公开(公告)号：US08283401B2

公开(公告)日：2012-10-09

申请号：US13133084

申请日：2009-12-04

申请人： Masato Murakami ,  Koji Shiba ,  Takeshi Shoda ,  Mitsuharu Anbe

发明人： Masato Murakami ,  Koji Shiba ,  Takeshi Shoda ,  Mitsuharu Anbe

IPC分类号： C08K3/34 ,  C08L9/00

CPC分类号： C08F4/545 ,  C08F36/04 ,  C08K3/36 ,  C08K5/548 ,  C08L7/00 ,  C08L9/00 ,  C08L2666/08

摘要： Provided by using a catalyst containing an yttrium compound is conjugated diene polymer with very low solution viscosity, improved workability, high degree of branching, and high content of cis-1,4 structures. Also provided is a rubber composition utilizing the polymer and allowing excellent dispersion of reinforcing agent. According to a method of manufacturing a conjugated diene polymer characterized by polymerizing a conjugated diene at 50 to 120° C. in the presence of a catalyst obtained from (A) an yttrium compound, (B) an ionic compound consisting of a non-coordinating anion and a cation, and (C) an organoaluminum compound, the conjugated diene polymer has the following characteristics that: (1) a ratio (Tcp/ML1+4) between a 5 wt % toluene solution viscosity (Tcp) measured at 25° C. and a Mooney viscosity (ML1+4) at 100° C. is 0.1 to 1.2; and (2) a content of cis-1,4 structures is 80% or higher, and a content of 1,2 structures is lower than 5%.

摘要翻译： 通过使用含有钇化合物的催化剂提供的是具有非常低的溶液粘度，改进的加工性，高支化度和高含量的顺式-1,4结构的共轭二烯聚合物。 还提供了一种利用该聚合物的橡胶组合物，并且能够提供增强剂的优异分散性。 根据制备共轭二烯聚合物的方法，其特征在于在（A）钇化合物得到的催化剂存在下，在50〜120℃下共聚共轭二烯，（B）由非配位的 阴离子和阳离子，和（C）有机铝化合物，共轭二烯聚合物具有以下特性：（1）在25℃下测量的5重量％甲苯溶液粘度（Tcp）之间的比率（Tcp / ML1 + 4） 在100℃下的门尼粘度（ML1 + 4）为0.1〜1.2; 和（2）顺式-1,4结构的含量为80％以上，1,2结构的含量低于5％。

公开(公告)号：US20110269899A1

公开(公告)日：2011-11-03

申请号：US13133084

申请日：2009-12-04

申请人： Masato Murakami ,  Koji Shiba ,  Takeshi Shoda ,  Mitsuharu Anbe

发明人： Masato Murakami ,  Koji Shiba ,  Takeshi Shoda ,  Mitsuharu Anbe

IPC分类号： C08K3/36 ,  C08L9/00 ,  C08F4/72 ,  C08F4/54 ,  C08F136/06

CPC分类号： C08F4/545 ,  C08F36/04 ,  C08K3/36 ,  C08K5/548 ,  C08L7/00 ,  C08L9/00 ,  C08L2666/08

摘要： Provided by using a catalyst containing an yttrium compound is conjugated diene polymer with very low solution viscosity, improved workability, high degree of branching, and high content of cis-1,4 structures. Also provided is a rubber composition utilizing the polymer and allowing excellent dispersion of reinforcing agent. According to a method of manufacturing a conjugated diene polymer characterized by polymerizing a conjugated diene at 50 to 120° C. in the presence of a catalyst obtained from (A) an yttrium compound, (B) an ionic compound consisting of a non-coordinating anion and a cation, and (C) an organoaluminum compound, the conjugated diene polymer has the following characteristics that: (1) a ratio (Tcp/ML1+4) between a 5 wt % toluene solution viscosity (Tcp) measured at 25° C. and a Mooney viscosity (ML1+4) at 100° C. is 0.1 to 1.2; and (2) a content of cis-1,4 structures is 80% or higher, and a content of 1,2 structures is lower than 5%.

