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    Modified conjugated diene polymer and process for production thereof
    1.
    发明授权
    Modified conjugated diene polymer and process for production thereof 失效
    改性共轭二烯聚合物及其制备方法

    公开(公告)号：US4906706A

    公开(公告)日：1990-03-06

    申请号：US90347

    申请日：1987-08-28

    申请人： Iwakazu Hattori ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Masao Yoshizawa

    发明人： Iwakazu Hattori ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Masao Yoshizawa

    IPC分类号： C08C19/00 ,  C08F36/04

    CPC分类号： C08C19/00 ,  C08F36/04

    摘要： A process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth element compound, (b) an organoaluminum compound represented by the general formula, Alr.sup.1 R.sup.2 R.sup.3 (wherein R.sup.1, R.sup.2 and R.sup.3 which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R.sup.1, R.sup.2 and R.sup.3 is said hydrocarbon group) and, if necessary, at least one member selected from the group consisting of (c) a Lewis acid and/or (d) a Lewis base, and then (II) modifying the resulting reactive polymer with a modifying compound selected from the group consisting of the following components (e), (f) and (g): (e) an organometal halide compound represented by the general formula, R.sub.n .sup.4 MX.sub.4-n (wherein R.sup.4 is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin or germanium atom, X is a halogen atom, and n is an integer of 1 to 3), (f) a heterocumulene compound or a three-membered heterocyclic compound having, in the molecule, a bond represented by the general formula, ##STR1## (wherein X.sup.1 is a carbon, nitrogen, oxygen or sulfur atom, Y is a carbon or sulfur atom, Z is a nitrogen, oxygen or sulfur atom, and X.sup.2 is a nitrogen, oxygen or sulfur atom), and (g) a halogen compound having, in the molecule, a bond represented by the general formula, ##STR2## (wherein Y.sup.1 is a nitrogen or oxygen atom and X is a halogen atom). Said modified conjugated diene polymer has excellent characteristics in wear resistance, heat generation, mechanical properties, etc.

    摘要翻译： 一种制备改性共轭二烯聚合物的方法，包括以下步骤：（I）在惰性有机溶剂中，在催化剂存在下使共轭二烯聚合，所述催化剂包含（a）镧系稀土元素化合物，（b）有机铝化合物 由通式Alr 1 R 2 R 3（其中可以相同或不同的R 1，R 2和R 3是氢原子或具有1至8个碳原子的烃基，并且R 1，R 2和R 3中的至少一个是所述烃基） 必要时选自（c）路易斯酸和/或（d）路易斯碱中的至少一种，然后（II）用选自以下的修饰化合物改性所得的反应性聚合物： 以下组分（e），（f）和（g）：（e）由通式Rn4MX4-n（其中R4是1-20个碳原子的烷基或芳基）表示的有机金卤化物 是锡或锗原子，X是卤素原子，n是i 1至3的整数），（f）在分子中具有由通式表示的键的杂多烯烃化合物或三元杂环化合物，其中X1是碳，氮，氧或硫原子 Y为碳原子或硫原子，Z为氮，氧或硫原子，X2为氮，氧或硫原子），（g）分子中具有由通式 （其中Y1是氮原子或氧原子，X是卤素原子）。 所述改性共轭二烯聚合物在耐磨性，发热性，机械性能等方面具有优异的特性。

    Preparation of conjugated diene polymers modified with an organo-tin or germanium halide
    2.
    发明授权
    Preparation of conjugated diene polymers modified with an organo-tin or germanium halide 失效
    用有机锡或卤化锗改性的共轭二烯聚合物的制备

    公开(公告)号：US5064910A

    公开(公告)日：1991-11-12

    申请号：US448332

    申请日：1989-12-11

    申请人： Iwakazu Hattori ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Masao Yoshizawa

    发明人： Iwakazu Hattori ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Masao Yoshizawa

    IPC分类号： C08C19/00 ,  C08F36/04

    CPC分类号： C08C19/00 ,  C08F36/04

    摘要： A process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth element compound, (b) an organoaluminum compound represented by the general formula, AlR.sup.1 R.sup.2 R.sup.3 (wherein R.sup.1, R.sup.2 and R.sup.3 which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R.sup.1, R.sup.2 and R.sup.3 is said hydrocarbon group) and, if necessary, at least one member selected from the group consisting of (c) a Lewis acid and/or (d) a Lewis base, and then (II) modifying the resulting reactive polymer with a modifying compound of the general formula, R.sup.4.sub.n MX.sub.4-n (wherein R.sup.4 is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin atom, X is a halogen atom, and n is an integer of 1 to 3).

