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    • 4. 发明申请
    • ETHYLENIC RANDOM COPOLYMER, PROCESS FOR PREPARING THE SAME, AND RUBBER COMPOSITION
    • 乙烯随机共聚物,其制备方法和橡胶组合物
    • WO1997045466A1
    • 1997-12-04
    • PCT/JP1997001815
    • 1997-05-28
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.HAKUTA, TakashiHOSOYA, MikioTOJO, TetsuoKAWASAKI, Masaaki
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.
    • C08F210/18
    • C08F210/18C08F4/68C08F210/06C08F232/00C08F2500/25C08F2500/17
    • A process for preparing an ethylene/ alpha -olefin/norbornene nonconjugated polyene random copolymer, comprising preparing an ethylene random copolymer simultaneously meeting the following requirements (1) to (5): (1) the molar ratio of ethylene (a) to an alpha -olefin (b) having 3 to 20 carbon atoms ranges from 40:60 to 95:5; (2) a given amount of non conjugated polyene (c) has a norbornene skeleton; (3) the available network chain density nu is not less than 1.5 x 10 /cm after press cross-linking of the copolymer using a dicumyl peroxyde; (4) the ratio of the rate gamma 1 of shear showing a shearing stress of 0.4 x 10 dyn/cm as determined from the melt flow curve at 100 DEG C and the rate gamma 2 of shear showing a shearing stress of 2.4 x 10 dyn/cm , that is, gamma 2/ gamma 1 and the available network chain density nu has a relationship represented by the following general formula: 0.04 x 10 ; and (5) the intrinsic viscosity [ eta ] ranges from 0.5 to 10 dl/g as measured in decalin at 135 DEG C. The copolymer has excellent cross-linkability, can be cross-linked with a small amount of a peroxide or the like, and a cross-linked rubber composition prepared using this copolymer has excellent heat aging resistance, mechanical strength, weather resistance, and ozone resistance.
    • 一种制备乙烯/α-烯烃/降冰片烯非共轭多烯无规共聚物的方法,包括同时满足以下要求(1)至(5)制备乙烯无规共聚物:(1)乙烯(a)与α- 具有3-20个碳原子的α-烯烃(b)的范围为40:60至95:5; (2)给定量的非共轭多烯(c)具有降冰片烯骨架; (3)使用二枯基过氧化物进行共聚物的压制交联后,可用网络链密度nu不小于1.5×10 20 / cm 3; (4)从100℃的熔体流动曲线确定的剪切应力为剪切应力为0.4×10 6 dyn / cm 2的剪切速率γ1与剪切速率γ2的剪切比 2.4×10 6 dyn / cm 2的应力,即γ2 /γ1,可用的网络链密度nu具有由以下通式表示的关系:0.04×10 对数(γ2 /γ1)/ nu <0.20×10 <-19>; 和(5)在135℃萘烷中测定的特性粘度η为0.5-10dl / g。该共聚物具有优异的交联性,可与少量的过氧化物等进行交联 并且使用该共聚物制备的交联橡胶组合物具有优异的耐热老化性,机械强度,耐候性和耐臭氧性。
    • 5. 发明申请
    • RUBBER COMPOSITION AND PROCESS FOR THE PRODUCTION THEREOF
    • 橡胶组合物及其生产方法
    • WO1997002316A1
    • 1997-01-23
    • PCT/JP1996001865
    • 1996-07-05
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.NAKAHAMA, HidenariKAWASAKI, MasaakiISHII, YujiTOJO, TetsuoKODA, TakuMAEJIMA, YoshioMIURA, YujiHOSOMI, Yasuhiro
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.
    • C08L23/02
    • C08L23/02C08K3/04C08K3/22C08K5/0025C08K5/09C08L23/04C08L23/06C08L23/0815C08L23/10C08L23/16C08L91/00C08L2205/18C08L2666/04
    • A vulcanizable rubber composition comprising a blend which is prepared by micro-dispersing a polyolefin resin (B) in an ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A) comprising ethylene, a C3-C20 alpha -olefin and a nonconjugated polyene in a molten state and in which the mean diameter of dispersed particles of the polyolefin resin (B) is 2 mu m or below and the (B) to (A) weight ratio ranges from 5/95 to 50/50. The micro-dispersion of a polyolefin resin (B) can easily be attained by kneading the components (A) and (B) together with compounding ingredients (such as reinforcement, filler, softener, vulcanization accelerator, vulcanizing agent and so on) in a rubber kneader, through the resin (B) is essentially difficult of micro-dispersion. Further, the composition enables the provision of rubber articles having a high and constant quality at a low cost, because the resin (B) can well be dispersed by conventional rubber kneaders in a short time without fail. The process for producing the above composition comprises introducing a rubber mixture (E) comprising 100 parts by weight of the copolymer rubber (B) and 3 to 10 parts by weight of an organic solvent (D) into a multi-stage vented extruder through a feed port, while introducing a polyolefin resin (B) thereinto in an inert gas atmosphere through another feed port, kneading the rubber mixture (E) and the polyolefin resin (B) with the removal of the solvent. This process can easily give nonblocking vulcanizable pellets of an ethylenic copolymer rubber composition comprising an ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A) and a polyolefin resin (B) wherein the resin (B) is micro-dispersed in a good state.