摘要翻译： 通过使用含有钇化合物的催化剂提供的是具有非常低的溶液粘度，改进的加工性，高支化度和高含量的顺式-1,4结构的共轭二烯聚合物。 还提供了一种利用该聚合物的橡胶组合物，并且能够提供增强剂的优异分散性。 根据制备共轭二烯聚合物的方法，其特征在于在（A）钇化合物得到的催化剂存在下，在50〜120℃下共聚共轭二烯，（B）由非配位的 阴离子和阳离子，和（C）有机铝化合物，共轭二烯聚合物具有以下特性：（1）在25℃下测量的5重量％甲苯溶液粘度（Tcp）之间的比率（Tcp / ML1 + 4） 在100℃下的门尼粘度（ML1 + 4）为0.1〜1.2; 和（2）顺式-1,4结构的含量为80％以上，1,2结构的含量低于5％。

公开(公告)号：US07851537B2

公开(公告)日：2010-12-14

申请号：US11577475

申请日：2007-01-16

申请人： Mitsuharu Anbe ,  Naomi Okamoto ,  Takashi Wada

发明人： Mitsuharu Anbe ,  Naomi Okamoto ,  Takashi Wada

IPC分类号： C08K3/34 ,  C08J5/14

CPC分类号： B60C1/00 ,  B60C1/0016 ,  B60C1/0025 ,  C08K3/04 ,  C08K3/36 ,  C08K5/0008 ,  C08L7/00 ,  C08L9/00 ,  C08L21/00 ,  C08L2666/08

摘要： The invention has an object to provide a rubber composition for tire with improved processability and abrasion resistance. The invention relates to a rubber composition for tire, comprising: (a) 5-90 weight parts of a high cis polybutadiene having a cis structure in a proportion of 95 wt % or higher in a microstructure analysis; (b) 90-5 weight parts of a diene-based rubber other than (a); and (c) 1-100 weight parts of a reinforcing agent blended in 100 weight parts of a rubber component including (a)+(b). The high cis polybutadiene is synthesized using a cobalt-based catalyst and satisfies the requirements of: (i) a Mooney viscosity (ML) of 40-49; (ii) a molecular weight distribution [Weight average molecular weight (Mw)/Number average molecular weight (Mn)] of 3.0-3.9; and (iii) a velocity dependence index (n-value) of the Mooney viscosity of 2.3-3.0.

摘要翻译： 本发明的目的是提供一种具有改善的加工性和耐磨性的轮胎用橡胶组合物。 本发明涉及一种轮胎用橡胶组合物，其包含：（a）在组织分析中5-90重量份具有95重量％以上的顺式结构的高顺式聚丁二烯; （b）90-5重量份除（a）以外的二烯类橡胶; 和（c）在100重量份包含（a）+（b）的橡胶组分中混合1-100重量份的增强剂。 高顺式聚丁二烯使用钴基催化剂合成，满足以下要求：（i）门尼粘度（ML）为40-49; （ii）3.0-3.9的分子量分布[重均分子量（Mw）/数均分子量（Mn）]; 和（iii）门尼粘度的速度依赖指数（n值）为2.3-3.0。

公开(公告)号：US20070155889A1

公开(公告)日：2007-07-05

申请号：US10596755

申请日：2005-12-20

申请人： Naomi Okamoto ,  Mitsuharu Anbe

发明人： Naomi Okamoto ,  Mitsuharu Anbe

IPC分类号： B60C1/00

CPC分类号： C08L9/00 ,  B60C1/0016 ,  B60C1/0025 ,  B60C2001/0066 ,  C08K3/36 ,  C08K5/54 ,  C08K7/02 ,  C08L7/00 ,  C08L9/06 ,  C08L21/00 ,  C08L2666/08

摘要： The rubber composition of the invention includes a rubber composition which is a silica compounded rubber composition for tire containing 100 parts by weight of a rubber component made of (a) from 20 to 80% by weight of a vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene having a melting point of 170° C. or higher and a high-molecular substance having at least one unsaturated double bond per a repeating unit and comprising at least one member selected from polyisoprene, crystalline polybutadiene having a melting point of not higher than 150° C., liquid polybutadiene and derivatives thereof and (b) from 80 to 20% by weight of a diene-based rubber other than (a); and (c) from 40 to 100 parts by weight of a rubber reinforcing agent containing 40% or more of silica, wherein the 1,2-polybutadiene is dispersed in a short crystalline fiber state and the high-molecular substance is dispersed in a granular state in the cis-polybutadiene rubber which is a matrix component of the subject vinyl-cis-polybutadiene rubber (a); and the short crystalline fiber of the 1,2-polybutadiene is dispersed in particles of the high-molecular substance.

