbyl or substituted hydrocarbyl, or R
3
and R
6
together may form a ring;
R
7
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
3
, R
6
and R
7
together may form an aromatic ring, or R
6
and R
7
taken together may form a ring;
R
8
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
9
is hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
4
and R
9
taken together may be part of a double bond to an imino nitrogen atom, or R
8
and R
9
taken together may form a ring, or R
4
, R
5
, R
8
and R
9
taken together may form an aromatic ring, or R
4
and R
9
taken together may form a ring, or R
4
, R
8
and R
9
taken together may form a ring, or R
4
, R
5
, R
6
, R
7
, R
8
and R
9
taken together may form a fused aromatic ring system;
R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R
10
, R
11
, R
12
and R
13
taken together are ortho-arylene;
R
14
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
4
and R
15
together are part of a double bond to an imino nitrogen atom;
n is an integer of 1 or more;
G is hydrogen, —CO
2
R
16
, or —C(O)NR
16
2
;
each R
16
is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
M is a Group 3 to Group 10 transition metal;
m is an integer equal to the valence of M minus 1; and
each L
1
is independently a monodentate monoanionic ligand and at least for one of L
1
an ethylene molecule may insert between L
1
and M, and L
2
is a monodentate neutral ligand which may be displaced by ethylene or an empty coordination site, or an L
1
and L
2
taken together are a monoanionic polydentate ligand and at least for one of these polydentate ligands ethylene may insert between said monoanionic polydentate ligand and M.
In the above-mentioned processes, (IV) and/or the transition metal complex of (I) may in and of themselves be active catalysts, or may be “activated” by contact with a co-catalyst/activator.
The present invention also concerns a compound of the formula (V)
wherein R
1
, R
2
, R
3
, R
4
, R
5
, Q, Z (and all R groups associated with Z), M and m are as defined above for (IV),
p is 0 or 1; and
each L
3
is independently a monodentate monoanionic ligand, and L
4
is a monodentate neutral ligand or an empty coordination site, or an L
3
and L
4
taken together are a monoanionic bidentate ligand.
Further aspects of the present invention include, for example, the anion of the formula (I) as defined above, as well as a Group 3 to Group 10 transition metal complex of such anion.
REFERENCES:
patent: 3661898 (1972-05-01), Dehnert et al.
patent: 3933785 (1976-01-01), Back et al.
patent: 5714556 (1998-02-01), Johnson et al.
patent: 5880241 (1999-03-01), Brookhart et al.
patent: 6060569 (2000-05-01), Bennett et al.
patent: 99 556 (1973-08-01), None
patent: 0 874 005 (1998-10-01), None
patent: 2013609 (1970-03-01), None
patent: WO 98/30609 (1998-07-01), None
patent: WO 98/42664 (1998-10-01), None
patent: WO 98/42665 (1998-10-01), None
Beringhelli et al., Gazzeta Chimica Italiana 115, 1985, pp. 181-186.*
Tisato et al., J. Chem. Soc. Dalton Trans. 1990, pp. 2225-2232.*
Dahl et al., ACTA
Ittel Steven Dale
Wang Ying
E. I. du Pont de Nemours and Company
Harlan R.
Wu David W.
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