Copolymerization of norbornene and functional norbornene...

Details Copolymerization of norbornene and functional norbornene... Copolymerization of norbornene and functional norbornene...

2000-06-09

2002-02-26

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...

C526S082000, C526S087000, C526S286000, C526S332000, C526S269000, C526S270000, C526S273000, C526S282000, C526S314000

Reexamination Certificate

active

06350837

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to polymer compositions derived from norbornene and functional norbornene comonomers and process to prepare such polymer compositions.
BACKGROUND OF THE INVENTION
Cycloolefin polymers (e.g., norbornene-based polymers) and copolymers have received a great deal of attention in recent years. They have found application in dielectric, optical, and photolithographic applications. In addition, the utility of these materials as engineering thermoplastics has been explored. As such, new cyclic olefin copolymers and catalysts for the efficient preparation of cyclic olefin polymers are constantly being sought.
The addition polymer of norbornene (i.e., polynorbornene or poly(bicyclo[2.2.1]hept-2-ene) was originally described in U.S. Pat. No. 2,721,189. In this patent, 2 types of norbornene polymers were prepared. The first polymer was prepared by the addition polymerization of norbornene giving a fully saturated cyclic olefin polymer.
The second polymer was formed by “Ring Opening Metathesis Polymerization” (ROMP) giving an unsaturated polymer backbone.
Conventional “Ziegler-Natta” transition metal catalysts, such as those based on titanium compounds (e.g. TiCl
3
or TiCl
4
) in combination with organoaluminum cocatalysts, have been used to prepare the addition polymer of norbornene (see U.S. Pat. No. 3,330,815). These so-called “Ziegler-Natta” catalysts are quite sensitive to oxygen and are generally ineffective for the copolymerization of nonpolar and polar monomers. Following the early discovery of Zielger-Nata catalysts, there has been intense interest in the development and study of homogeneous early transition metal (Group 4-6) catalysts (“metallocene catalysts”) for the polymerization of olefins. Addition polymers of norbornene have been prepared using such metallocene catalysts as shown in Kaminsky et. al.
J. Mol. Cat.
1992, 72, 109; Kaminsky et. al. Makromol. Chem, Macromol. Symp. 1991, 47, 83.
More recently, others have described the use of Group 8-10 catalysts for the polymerization of norbornene and substituted norbornene. See, for example, WO 95 140448; WO 98 56839; WO 98 56837; U.S. Pat. Nos. 5,571,881; 5,468,819; and 5,569,730.
Recent advances in Group 8-10 catalysts for the polymerization of olefins include the following.
European Patent Application No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts, which contain selected bidentate phosphorous containing ligands.
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 8 K and 350 K. 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.
U.S. Pat. Nos. 4,689,437 and 4,716,138, describe 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, i 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.
L. K. Johnson et al., WO 96/23010; U.S. Pat. Nos. 5,866,663; 5,886,224; 5,891,963; 5,880,323; and 5,880,241; disclose the polymerization of olefins using cationic nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands. These documents also describe 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.
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.
WO 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.
Further examples of Group 8-10 transition metal catalysts for the polymerization of olefins are illustrated in WO 98/40374, WO 98/37110, WO 98/47933, and WO 98/40420. Also described are several new polymer compositions derived from epoxybutene and derivatives thereof.
Brown et al., WO 97/17380, WO 97/48777, WO 97/48739, and WO 97/48740, describe the use of Pd &agr;-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and water.
Fink et al., U. S. Pat. No. 4,724,273, describe 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 97/48736, Denton et al., WO 97/48742, and Sugimura et al., WO 97/38024, describe the polymerization of ethylene using silica supported &agr;-diimine nickel catalysts.
EP 884,331, discloses the use of nickel &agr;-diimine catalysts for the polymerization of ethylene in their slurry loop process.
Neutral nickel catalysts for the polymerization of olefins are set forth in WO 98/30610, WO 98/30609, WO 98/42665, and WO 98/42664.
Iron and cobalt catalysts ligated by pyridine bis(imines) for the polymerization and oligomerization of ethylene are described inWO 99/02472, WO 98/27124, and WO 99/12981.
Canich et al., WO 97/48735, and Mecking, DE 19707236 A1, describe the use of mixed &agr;-diimine catalysts with group IV transition metal catalysts for the polymerization of olefins. Additional recent developments are described by Sugimura et al. in JP 96-84344 and JP 96-84343, by Yorisue at al. in JP 96-70332, by McLain et al. in WO 98/03559, by Weinberg et al. in WO 98/03521, by Wang et al. in WO 99/09078, by Coughlin in WO 99/10391, and by Matsunaga et al. in WO 97/48737.
Notwithstanding these advances in catalysis, there remains a need for new transition metal catalysts, particularly those which are more thermally stable, allow for new polymer microstructures, or are more functional group tolerant. In addition, there is a need for novel methods of polymerizing olefins employing such catalysts, and for the novel polymers, which result.
SUMMARY OF THE INVENTION
The present invention is directed to copolymers of norbornene and functional group containing norbornene comonomers and processes for the preparation thereof. These polymers may be random, alternating or block copolymers or terpolymers, etc. In general, the present invention describes a polymer composition comprising repeat units of the formula:
[A]
S
— and
—[B]
T
wherein A is monomer repeat unit derived from one or more norbornene or substituted norbornene monomers of the formula:
and B is a monomer repeat unit derived from one or more functional norbornene monomers as set forth herein. The polymers of the inventio

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