摘要翻译： 本发明的橡胶组合物包括橡胶组合物，其是用于轮胎的二氧化硅复合橡胶组合物，其包含100重量份由（a）20至80重量％的乙烯基 - 顺式聚丁二烯橡胶制成的橡胶组分，其含有1 ，熔点为170℃以上的2-聚丁二烯和每重复单元具有至少一个不饱和双键的高分子物质，并且包含至少一种选自聚异戊二烯，不溶于熔点的结晶聚丁二烯 高于150℃，液体聚丁二烯及其衍生物和（b）80至20重量％的除（a）之外的二烯基橡胶; 和（c）40〜100重量份含有40重量％以上二氧化硅的橡胶增强剂，其中1,2-聚丁二烯以短的结晶纤维状态分散，高分子物质分散在粒状 在作为本发明的乙烯基 - 顺式聚丁二烯橡胶（a）的基体组分的顺式聚丁二烯橡胶中的状态; 1,2-聚丁二烯的短结晶纤维分散在高分子物质的颗粒中。

公开(公告)号：US20090176910A1

公开(公告)日：2009-07-09

申请号：US11577475

申请日：2007-01-16

申请人： Mitsuharu Anbe ,  Naomi Okamoto ,  Takashi Wada

发明人： Mitsuharu Anbe ,  Naomi Okamoto ,  Takashi Wada

IPC分类号： C08J5/14

CPC分类号： B60C1/00 ,  B60C1/0016 ,  B60C1/0025 ,  C08K3/04 ,  C08K3/36 ,  C08K5/0008 ,  C08L7/00 ,  C08L9/00 ,  C08L21/00 ,  C08L2666/08

摘要： The invention has an object to provide a rubber composition for tire with improved processability and abrasion resistance. The invention relates to a rubber composition for tire, comprising: (a) 5-90 weight parts of a high cis polybutadiene having a cis structure in a proportion of 95 wt % or higher in a microstructure analysis; (b) 90-5 weight parts of a diene-based rubber other than (a); and (c) 1-100 weight parts of a reinforcing agent blended in 100 weight parts of a rubber component including (a)+(b). The high cis polybutadiene is synthesized using a cobalt-based catalyst and satisfies the requirements of: (i) a Mooney viscosity (ML) of 40-49; (ii) a molecular weight distribution [Weight average molecular weight (Mw)/Number average molecular weight (Mn)] of 3.0-3.9; and (iii) a velocity dependence index (n-value) of the Mooney viscosity of 2.3-3.0.

摘要翻译： 本发明的目的是提供一种具有改善的加工性和耐磨性的轮胎用橡胶组合物。 本发明涉及一种轮胎用橡胶组合物，其包含：（a）在组织分析中5-90重量份具有95重量％以上的顺式结构的高顺式聚丁二烯; （b）90-5重量份除（a）以外的二烯类橡胶; 和（c）在100重量份包含（a）+（b）的橡胶组分中混合1-100重量份的增强剂。 高顺式聚丁二烯使用钴基催化剂合成，满足以下要求：（i）门尼粘度（ML）为40-49; （ii）3.0-3.9的分子量分布[重均分子量（Mw）/数均分子量（Mn）]; 和（iii）门尼粘度的速度依赖指数（n值）为2.3-3.0。

