Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-05-12
2001-10-16
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S131000, C526S348600, C526S352000, C556S035000, C556S137000, C556S138000, C502S121000, C502S122000, C502S123000, C502S162000, C502S167000, C502S168000
Reexamination Certificate
active
06303720
ABSTRACT:
FIELD OF THE INVENTION
The present invention is directed to Group 8-10 transition metal-containing complexes, their use in olefin polymerizations, and to novel olefin polymers produced thereby.
BACKGROUND OF THE INVENTION
Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes, and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, permeability, optical properties, and the like, for particular uses. Chain length, polymer branching and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic process for polymerizing olefins which permits more efficient and better controlled polymerization of olefins.
Conventional polyolefins are prepared by a variety of polymerization techniques, including homogeneous liquid phase, gas phase, and slurry polymerization. Certain transition metal catalysts, such as those based on titanium compounds (e.g. TiCl
3
or TiCl
4
) in combination with organoaluminum cocatalysts, are used to make linear and linear low density polyethylenes as well as poly-&agr;-olefins such as polypropylene. These so-called “Ziegler-Natta” catalysts are quite sensitive to oxygen and are ineffective for the copolymerization of nonpolar and polar monomers.
Recent advances in non-Ziegler-Natta olefin polymerization catalysis include the following.
L. K. Johnson et al., WO Patent Application 96/23010, disclose the polymerization of olefins using cationic nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands. This document also describes the polymerization of ethylene, acyclic olefins, and/or selected cyclic olefins and optionally selected unsaturated acids or esters such as acrylic acid or alkyl acrylates to provide olefin homopolymers or copolymers.
European Patent Application Serial No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts which contain selected bidentate phosphorous containing ligands.
L. K. Johnson et al.,
J. Am. Chem. Soc.,
1995, 117, 6414, describe the polymerization of olefins such as ethylene, propylene, and 1 -hexene using cationic &agr;-diimine-based nickel and palladium complexes. These catalysts have been described to polymerize ethylene to high molecular weight branched polyethylene. In addition to ethylene, Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate.
G. F. Schmidt et al.,
J. Am. Chem. Soc.
1985, 107, 1443, describe a cobalt(III) cyclopentadienyl catalytic system having the structure [C
5
Me
5
(L)CoCH
2
CH
2
-&mgr;-H]
+
, which provides for the “living” polymerization of ethylene.
M. Brookhart et al.,
Macromolecules
1995, 28, 5378, disclose using such “living” catalysts in the synthesis of end-functionalized polyethylene homopolymers.
U. Klabunde, U. S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and 5,175,326, describes the conversion of ethylene to polyethylene using anionic phosphorous, oxygen donors ligated to Ni(II). The polymerization reactions were run between 25 and 100° C. with modest yields, producing linear polyethylene having a weight-average molecular weight ranging between 8K and 350K. In addition, Klabunde describes the preparation of copolymers of ethylene and functional group containing monomers.
M. Peuckert et al.,
Organomet.
1983, 2(5), 594, disclose the oligomerization of ethylene using phosphine, carboxylate donors ligated to Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s). The oligomerizations were carried out at 60 to 95° C. and 10 to 80 bar ethylene in toluene, to produce &agr;-olefins.
R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138, describes the oligomerization of ethylene using phosphine, sulfonate donors ligated to Ni(II). These complexes show catalyst activities approximately 15 times greater than those reported with phosphine, carboxylate analogs.
W. Keim et al.,
Angew. Chem. Int. Ed. Eng.
1981, 20, 116, and V. M. Mohring, et al.,
Angew. Chem. Int. Ed. Eng.
1985, 24, 1001, disclose the polymerization of ethylene and the oligomerization of &agr;-olefins with aminobis(imino)phosphorane nickel catalysts: G. Wilke.
Angew. Chem. Int. Ed. Engl.
1988, 27, 185, describes a nickel allyl phosphine complex for the polymerization of ethylene.
K. A. O. Starzewski et al.,
Angew. Chem. Int. Ed. Engl.
1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickel complexes, used to polymerize ethylene to provide high molecular weight linear polyethylene.
WO Patent Application 97/02298 discloses the polymerization of olefins using a variety of neutral N, O, P, or S donor ligands, in combination with a nickel(0) compound and an acid.
Brown et al., WO 97/17380, describes the use of Pd &agr;-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and moisture.
Fink et al., U. S. Pat. No. 4,724,273, have described the polymerization of &agr;-olefins using aminobis(imino)phosphorane nickel catalysts and the compositions of the resulting poly(&agr;-olefins).
Recently Vaughan et al. WO 9748736, Denton et al. WO 9748742, and Sugimura et al. WO 9738024 have described the polymerization of ethylene using silica supported &agr;-diimine nickel catalysts.
Additional recent developments are described by Sugimura et al., in JP96-84344, JP96-84343, by Yorisue et al., in JP96-70332, by Canich et al. WO 9748735, McLain et al. WO 9803559, Weinberg et al. WO 9803521 and by Matsunaga et al. WO 9748737.
Notwithstanding these advances in non-Ziegler-Natta catalysis, there remains a need for efficient and effective Group 8-10 transition metal catalysts for effecting polymerization of olefins. In addition, there is a need for novel methods of polymerizing olefins employing such effective Group 8-10 transition metal catalysts. In particular, there remains a need for Group 8-10 transition metal olefin polymerization catalysts with both improved temperature stability and functional group compatibility. Further, there remains a need for a method of polymerizing olefins utilizing effective Group 8-10 transition metal catalysts in combination with a Lewis acid so as to obtain a catalyst that is more active and more selective.
SUMMARY OF THE INVENTION
The present invention is directed to novel Group 8-10 transition metal catalysts, to batch or continuous olefin polymerizations using these catalysts, and to the polymers produced thereby.
The process of the present invention comprises contacting one or more olefin monomers of the formula LI:
RCH═CHR
8
LI
wherein R and R
8
each, independently, represent a hydrogen, a hydrocarbyl or a fluoroalkyl, and may be linked to form a cyclic olefin;
with a Group 8-10 transition metal having coordinated thereto a bidentate ligand having the formula X:
wherein R
1
and R
6
are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
A and B are each, independently, a heteroatom connected mono-radical wherein the connected heteroatom is selected from Group 15 or 16, preferably N, O, S, and wherein A and B may be linked by a bridging group;
and, optionally, a Bronsted or Lewis acid and polymerization is carried out to obtain a polymer comprising units of the aforementioned olefin monomer.
In the above process, it should be appreciated that the Group 8-10 transition metal has coordinated thereto a bidentate ligand having the formula X and that the Bronsted or Lewis acid is optionally reacted with this metal-ligand complex. In add
Killian Christopher Moore
Lavoie Gino Georges
Mackenzie Peter Borden
McDevitt Jason Patrick
Moody Leslie Shane
Eastman Chemical Company
Graves, Jr. Bernard J.
Harlan R.
Wood Jonathan D.
Wu David W.
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