    摘要翻译： 一种制备改性共轭二烯聚合物的方法，包括以下步骤：（I）在惰性有机溶剂中，在催化剂存在下使共轭二烯聚合，所述催化剂包含（a）镧系稀土元素化合物，（b）有机铝化合物 由通式表示的AlR1R2R3（其中R1，R2和R3可以相同或不同，为氢原子或碳原子数1〜8的烃基，R1，R2和R3中的至少一个为所述烃基） 必要时，选自（c）路易斯酸和/或（d）路易斯碱中的至少一种，然后（II）用下列通式的修饰化合物R4nMX4- n（其中，R 4为碳原子数1〜20的烷基或芳基，M为锡原子，X为卤素原子，n为1〜3的整数）。

    Styrene-butadiene block copolymer
    3.
    发明授权
    Styrene-butadiene block copolymer 失效
    苯乙烯 - 丁二烯嵌段共聚物

    公开(公告)号：US4433109A

    公开(公告)日：1984-02-21

    申请号：US330862

    申请日：1981-12-15

    申请人： Yasumasa Takeuchi ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Akio Takashima ,  Iwakazu Hattori

    发明人： Yasumasa Takeuchi ,  Mitsuhiko Sakakibara ,  Fumio Tsutsumi ,  Akio Takashima ,  Iwakazu Hattori

    IPC分类号： C08F297/04 ,  C08G81/02

    CPC分类号： C08G81/022 ,  C08F297/04

    摘要： A styrene-butadiene block copolymer having a Mooney viscosity (ML.sub.1+4, 100.degree. C.) of 10 to 150 comprising two specific random styrene-butadiene copolymer blocks different in bound styrene content and in vinyl content in the butadiene portion, and optionally polybutadiene blocks, wherein the total vinyl content in the whole bound butadiene is 30 to 70% and the total bound styrene content is 10 to 40% by weight. Said block copolymer is excellent in wet skid resistance and rolling resistance, well-balanced in fracture and wear characteristics and also satisfactory in processability and cold flow property.

    摘要翻译： 具有10至150的门尼粘度（ML1 + 4,100℃）的苯乙烯 - 丁二烯嵌段共聚物，其包含在结合的苯乙烯含量中不同的两种特定的无规苯乙烯 - 丁二烯共聚物嵌段和丁二烯部分中的乙烯基含量，以及任选的聚丁二烯 嵌段，其中整个结合的丁二烯中的总乙烯基含量为30〜70％，总结合苯乙烯含量为10〜40重量％。 所述嵌段共聚物的耐湿滑性和滚动阻力优异，断裂和磨损特性平衡，加工性和冷流动性也令人满意。

    Vulcanized rubber composition
    7.
    发明授权
    Vulcanized rubber composition 失效
    硫化橡胶组合物

    公开(公告)号：US5011888A

    公开(公告)日：1991-04-30

    申请号：US449308

    申请日：1989-12-06

    申请人： Fumio Tsutsumi ,  Akihiko Morikawa ,  Mitsuhiko Sakakibara ,  Noboru Oshima ,  Tatsuro Hamada ,  Tatsuo Fujimaki ,  Masayuki Ohashi

    发明人： Fumio Tsutsumi ,  Akihiko Morikawa ,  Mitsuhiko Sakakibara ,  Noboru Oshima ,  Tatsuro Hamada ,  Tatsuo Fujimaki ,  Masayuki Ohashi

