Mitsui Petrochemical Industries, Ltd.

Hoechst Aktiengesellschaft

Mitsui Chemicals, Inc.

Toshihiro Sagane

Toshiyuki Tsutsui

Masaaki Kawasaki

Tetsuo Tojo

Hidenari Nakahama

Yoshiharu Abe

Masayuki Okabe

Keiji Okada

Shuji Minami

Hideaki Yamaguchi

Yoichiro Tsuji

Noriaki Kihara

Kyoko Kobayashi

Riichiro Nagano

Masaaki Yasuda

Tatsuyoshi Ishida

Akira Mizuno

Toshimasa Takata

Hiroo Wamura

Masahiro Kishine

Hitoshi Onishi

Akinori Toyota

Takashi Ueda

Akira Uchiyama

Yuichi Itoh

Shigemi Shiraki

Katsuya Takahashi

Tatsuya Tanizaki

Kenji Wakatsuru

Toshiaki Kuroiwa

Ryosuke Tomita

Totshiyuki Tsutsui

Takehiko Kawate

Yoshihisa Toda

Hitoshi Ohnishi

An olefin thermoplastic elastomer composition comprises a crystalline polyolefin resin (A) and an ethylene/&agr;-olefin/nonconjugated polyene copolymer rubber (B), and optionally a softener (C) and/or an inorganic filler (D), in a specific ratio. The copolymer rubber (B) is prepared by the use of a metallocene catalyst and comprises ethylene, an &agr;-olefin of 3 to 20 carbon atoms and a nonconjugated polyene. This composition ca provide molded products of more excellent tensile strength, elongation at break, elastomeric properties (elongation set, permanent compression set, etc.), heat resistance and low-temperature properties than the conventional non-crosslinked olefin thermoplastic elastomers, even if the composition is in the non-crosslinked form. The composition in the partially or completely crosslinked form can provided molded products of more excellent low-temperature properties, tensile strength, elongation at break and elastomeric properties than the conventional vulcanized rubbers.

Olefin thermoplastic elastomer composition comprising crystalline polyolefin resin and ethylene/&agr;-olefin/nonconjugated polyene copolymer rubber

Chain polyene group-containing norbornene compound and unsaturated

Disclosed is a process for preparing an ethylene-.alpha.-olefin-nonconjugated polyene random copolymer comprising random copolymerizing (a) ethylene, (b) an .alpha.-olefin of 3 or more carbon atoms and (c) a nonconjugated polyene in the presence of a metallocene catalyst containing a specific metallocene compound. The ethylene-.alpha.-olefin-nonconjugated polyene random copolymer prepared by the process has such properties that (i) the copolymer contains units derived from ethylene (a) and units derived from the .alpha.-olefin of 3 or more carbon atoms (b) in a molar ratio of 40/60 to 95/5 �(a)/(b)!, (ii) the iodine value is 1 to 50, (iii) the intrinsic viscosity (.eta.) is more than 0.1 dl/g and less than 8.0 10 dl/g, (iv) the intensity ratio D of T.alpha..beta. to T.alpha..alpha. in the .sup.13 C-NMR spectrum, T.alpha..beta./T.alpha..alpha., is not more than 0.5, (v) the B value is 1.00 to 1.50, (vi) the glass transition temperature Tg is not higher than -50.degree. C., and (vii) the ratio g.eta.* of the intrinsic viscosity (.eta.) of this copolymer defined above to the intrinsic viscosity (.eta.).sub.blank of a straight-chain ethylene-propylene copolymer having the same weight-average molecular weight as this random copolymer and having an ethylene content of 70% by mol, (.eta.)/(.eta.).sub.blank, is more than 0.9. Also disclosed is a vulcanizable rubber composition containing the random copolymer. The ethylene-.alpha.-olefin-nonconjugated polyene random copolymer and the rubber composition are excellent in mechanical strength, weathering resistance, ozone resistance, processability, low-temperature flexibility and heat resistance.