公开(公告)号：US08586680B2

公开(公告)日：2013-11-19

申请号：US11994956

申请日：2007-06-26

申请人： Naomi Okamoto ,  Mitsuharu Anbe ,  Takashi Wada

发明人： Naomi Okamoto ,  Mitsuharu Anbe ,  Takashi Wada

IPC分类号： C08F36/00 ,  A63B37/00

CPC分类号： C08L9/00 ,  A63B37/0003 ,  A63B37/0094 ,  C08K5/0025 ,  C08K5/098 ,  C08K5/14

摘要： The object is to provide a rubber composition for a high-strength golf ball which has a high hardness, high resiliency, excellent processability and improved filler dispersibility, by adjusting each of the Mooney viscosity, the molecular weight distribution and the n value (the rate-dependent index for Mooney viscosity) of a high-cis-polybutadiene rubber using a cobalt catalyst to a value falling within a specific range. The rubber composition comprises 100 parts by weight of a high-cis-polybutadiene synthesized using a cobalt catalyst and 10 to 50 parts by weight of a co-crosslinking agent, wherein the high-cis-polybutadiene satisfies the following requirements (a) to (c): (a) the Mooney viscosity (ML) is 40 to 55; (b) the molecular weight distribution [a weight average molecular weight MW)/a number average molecular weight (Mn)] is 3.0 to 4.2; and (c) the rate-dependent index of Mooney viscosity (n value) is 2.3 to 3.0.

摘要翻译： 本发明的目的是提供一种高强度高尔夫球用橡胶组合物，其通过调节每个门尼粘度，分子量分布和n值（具有高的硬度，高回弹性，优异的加工性和改进的填料分散性） 使用钴催化剂的高顺式聚丁二烯橡胶的滞留指数为门尼粘度，其值落在特定范围内。 橡胶组合物包含100重量份使用钴催化剂合成的高顺式聚丁二烯和10至50重量份共交联剂，其中高顺式聚丁二烯满足以下要求（a）至（ c）：（a）门尼粘度（ML）为40〜55; （b）分子量分布[重均分子量MW] /数均分子量（Mn）]为3.0〜4.2; 和（c）门尼粘度（n值）的速率依赖指数为2.3〜3.0。

公开(公告)号：US07884155B2

公开(公告)日：2011-02-08

申请号：US10596757

申请日：2005-12-20

申请人： Naomi Okamoto ,  Mitsuharu Anbe ,  Jyun Yamashita ,  Tetsuji Nakajima ,  Takashi Kitamura ,  Osamu Kimura ,  Takashi Wada

发明人： Naomi Okamoto ,  Mitsuharu Anbe ,  Jyun Yamashita ,  Tetsuji Nakajima ,  Takashi Kitamura ,  Osamu Kimura ,  Takashi Wada

IPC分类号： C08K3/34

CPC分类号： C08L9/00 ,  C08F136/06 ,  C08K3/013 ,  C08L7/00 ,  C08L9/06 ,  C08L21/00 ,  C08F4/7096 ,  C08L2666/08

摘要： A process for producing a vinyl-cis-polybutadiene rubber, including mixing (A) vinyl-cis-polybutadiene obtained by (1) a step of adding a cis-1,4-polymerization catalyst obtainable from an organoaluminum compound and a soluble cobalt compound to a mixture containing 1,3-butadiene and a hydrocarbon-based organic solvent as the major components and having an adjusted water content, thereby subjecting the 1,3-butadiene to cis-1,4-polymerization and subsequently, (2) a step of making a catalyst obtainable from a soluble cobalt compound, an organoaluminum compound represented by the general formula, AlR3 (wherein R represents an alkyl group having from 1 to 6 carbon atoms, a phenyl group, or a cycloalkyl group), and carbon disulfide present in the resulting polymerization reaction mixture, thereby subjecting the 1,3-butadiene to 1,2-polymerization; and (B) cis-polybutadiene obtained by a step of adding the foregoing cis-1,4-polymerization catalyst, thereby subjecting the 1,3-butadiene to cis-1,4-polymerization and a rubber composition containing the resulting rubber.