    • 一种可硫化橡胶组合物,其包含通过将聚烯烃树脂(B)在包含乙烯,C 3 -C 20α-烯烃和非共轭多烯的乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A)中微分散而制备的共混物 熔融状态,其中聚烯烃树脂(B)的分散颗粒的平均直径为2μm或更低,(B)至(A)重量比为5/95至50/50)。 聚烯烃树脂(B)的微分散体可以通过将组分(A)和(B)与配混成分(如增强剂,填料,软化剂,​​硫化促进剂,硫化剂等)混合在一起而容易地实现 橡胶捏合机,通过树脂(B)基本上难以微分散。 此外,由于通过常规橡胶捏合机很好地分散树脂(B),所以能够以低成本提供具有高质量和高质量的橡胶制品。 制备上述组合物的方法包括将包含100重量份的共聚物橡胶(B)和3至10重量份的有机溶剂(D)的橡胶混合物(E)引入多级排气挤出机中,通过 进料口,同时通过另一个进料口在惰性气体气氛中引入聚烯烃树脂(B),同时除去溶剂来捏合橡胶混合物(E)和聚烯烃树脂(B)。 该方法可以容易地得到包含乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A)和聚烯烃树脂(B)的乙烯共聚物橡胶组合物的非阻塞可硫化丸粒,其中树脂(B)以良好的状态微分散 。
    • 7. 发明申请
    • HEAT-RESISTANT RUBBER COMPOSITIONS
    • 耐热橡胶组合物
    • WO1996032442A1
    • 1996-10-17
    • PCT/JP1996000991
    • 1996-04-11
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.HAKUTA, TakashiTOJO, TetsuoKAWASAKI, MasaakiHOSOYA, Mikio
    • MITSUI PETROCHEMICAL INDUSTRIES, LTD.
    • C08L23/08
    • C08K5/14C08K5/0025C08L23/0815C08L2312/00C08L23/16C08L2666/04
    • A heat-resistant rubber composition that is vulcanizable and comprises a specified ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A) and an organic peroxide (B). It has a high efficiency of cross-linking with organic peroxides and can provide vulcanized rubber moldings having a high modulus and excellent resistances to environmental deteriorations such as resistance to thermal aging. Another heat-resistant rubber composition that is vulcanizable and comprises 100 parts by weight of a specified ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A) prepared from ethylene, a C3-C20 alpha -olefin and a vinyl-terminated norbornene compound as the nonconjugated polyene, 0.2-5 parts by weight of an amine age resister (C) and/or a hindered phenol age resister (D), 1-10 parts by weight of a sulfur age resister (E), and an organic peroxide (B). It can provide vulcanized rubber moldings having excellent mechanical and electrical characteristics and remarkably excellent resistance to thermal aging. When the ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A) is a blend of an ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A1) having a limiting viscosity [ eta ] of 1-10 dl/g and containing 0.01-2 mol.% of a nonconjugated polyene and another ethylene- alpha -olefin-nonconjugated polyene copolymer rubber (A2) having a limiting viscosity [ eta ] of 0.1-5 dl/g, containing 0.01-2 mol.% of a nonconjugated polyene, and having a limiting viscosity different from that of the component (A), the obtained heat-resistant rubber composition is extremely excellent in flowability and can provide vulcanized moldings having excellent mechanical and electrical characteristics and remarkably excellent resistance to thermal aging.
    • 一种耐硫橡胶组合物,其是可硫化的并且包含特定的乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A)和有机过氧化物(B)。 它具有与有机过氧化物交联的高效率,并且可以提供具有高模量和优异的耐老化耐热性的耐硫化橡胶模制品。 另一种可硫化的耐热橡胶组合物,其包含100重量份由乙烯,C3-C20α-烯烃和乙烯基封端的降冰片烯化合物制备的特定乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A) 非共轭多烯,0.2-5重量份的胺抗老化剂(C)和/或受阻酚抗老化剂(D),1-10重量份的硫抗老化剂(E)和有机过氧化物( B)。 它可以提供具有优异机械和电气特性以及非常优异的耐热老化性能的硫化橡胶模制品。 当乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A)是特性粘度η为1-10dl / g的含乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A1)和0.01 -2摩尔%的非共轭多烯和另一种乙烯-α-烯烃 - 非共轭多烯共聚物橡胶(A2),其特性粘度η为0.1-5dl / g,含有0.01-2mol%的非共轭多烯 并且具有与(A)成分不同的特性粘度的情况下,得到的耐热橡胶组合物的流动性极其优异,能够提供具有优异的机械特性和电气特性的硫化成形体,耐热老化性优异。