Ethylene-.alpha.-olefin-nonconjugated polyene random copolymer

A terpolymer rubber prepared from ethylene, .alpha.-olefin having 3 to 20 carbon atoms and branched chain polyene of the formula ##STR1## wherein R.sup.1 represents C.sub.1 -C.sub.5 alkyl, and R.sup.2 and R.sup.3 represent hydrogen atom or C.sub.1 -C.sub.5 alkyl, such as, for example, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, and 9-methyl-4-ethylidene-1,8-decadiene; when added to a rubber (diene rubber, nitrile rubber or random copolymer rubber from ethylene, C.sub.3 -C.sub.20 .alpha.-olefin, and optionally a nonconjugated diene) provides curable rubber compositions having rapid vulcanization rates, for example, as lows as about 7 to 10 seconds. The diene rubber compositions also have excellent resistances to weather,ozone and heat aging while maintaining excellent mechanical strength characteristics. The nitrile rubber compositions also have excellent oil resistance.

Ethylene/.alpha.-olefin/nonconjugated polyene terpolymer rubber

The ethylene/.alpha.-olefin/nonconjugated polyene copolymer rubber composition of the present invention comprises in specified proportions a crystalline polyolefin resin (A) and an ethylene/.alpha.-olefin/nonconjugated polyene copolymer rubber (B) composed of ethylene, an .alpha.-olefin having 3 to 20 carbon atoms and a specific branched chain polyene compound. The molar ratio of ethylene units to .alpha.-olefin units, iodine value and intrinsic viscosity �.eta.! of the ethylene/.alpha.-olefin/nonconjugated polyene copolymer rubber (B) are within respective specified ranges. This rubber composition is excellent in low temperature properties. When the above olefinic thermoplastic elastomer composition is partially or entirely crosslinked, a molding can be provided which is superior to the conventional vulcanized rubbers in low temperature properties, tensile strength, elongation at break and rubber properties.

Ethylene/.alpha.-olefin/nonconjugated polyene copolymer rubber

Disclosed is a cycloolefin copolymer composition (C) obtained by copolymerizing an .alpha.-olefin of two or more carbon atoms (a) and a specific cycloolefin (b) in the presence of an aromatic ring-containing vinyl hydrocarbon/conjugated diene copolymer or a product of hydrogenation thereof (A) which has an intrinsic viscosity (.eta.) of 0.5 to 5.0 dl/g; at least one glass transition temperature (measured by DSC) of lower than 15.degree. C.; polymerizable carbon-to-carbon double bonds in an amount of 2 to 150 in terms of iodine value; and a refractive index n.sub.D (A) of 1.50 to 1.65. In the composition (C), the component (A) is contained in an amount of 1 to 40% by weight, and a difference .DELTA.n.sub.D between the refractive index n.sub.D (A) of the component (A) and a refractive index n.sub.D (B) of a cycloolefin copolymer component (B) obtained by copolymerizing the .alpha.-olefin (a) and the cycloolefin (b) in the absence of the component (A) is not more than 0.015. The cycloolefin copolymer composition is excellent in impact resistance, transparency and heat resistance.

Cycloolefin copolymer composition

A novel unsaturated copolymer of ethylene comprises a random copolymer of (i) ethylene, (ii) an .alpha.-olefin of 3 to 20 carbon atoms and (iii) at least one straight chain or branched chain nonconjugated triene or tetraene having one vinyl group in the molecule, which contains 30-92% by mol of ethylene units (i), 6-70% by mol of .alpha.-olefin units (ii) and 0.1-30% by mol of triene or tetraene units (iii), and which has a molar ratio of ethylene units (i) to .alpha.-olefin units (ii) of 40/60 to 92/8 (ethylene units (i)/.alpha.-olefin units (ii)) and an intrinsic viscosity (.eta.), measured in Decalin at 135.degree. C., of 0.05 to 10 dl/g. This novel unsaturated copolymer of ethylene is excellent in weathering resistance, heat resistance and ozone resistance and has a high vulcanizing rate.

Unsaturated copolymer of ethylene and process for preparing the same

Vulcanizable rubber composition containing

A polymer composition comprising �A! a polymer selected from a copolymer of .alpha.-olefin having at least 2 carbon atoms and a specific cyclic olefin, a ring-opening polymer of said specific cyclic olefin and a hydroganted, ring-opening polymer thereof and �B! a core-shell elastomer containing 40 to 85 parts of weight of a core component which comprises a styrene-butadiene copolymer and 15 to 60 parts by weight of a shell component which comprises a copolymer of an acrylate or methacrylate having a specific cyclic structure, a monovinyl aromatic monomer, other monovinyl monomer and a plyfunctional monomer. This polymer composition is excellent in transparency and impact resistance.