摘要翻译： 一种乙烯基 - 顺式聚丁二烯橡胶的制备方法，包括混合（A）乙烯基 - 顺式聚丁二烯，其通过以下步骤获得：（1）将由有机铝化合物获得的顺式-1,4-聚合催化剂和可溶性钴化合物 以含有1,3-丁二烯和烃类有机溶剂为主要成分并具有调节水含量的混合物，由此使1,3-丁二烯进行顺式-1,4-聚合，随后将（2）a 由可溶性钴化合物，由通式表示的有机铝化合物AlR 3（其中R表示具有1至6个碳原子的烷基，苯基或环烷基）制备催化剂的步骤和二硫化碳 存在于所得聚合反应混合物中，由此使1,3-丁二烯进行1,2-聚合; 和（B）通过加入上述顺式-1,4-聚合催化剂的步骤得到的顺式聚丁二烯，由此使1,3-丁二烯进行顺式-1,4-聚合和含有所得橡胶的橡胶组合物。

公开(公告)号：US07884154B2

公开(公告)日：2011-02-08

申请号：US10596755

申请日：2005-12-20

申请人： Naomi Okamoto ,  Mitsuharu Anbe

发明人： Naomi Okamoto ,  Mitsuharu Anbe

IPC分类号： C08K3/34 ,  B60C1/00

CPC分类号： C08L9/00 ,  B60C1/0016 ,  B60C1/0025 ,  B60C2001/0066 ,  C08K3/36 ,  C08K5/54 ,  C08K7/02 ,  C08L7/00 ,  C08L9/06 ,  C08L21/00 ,  C08L2666/08

摘要： The rubber composition of the invention includes a rubber composition which is a silica compounded rubber composition for tire containing 100 parts by weight of a rubber component made of (a) from 20 to 80% by weight of a vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene having a melting point of 170° C. or higher and a high-molecular substance having at least one unsaturated double bond per a repeating unit and comprising at least one member selected from polyisoprene, crystalline polybutadiene having a melting point of not higher than 150° C., liquid polybutadiene and derivatives thereof and (b) from 80 to 20% by weight of a diene-based rubber other than (a); and (c) from 40 to 100 parts by weight of a rubber reinforcing agent containing 40% or more of silica, wherein the 1,2-polybutadiene is dispersed in a short crystalline fiber state and the high-molecular substance is dispersed in a granular state in the cis-polybutadiene rubber which is a matrix component of the subject vinyl-cis-polybutadiene rubber (a); and the short crystalline fiber of the 1,2-polybutadiene is dispersed in particles of the high-molecular substance.

摘要翻译： 本发明的橡胶组合物包括橡胶组合物，其是用于轮胎的二氧化硅复合橡胶组合物，其包含100重量份由（a）20至80重量％的乙烯基 - 顺式聚丁二烯橡胶制成的橡胶组分，其含有1 ，熔点为170℃以上的2-聚丁二烯和每重复单元具有至少一个不饱和双键的高分子物质，并且包含至少一种选自聚异戊二烯，不溶于熔点的结晶聚丁二烯 高于150℃，液体聚丁二烯及其衍生物和（b）80至20重量％的除（a）之外的二烯基橡胶; 和（c）40〜100重量份含有40重量％以上二氧化硅的橡胶增强剂，其中1,2-聚丁二烯以短的结晶纤维状态分散，高分子物质分散在粒状 在作为本发明的乙烯基 - 顺式聚丁二烯橡胶（a）的基体组分的顺式聚丁二烯橡胶中的状态; 1,2-聚丁二烯的短结晶纤维分散在高分子物质的颗粒中。

公开(公告)号：US20100151965A1

公开(公告)日：2010-06-17

申请号：US11994956

申请日：2007-06-26

申请人： Naomi Okamoto ,  Mitsuharu Anbe ,  Takashi Wada

发明人： Naomi Okamoto ,  Mitsuharu Anbe ,  Takashi Wada

IPC分类号： A63B37/00 ,  C08F4/00

CPC分类号： C08L9/00 ,  A63B37/0003 ,  A63B37/0094 ,  C08K5/0025 ,  C08K5/098 ,  C08K5/14

摘要： The object is to provide a rubber composition for a high-strength golf ball which has a high hardness, high resiliency, excellent processability and improved filler dispersibility, by adjusting each of the Mooney viscosity, the molecular weight distribution and the n value (the rate-dependent index for Mooney viscosity) of a high-cis-polybutadiene rubber using a cobalt catalyst to a value falling within a specific range. The rubber composition comprises 100 parts by weight of a high-cis-polybutadiene synthesized using a cobalt catalyst and 10 to 50 parts by weight of a co-crosslinking agent, wherein the high-cis-polybutadiene satisfies the following requirements (a) to (c): (a) the Mooney viscosity (ML) is 40 to 55; (b) the molecular weight distribution [a weight average molecular weight MW)/a number average molecular weight (Mn)] is 3.0 to 4.2; and (c) the rate-dependent index of Mooney viscosity (n value) is 2.3 to 3.0.