    IPC分类号： C08L9/06 ,  B60C1/00 ,  C08F297/04 ,  C08G18/69 ,  C08L21/00 ,  C08L53/00 ,  C08L53/02

    CPC分类号： C08L53/02 ,  B60C1/0016 ,  C08G18/69 ,  C08L21/00 ,  C08G2380/00

    摘要： A rubber composition is disclosed which contains not less than 20% by weight in a rubber component of a block copolymer composed of polymer or copolymer block units (A) and a random copolymer block units (B). The polymer or copolymer block units (A) are obtained by singly polymerizing a conjugated diolefine or copolymerizing the conjugated diolefine and a monovinyl aromatic hydrocarbon with use of a lithium initiator and contains not more than 10% by weight of the bound monovinyl aromatic hydrocarbon. The random copolymer block unit (B) are obtained by copolymerizing the conjugated diolefine and the monovinyl aromatic hydrocarbon and contain 15 to 80% by weight of the bound monovinyl aromatic hydrocarbon. In the block copolymer, (i) the block copolymer contains not less than 10% by weight of each of the block units (A) and the block units (B); (ii) the total content of the bound monovinyl aromatic hydrocarbon is from 10 to 40% by weight; (iii) the average content of the vinyl bonds in the conjugated diolefine portions is from 20 to 70%; and (iv) polymerizable terminals of the block copolymer are reacted with an isocyanate compound.

    摘要翻译： 公开了在由聚合物或共聚物嵌段单元（A）和无规共聚物嵌段单元（B）组成的嵌段共聚物的橡胶组分中不少于20重量％的橡胶组合物。 聚合物或共聚物嵌段单元（A）是通过使共轭二烯烃单独聚合或使用锂引发剂共轭共轭二烯和单乙烯基芳族烃而得到的，并且含有不超过10重量％的结合的单乙烯基芳烃。 无规共聚物嵌段单元（B）通过使共轭二烯烃和单乙烯基芳族烃共聚而得到，并含有15〜80重量％的结合的单乙烯基芳烃。 在嵌段共聚物中，（i）嵌段共聚物含有不少于块单元（A）和嵌段单元（B）的10重量％。 （ii）结合的单乙烯基芳烃的总含量为10〜40重量％ （iii）共轭二烯烃部分中的乙烯基键的平均含量为20〜70％。 和（iv）嵌段共聚物的可聚合端与异氰酸酯化合物反应。

    Rubber composition comprising a styrene-butadiene block copolymer having two kinds of blocks
    8.
    发明授权
    Rubber composition comprising a styrene-butadiene block copolymer having two kinds of blocks 失效
    包含具有两种嵌段的苯乙烯 - 丁二烯嵌段共聚物的橡胶组合物

    公开(公告)号：US4782119A

    公开(公告)日：1988-11-01

    申请号：US769923

    申请日：1985-08-27

    申请人： Fumio Tsutsumi ,  Akio Iakashima ,  Mitsuhiko Sakakibara ,  Noboru Oshima ,  Tatsuo Fujimaki ,  Yoshiyuki Morimoto

    发明人： Fumio Tsutsumi ,  Akio Iakashima ,  Mitsuhiko Sakakibara ,  Noboru Oshima ,  Tatsuo Fujimaki ,  Yoshiyuki Morimoto

    IPC分类号： C08L7/00 ,  B60C1/00 ,  C08F297/04 ,  C08L1/00 ,  C08L9/06 ,  C08L21/00 ,  C08L23/00 ,  C08L27/00 ,  C08L51/00 ,  C08L51/02 ,  C08L53/00 ,  C08L53/02 ,  C08L77/00 ,  C08L101/00

    CPC分类号： B60C1/0016 ,  C08F297/044 ,  Y10S525/914

    摘要： A rubber composition containing at least 20% by weight of a styrene-butadiene block copolymer consisting of a block (A) and a block (B) characterized in that: (i) the block (A) is a styrene-butadiene copolymer block having the content of styrene of 10-80% by weight and the average content of the vinyl bonds in the butadiene portion of 30-70% by weight; (ii) the block (B) is a polybutadiene block with the average content of the vinyl bonds in the butadiene portion being not more than 60% by weight (iii) the styrene-butadiene block copolymer contains at least 20% by weight of each of the block (A) and the block (B); (iv) the average content of the vinyl bonds in the butadiene portion of the block (A) is greater by at least 5% by weight than that of the block (B); (v) the glass transition temperature of the block (A) is higher by at least 30.degree. C. than that of the block (B); (vi) the whole content of the bound styrene in the above block copolymer is 5-40% by weight; (vii) the ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn of the block copolymer is 1.8-5.0 when calculated as polystyrene according to the gel permeation chromatogram; and (viii) the Mooney's viscosity (ML.sub.1+4.sup.100.degree. C.) of the block copolymer is 20-150.