Polymer composition and core-shell elastomer used therefor

A branched polyene compound represented by the formula ##STR1## wherein f is an integer of 1-5; R.sup.1 and R.sup.2 represent hydrogen atoms or alkyl groups of 1-5 carbons; R.sup.3 represents a hydrogen atom or an alkyl group of 1-5 carbons or an alkenyl group represented by the formula ##STR2## wherein n is an integer of 1-5; R.sup.4, R.sup.5 and R.sup.6 represent hydrogen atoms or alkyl groups of 1-5 carbons; all of R.sup.1, R.sup.2, R.sup.3 are not simultaneously hydrogen atoms; and all of R.sup.4, R.sup.5 and R.sup.6 are not simultaneously hydrogen atoms.

Branched polyene compounds and production thereof

Process for preparing ethylene-.alpha.-olefin-nonconjugated polyene

There is provided a process for the production of a cycloolefin copolymer which comprises copolymerizing an .alpha.-olefin having 2 or more carbon atoms and a specific cycloolefin in the presence of a specific metallocene type catalyst in a solvent mixture of a hydrocarbon solvent having a solubility parameter (value of .delta.) of 7.7 [(cal/cm.sup.3).sup.1/2 ] or more and a hydrocarbon solvent having a solubility parameter (value of .delta.) of 7.5 [(cal/cm.sup.3).sup.1/2 ] or less as a polymerization solvent. A cycloolefin copolymer having a high molecular weight can be produced in a high concentration by this process at a high yield.

Process for the production of cycloolefin random copolymer

Disclosed is an ethylene-.alpha.-olefin-nonconjugated polyene random copolymer which is a random copolymer of (a) ethylene, (b) an .alpha.-olefin of 3 or more carbon atoms and (c) a nonconjugated polyene, and has such properties that (i) the copolymer contains (a) units derived from ethylene and (b) units derived from the .alpha.-olefin of 3 or more carbon atoms in a molar ratio of 40/60 to 95/5 ((a)/(b)), (ii) the iodine value is in the range of 1 to 50, (iii) the intrinsic viscosity (.eta.), as measured in decahydronaphthalene at 135.degree. C., is in the range of 0.1 to 8.0 dl/g, and (iv) the ratio g.eta.* of the intrinsic viscosity (.eta.) of the copolymer defined above to the intrinsic viscosity (.eta.).sub.blank of a linear ethylene-propylene copolymer having the same weight-average molecular weight as the ethylene-.alpha.-olefin-nonconjugated polyene random copolymer and having an ethylene content of 70% by mol, (.eta.)/(.eta.).sub.blank, is in the range of 0.2 to 0.9 or the ratio g' of the intrinsic viscosity (.eta.) of said random copolymer defined above to the intrinsic viscosity (.eta.).sub.blank' of a linear ethylene-propylene copolymer having an ethylene content of 70% by mol which is determined by measurement of gel permeation chromatography (GPC) of ethylene-.alpha.-olefin-nonconjugated polyene random copolymer in orthodichlorobenzene at 140.degree. C., (.eta.)/(.eta.).sub.blank', is in the reange of 0.2 to 0.9.

Ethylene-.alpha.-olefin-nonconjugated polyene random copolymer, rubber

A polymer composition comprising [A] a polymer selected from a copolymer of .alpha.-olefin having at least 2 carbon atoms and a specific cyclic olefin, a ring-opening polymer of said specific cyclic olefin and a hydroganted, ring-opening polymer thereof and [B] a core-shell elastomer containing 40 to 85 parts of weight of a core component which comprises a styrene-butadiene copolymer and 15 to 60 parts by weight of a shell component which comprises a copolymer of an acrylate or methacrylate having a specific cyclic structure, a monovinyl aromatic monomer, other monovinyl monomer and a plyfunctional monomer. This polymer composition is excellent in transparency and impact resistance.

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Tokyo, Japan

Toshihiro Sagane