Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2002-01-25
2004-03-23
Harlan, Robert (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S167000, C526S161000, C526S171000, C526S172000, C556S035000, C556S137000, C556S138000
Reexamination Certificate
active
06710007
ABSTRACT:
FIELD OF THE INVENTION
The polymerization of olefins is catalyzed by transition metal complexes of selected imines, amines or phosphines containing another group such as ester or amide, and in some instances other olefinic compounds such as unsaturated esters may be copolymerized with olefins. Useful transition metals include Ni, Fe, Ti and Zr. Certain types of late transition metal complexes are especially useful in making polymers containing polar comonomers.
TECHNICAL BACKGROUND
The polymerization of olefins such as ethylene and propylene is a very important commercial activity, and such polymers in various forms are made in enormous quantities for very many uses. Various methods are known for polymerizing olefins, such as free radical polymerization of ethylene, and coordination polymerization using catalysts such as Ziegler-Natta-type and metallocene-type catalysts. Nevertheless, given the importance of polyolefins new catalysts are constantly being sought for such polymerizations, to lower the cost of production and/or make new, and hopefully improved, polymer structures. More recently so-called single site catalysts using late transition metal complexes have been developed, and they have proved in many instances to give different polymers than the earlier known early transition metal catalysts. See, for example, U.S. Pat. Nos. 5,714,556, 5,880,241 and 6,103,658 (all of which are incorporated by reference herein for all purposes as if fully set forth).
Another type of useful polyolefin is one that contains polar comonomers, such as acrylates. These copolymers are made especially well by a new type of complex in which a certain type of ligand is used.
SUMMARY OF THE INVENTION
This invention concerns new transition metal complexes, and processes for the polymerization of olefins using such new transition metal complexes.
A first aspect of the present invention concerns a Group 3 through 11 (IUPAC) transition metal or a lanthanide metal complex of a ligand of the formula (I)
wherein:
Z is nitrogen or oxygen; and
Q is nitrogen or phosphorous;
provided that:
when Q is phosphorous and Z is nitrogen: R
1
and R
2
are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an E
S
of about −0.90 or less; R
3
, R
4
, R
5
, and R
6
are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl; R
7
is hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; and R
8
is hydrocarbyl, substituted hydrocarbyl or silyl; provided that any two of R
3
, R
4
, R
5
, R
6
, R
7
and R
8
vicinal or geminal to one another together may form a ring;
when Q is phosphorous and Z is oxygen:
R
1
and R
2
are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an E
S
of about −0.90 or less; R
3
and R
4
are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl; R
5
and R
7
taken together form a double bond; R
8
is not present; and R
6
is —OR
9
, —NR
1
OR
11
, hydrocarbyl or substituted hydrocarbyl, wherein R
9
is hydrocarbyl or substituted hydrocarbyl, and R
10
and R
11
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and provided that any two of R
3
, R
4
, and R
6
vicinal or geminal to one another may form a ring; or
R
1
and R
2
are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an E
S
of about −0.90 or less; R
3
, R
4
, R
5
and R
6
are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl; R
7
is hydrocarbyl, silyl, or substituted hydrocarbyl; and R
8
is not present; and provided that any two of R
3
, R
4
, R
5
, R
6
, and R
7
vicinal or geminal to one another may form a ring;
when Q is nitrogen: R
1
is hydrocarbyl, silyl, or substituted hydrocarbyl having an E
S
of about −0.90 or less; R
2
and R
3
are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl, or taken together form a double bond; R
4
is hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl; Z is oxygen; R
6
and R
7
taken together form a double bond; R
8
is not present; R
5
is —OR
12
, —R
13
or —NR
14
R
15
, wherein R
12
and R
13
are each independently hydrocarbyl or substituted hydrocarbyl, and R
14
and R
15
are each hydrogen, hydrocarbyl or substituted hydrocarbyl; provided that when R
2
and R
3
taken together form an aromatic ring, R
1
and R
4
are not present; and further provided that any two of R
2
, R
3
, R
4
and R
5
vicinyl or germinal to one another together may form a ring.
A second aspect of the present invention concerns a “first” process for the polymerization of olefins, comprising the step of contacting, under polymerizing conditions, one or more polymerizable olefins with an active polymerization catalyst comprising the aforementioned transition metal complex.
A third aspect of this invention is a “second” process for the manufacture of a polar copolymer by contacting, under polymerizing conditions, a hydrocarbon olefin, a polar olefin, and a polymerization catalyst comprising a nickel complex of a bidentate ligand which is an active ligand. This third aspect also includes an improved process for the manufacture of a polar copolymer by contacting, under polymerizing conditions, a hydrocarbon olefin, a polar olefin, and a polymerization catalyst comprising a nickel complex, wherein the improvement comprises that the polymerization catalyst comprises a nickel metal complex of a bidentate ligand which is an active ligand.
These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed description. It is to be appreciated that certain features of the invention which are, for clarity, described below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.
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 (and alkyl groups) herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below). The substituent groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. 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 chains or rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the heteroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.
By “(inert) functional group” herein is meant a group other than hydrocarbyl or substituted hydrocarbyl that 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 that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), and ether such as —OR
22
wherein R
22
is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a transition metal atom the functional group should not coordinate to the metal atom more strongly than the groups in those compounds are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
By “silyl” h
Brookhart Maurice S.
Ittel Steven Dale
Johnson Lynda Kaye
Kreutzer Kristina A.
Kunitsky Keith
E. I. du Pont de Nemours and Company
Harlan Robert
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