    摘要翻译： 一种含有至少20重量％由嵌段（A）和嵌段（B）组成的苯乙烯 - 丁二烯嵌段共聚物的橡胶组合物，其特征在于：（i）嵌段（A）是苯乙烯 - 丁二烯共聚物嵌段，其具有 苯乙烯含量为10-80重量％，丁二烯部分中乙烯基键的平均含量为30-70重量％; （ii）嵌段（B）是丁二烯部分中乙烯基键的平均含量不大于60重量％的聚丁二烯嵌段（iii）苯乙烯 - 丁二烯嵌段共聚物含有至少20重量％ （A）和块（B）; （iv）嵌段（A）的丁二烯部分中的乙烯基键的平均含量比块（B）的平均含量高至少5重量％。 （v）嵌段（A）的玻璃化转变温度比嵌段（B）的玻璃化转变温度高至少30℃; （vi）上述嵌段共聚物中的结合苯乙烯的全部含量为5-40重量％ （vii）根据凝胶渗透色谱法计算，当以聚苯乙烯计算时，嵌段共聚物的重均分子量Mw与数均分子量Mn之比Mw / Mn为1.8-5.0; 和（viii）嵌段共聚物的门尼粘度（ML1 + 4100℃）为20-150℃。

    Butadiene-based rubber composition
    9.
    发明授权
    Butadiene-based rubber composition 失效
    丁二烯橡胶组合物

    公开(公告)号：US4824908A

    公开(公告)日：1989-04-25

    申请号：US29558

    申请日：1987-03-24

    申请人： Fumio Tsutsumi ,  Mitsuhiko Sakakibara ,  Noboru Shimada ,  Yoshihisa Fujinaga ,  Noboru Oshima ,  Tatsuro Hamada ,  Tatsuo Fujimaki

    发明人： Fumio Tsutsumi ,  Mitsuhiko Sakakibara ,  Noboru Shimada ,  Yoshihisa Fujinaga ,  Noboru Oshima ,  Tatsuro Hamada ,  Tatsuo Fujimaki

    IPC分类号： B60C1/00 ,  C08C19/44 ,  C08L9/00 ,  C08L21/00 ,  C08L7/00 ,  C08L9/06 ,  C08L53/02

    CPC分类号： B60C1/0025 ,  B60C1/0016 ,  C08C19/44 ,  C08L9/00 ,  Y10S152/905 ,  Y10T152/10846

    摘要： A butadiene-based rubber composition is disclosed, which contains not less than 20% by weight of a butadiene-based homopolymer or copolymer having a glass transition temperature (Tg) of not less than -105.degree. C., but less than -70.degree. C. and a Mooney viscosity (ML.sub.1+4, 100.degree. C.) of 10 to 150. The butadiene-based homopolymer or copolymer is obtained by polymerizing butadiene or random-copolymerizing butadiene with at least one kind of a monomer selected from the group consisting of another conjugated diene and an aromatic vinyl compound, and then reacting polymerization-active terminals thereof with an isocyanate compound and/or an isothiocyanate compound. The butadiene-based rubber composition has excellent resilience, fracture strength, and wear resistance as a vulcanizate as well as excellent processability as an unvulcanized rubber, and can be used as tire applications such as tire treads, undertreads, sidewalls, bead portions, etc. as well as vibration insulating rubber, hoses, belts and other industrial articles.

    摘要翻译： 公开了一种丁二烯基橡胶组合物，其含有不少于20重量％的玻璃化转变温度（Tg）不低于-105℃但小于-70℃的丁二烯基均聚物或共聚物 丁二烯类均聚物或共聚物是通过将丁二烯或无规共聚丁二烯与至少一种选自以下的单体进行聚合而获得的：丁二烯类均聚物或共聚物 由另一种共轭二烯和芳族乙烯基化合物组成，然后使其聚合活性末端与异氰酸酯化合物和/或异硫氰酸酯化合物反应。 丁二烯类橡胶组合物作为硫化橡胶具有优异的回弹性，断裂强度和耐磨性以及作为未硫化橡胶的优异加工性，并且可以用作轮胎胎面，胎面，胎侧，胎圈部等轮胎用途。 以及隔振橡胶，软管，皮带等工业用品。