Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-09-12
2004-08-17
Rabago, Roberto (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S161000, C526S169100, C526S329700, C526S344000, C526S341000, C502S150000, C502S155000, C502S162000, C502S167000, C502S213000, C556S032000
Reexamination Certificate
active
06777510
ABSTRACT:
TECHNICAL FIELD
This invention relates to the polymerization of olefinic monomers and compositions for catalyzing the polymerization of such monomers.
BACKGROUND
A revolution in the polymers industry has occurred over the last decade in which Single Site Organometallic Catalysts have been developed that lead to rapid polymerization of ethylene, propylene and other nonpolar olefins. The resulting polymers and co-polymers have excellent and controllable tacticity and other properties, with microstructures often tunable by the ligands in the catalyst. One generation of catalysts involves early transition metal metallocenes (pioneered by Kaminsky, Ewen, Brintzinger, and Bercaw and developed by Dow, Exxon, and other companies), as disclosed in A. Andersen, et al.,
Angew. Chem., Int. Ed. Engl.
1976, 15, 630; J. Ewen,
J. Am. Chem. Soc.
1984, 106, 6355; W. Kaminsky, et al.,
Angew. Chem., Int. Ed. Engl.
1985, 24, 507; J. Ewen, et al.,
J. Am. Chem. Soc.
1988, 110, 6255; E. Coughlin, et al.,
J. Am. Chem. Soc.
1992, 114, 7606; U.S. Pat. Nos. 5,015,749; 5,057,475; 4,544,762, 1985; 5,234,878, 1993; and U.S. Pat. No. 5,003,095, 1995. Another involves late transition metal di-imines or tri-imines (pioneered by Brookhart and Gibson and developed by Dupont), as disclosed in L. Johnson, et al.,
J. Am. Chem. Soc.
1995, 117, 6414; B. Small, et al.,
J. Am. Chem. Soc.
1998, 120, 4049; G. Britovsek, et al.,
Chem. Commun.
1998, 849; WO 96/23010; and WO 98/27124.
Despite the industrial success of these catalysts, however, there remain many important challenges in developing catalysts for important polymers. In particular, the current generations of catalysts are generally not effective with important polar monomers such as vinyl chloride, methyl acrylates, vinyl acetate, and acrylonitrile. Indeed, the activity of current catalysts to polymerize monomers containing polar functionalities has been limited to the polymerization of large monomers with the polar group far removed from the vinyl moiety. See, e.g. T. Chung,
Macromolecules
1988, 21, 865; T. Chung, et al.,
Macromolecules
1993, 26, 3019; M. Kesti, et al.,
J. Am. Chem. Soc.
1992, 114, 9679; P. Aaltonen, et al.,
Macromolecules
1995, 28, 5353; M. Galimberti, et al.,
J. Mol. Catal.
1995, 101, 1; and S. Mecking, et al.,
J. Am. Chem. Soc.
1998, 120, 888. For other polar monomers, these catalysts are generally inactive or become poisoned in the presence of basic polar monomers.
SUMMARY
Using the techniques described herein, the invention provides catalysts that overcome the problems associated with existing olefin polymerization catalysts and provide for the efficient catalysis of the polymerization of a variety of polar monomers.
In general, in one aspect, the invention provides catalyst compositions for use in an olefin polymerization process. The compositions include a late transition metal, and a ligand completed with the late transition metal. The late transition metal is selected from the (IUPAC convention) Group 7 (Mn column), Group 8 (Fe column), Group 9 (Co column), Group 10 (Ni column) and Group 11 (Cu column) transition metals. The ligand is characterized by the general formula:
Each E is an electronegative atom capable of donating electrons to the late transition metal. Each Y is a linking group independently selected from —O—, —NR—, —CR
2
—, —S—, —PR—, —SiR
2
—, and —G(CR
2
)
m
—, where each R is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, and where one or more R substituents can be incorporated in a ring structure, G is selected from O, N, and CR
2
, and m is an integer greater than or equal to 1. Each A is a Lewis acid, Each X is an electron-withdrawing group independently selected from Cl, F, Br, I, CF
3
, C
6
F
5
, H, alkyl, C
6
H
5
, C
6
R
5
, and CR
3
, where each R is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, and where one or more R substituents can be incorporated in a ring structure. Each Z is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, where one or more of X, Y and/or Z can be incorporated in a ring structure. Therein the late transition metal is also complexed with one or more additional ligands that are capable of adding to an olefin in a polymerization process and/or that are capable of being displaced by the olefin.
Particular embodiments can include one or more of the following features. E can be independently N or P. Each A can be independently selected from Al, B, Ga, In, Tl, Sc, Y, La and Lu. The late transition metal can be nickel, palladium or platinum. The late transition metal can be nickel, palladium or platinum, A can be aluminum or scandium, Y can be —O—, —S—, or —CH
2
—, X can be Cl, F, CF
3
or H, and Z can be H.
In general, in another embodiment, the invention provides compounds characterized by the general formula:
TM is a late transition metal selected from the Group 7-11 transition metals. Each E is an electronegative atom capable of donating electrons to the late transition metal. Each Y is a linking group independently selected from —O—, —NR—, —CR
2
—, —S—, —PR—, —SiR
2
—, and —G(CR
2
)
m
—, where each R is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, and where one or more R substituents can be incorporated in a ring structure, G is selected from O, N, and CR
2
, and m is an integer greater than or equal to 1. Each A is a Lewis acid. Each X is an electron-withdrawing group independently selected from Cl, F, Br, I, CF
3
, C
6
F
5
, H, alkyl, C
6
H
5
, C
6
R
5
, and CR
3
, where each R is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, and where one or more R substituents can be incorporated in a ring structure, Each Z is a substituent independently selected from H, halide, alkyl, substituted alkyl, heteroalkyl, aryl, substituted aryl, and heteroaryl, where one or more of X, Y and/or Z can be incorporated in a ring structure. M is a polymerizable olefinic monomer, and n is an integer greater than or equal to one, such that (M)
n
is polymer derived from one or more olefinic monomer subunits. Q
−
is a weakly coordinating anion.
Particular embodiments can include one or more of the following features. E can be independently N or P. Each A can be independently Al, B, Ga, In, Tl, Sc, Y, La or Lu. The late transition metal can be nickel, palladium or platinum. The late transition metal can be nickel, palladium or platinum, A can be aluminum or scandium, Y can be —O—, —S—, or —CH
2
—, X can be Cl, F, CF
3
or H, and Z can be H. (M)
n
can be a polymer derived from at least one polar functionalized &agr;-olefin. The &agr;-olefin(s) can be selected from vinyl chloride, vinyl acetate, acrylonitrile, methyl acrylate, methyl methacrylate, methyl vinyl ketone, and chloroprene. (M)
n
can be a copolymer derived from the one polar functionalized &agr;-olefin(s) and at least one non-polar &agr;-olefin. The non-polar &agr;-olefin can be ethylene, propylene, butene, styrene, butadiene, or norbornene.
In general, in still another aspect, the invention provides methods for polymerizing polar olefinic monomers. The methods include contacting a catalyst composition or compound as described above with at least one polar olefinic monomer under polymerization conditions sufficient to polymerize the at least one polar olefinic monomer. Copolymers with additional polar olefinic monomers or non-polar monomers can also be produced.
In general, in a fourth aspect, the invention provides computer-implemented methods for identifying polymerization catalyst for a polar olefin. The methods include providing mechanism information for a catalytic polymerization reaction, providing a catalyst template, assigning values to each of a plurality of variables representing the componen
Goddard, III William A.
Muller Richard P.
Philipp Dean M.
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