摘要翻译： 本发明的目的是提供一种高强度高尔夫球用橡胶组合物，其通过调节每个门尼粘度，分子量分布和n值（具有高的硬度，高回弹性，优异的加工性和改进的填料分散性） 使用钴催化剂的高顺式聚丁二烯橡胶的滞留指数为门尼粘度，其值落在特定范围内。 橡胶组合物包含100重量份使用钴催化剂合成的高顺式聚丁二烯和10至50重量份共交联剂，其中高顺式聚丁二烯满足以下要求（a）至（ c）：（a）门尼粘度（ML）为40〜55; （b）分子量分布[重均分子量MW] /数均分子量（Mn）]为3.0〜4.2; 和（c）门尼粘度（n值）的速率依赖指数为2.3〜3.0。

公开(公告)号：US20070197714A1

公开(公告)日：2007-08-23

申请号：US10596757

申请日：2005-12-20

申请人： Naomi Okamoto ,  Mitsuharu Anbe ,  Jyun Yamashita ,  Tetsuji Nakajima ,  Takashi Kitamura ,  Osamu Kimura ,  Takashi Wada

发明人： Naomi Okamoto ,  Mitsuharu Anbe ,  Jyun Yamashita ,  Tetsuji Nakajima ,  Takashi Kitamura ,  Osamu Kimura ,  Takashi Wada

IPC分类号： B60C1/00

CPC分类号： C08L9/00 ,  C08F136/06 ,  C08K3/013 ,  C08L7/00 ,  C08L9/06 ,  C08L21/00 ,  C08F4/7096 ,  C08L2666/08

摘要： A process for producing a vinyl-cis-polybutadiene rubber, including mixing (A) vinyl-cis-polybutadiene obtained by (1) a step of adding a cis-1,4-polymerization catalyst obtainable from an organoaluminum compound and a soluble cobalt compound to a mixture containing 1,3-butadiene and a hydrocarbon-based organic solvent as the major components and having an adjusted water content, thereby subjecting the 1,3-butadiene to cis-1,4-polymerization and subsequently, (2) a step of making a catalyst obtainable from a soluble cobalt compound, an organoaluminum compound represented by the general formula, AlR3 (wherein R represents an alkyl group having from 1 to 6 carbon atoms, a phenyl group, or a cycloalkyl group), and carbon disulfide present in the resulting polymerization reaction mixture, thereby subjecting the 1,3-butadiene to 1,2-polymerization; and (B) cis-polybutadiene obtained by a step of adding the foregoing cis-1,4-polymerization catalyst, thereby subjecting the 1,3-butadiene to cis-1,4-polymerization and a rubber composition containing the resulting rubber.

摘要翻译： 一种乙烯基 - 顺式聚丁二烯橡胶的制备方法，包括混合（A）乙烯基 - 顺式聚丁二烯，其通过以下步骤获得：（1）将由有机铝化合物获得的顺式-1,4-聚合催化剂和可溶性钴化合物 以含有1,3-丁二烯和烃类有机溶剂为主要成分并具有调节水含量的混合物，由此使1,3-丁二烯进行顺式-1,4-聚合，随后将（2）a 制备由可溶性钴化合物，由通式表示的有机铝化合物AlR 3（其中R表示具有1至6个碳原子的烷基，苯基或 环烷基）和二硫化碳存在于所得聚合反应混合物中，由此使1,3-丁二烯进行1,2-聚合; 和（B）通过加入上述顺式-1,4-聚合催化剂的步骤得到的顺式聚丁二烯，由此使1,3-丁二烯进行顺式-1,4-聚合和含有所得橡胶的橡胶组合物。