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71. 发明授权

US09803032B2 Processes for the preparation of high-cis polydienes 有权
公开(公告)号：US09803032B2
公开(公告)日：2017-10-31
申请号：US14116779
申请日：2012-05-08
申请人： Zengquan Qin
发明人： Zengquan Qin
IPC分类号： C08F2/02 , C08F2/04 , C08F36/04 , C08F236/10
CPC分类号： C08F2/02 , C08F2/04 , C08F36/04 , C08F236/10 , C08F4/7098
摘要： The present disclosure is directed towards a solution or bulk polymerization process for preparing high-cis polydienes that utilizes at least one vinyl aromatic compound as a molecular weight regulator. The disclosed solution or bulk polymerization processes are useful for preparing high-cis polydienes with a Mooney viscosity between 30 and 55 while allowing the use of lower amounts of catalyst.

72. 发明申请

US20130274430A1 Bulk Polymerization of Conjugated Dienes Using a Nickel-Based Catalyst System 有权
标题翻译：使用镍基催化剂体系共轭二烯的大量聚合
公开(公告)号：US20130274430A1
公开(公告)日：2013-10-17
申请号：US13976315
申请日：2011-12-30
申请人： Kevin M. McCauley , Steven Luo
发明人： Kevin M. McCauley , Steven Luo
IPC分类号： C08F4/52
CPC分类号： C08F4/52 , C08F2/02 , C08F4/70 , C08F36/04 , C08F4/7098
摘要： A process for preparing a polydiene, the process comprising the steps of (i) providing conjugated diene monomer; (ii) charging a nickel-based catalyst system to the conjugated diene monomer; and (iii) charging a modulating Lewis base to the conjugated diene monomer, to thereby polymerize the conjugated diene monomer in the presence of the modulating Lewis base, where said step of charging a modulating Lewis base is separate from said step of charging a nickel-based catalyst, and where said steps of providing conjugated diene monomer, charging a nickel-based catalyst system and charging a Lewis base form a polymerization mixture that includes less than 20% by weight of organic solvent based on the total weight of the polymerization mixture.
摘要翻译：一种制备聚二烯的方法，该方法包括以下步骤：（i）提供共轭二烯单体; （ii）将镍基催化剂体系装入共轭二烯单体; 和（iii）将调节的路易斯碱装入共轭二烯单体，从而在调节路易斯碱的存在下使共轭二烯单体聚合，其中所述调节路易斯碱的装入步骤与将镍 - 并且其中所述提供共轭二烯单体的步骤，加入镍基催化剂体系和加入路易斯碱形成聚合混合物，其包含基于聚合混合物的总重量小于20重量％的有机溶剂。

73. 发明授权

US07820580B2 Nickel-based catalysts for preparing high cis 1,4-polydienes 有权
标题翻译：用于制备高顺式1,4-聚二烯的镍基催化剂
公开(公告)号：US07820580B2
公开(公告)日：2010-10-26
申请号：US12270424
申请日：2008-11-13
申请人： Zengquan Qin , Jason T. Poulton , Michael W. Hayes
发明人： Zengquan Qin , Jason T. Poulton , Michael W. Hayes
IPC分类号： B01J31/28 , B01J31/18 , B01J27/12 , B01J27/128
CPC分类号： B01J31/2282 , B01J31/0201 , B01J31/0202 , B01J31/0204 , B01J31/128 , B01J31/143 , B01J31/2265 , B01J2531/847 , B01J2531/90 , C08F136/06 , C08F4/7098
摘要： A nickel-carbene polymerization catalyst system for preparing high cis polydienes is provided. The catalyst system comprises (a) a nickel N-heterocyclic carbene complex, (b) an organoaluminum compound, (c) a fluorine-containing compound, and (d) optionally, an alcohol. Also provided is a process for producing a polydiene comprising reacting a conjugated diene in the presence of a polymerization catalyst comprising (a) a nickel N-heterocyclic carbene complex, (b) an organoaluminum compound, (c) a fluorine-containing compound, and (d) optionally, an alcohol.
摘要翻译：提供了制备高顺式聚二烯的镍 - 卡宾聚合催化剂体系。催化剂体系包括（a）镍N-杂环卡宾络合物，（b）有机铝化合物，（c）含氟化合物和（d）任选的醇。还提供了一种制备聚二烯的方法，包括在聚合催化剂存在下使共轭二烯反应，所述聚合催化剂包含（a）镍N-杂环卡宾络合物，（b）有机铝化合物，（c）含氟化合物和（d）任选地，醇。

74. 发明申请

US20090221774A1 DIENE POLYMER AND PRODUCTION PROCESS THEREOF 有权
标题翻译：二烯聚合物及其生产方法
公开(公告)号：US20090221774A1
公开(公告)日：2009-09-03
申请号：US12372815
申请日：2009-02-18
申请人： Kohtaro Osakada , Daisuke Takeuchi , Yusuke Fukuda , Osamu Ihata , Hiroshi Kuribayashi
发明人： Kohtaro Osakada , Daisuke Takeuchi , Yusuke Fukuda , Osamu Ihata , Hiroshi Kuribayashi
IPC分类号： C08F2/00 , C08F14/14
CPC分类号： C08F36/20 , C08F4/7098
摘要： A polymer comprising a unit represented by the following formula (1); and a process for producing the polymer comprising the step of polymerizing a diene compound such as 9,9-diallylfluorene in the presence of a polymerization catalyst formed by contacting a nickel compound with an organoaluminum compound and/or a boron compound:
摘要翻译：包含由下式（1）表示的单元的聚合物; 以及一种制备聚合物的方法，包括在通过使镍化合物与有机铝化合物和/或硼化合物接触而形成的聚合催化剂的存在下聚合二烯化合物如9,9-二烯丙基芴的步骤：

75. 发明授权

US07081504B2 Synthesis of 1,4-polybutadiene 失效
公开(公告)号：US07081504B2
公开(公告)日：2006-07-25
申请号：US10929977
申请日：2004-08-30
申请人： Michael Joseph Rachita , Scott Edwards Johnson
发明人： Michael Joseph Rachita , Scott Edwards Johnson
IPC分类号： C08F2/06 , C08F136/06
CPC分类号： C08F36/06 , C08F136/06 , Y10S526/907 , C08F4/7098
摘要： This invention is based upon the unexpected discovery that alkylated diphenylamines can be used in conjunction with nickel based catalyst systems which contain (a) an organonickel compound, (b) an organoaluminum compound, and (c) a fluorine containing compound to produce cis-1,4-polybutadiene having reduced molecular weight and an increased level of branching. This results in the cis-1,4-polybutadiene exhibiting good processability without sacrificing cold flow characteristics. Additionally, the alkylated diphenylamine which remains in the rubber acts in a manner which provides it with antioxidant protection. In other words, the use of alkylated diphenylamines accomplishes the three major objectives that are realized by employing para-styrenated diphenylamines (reduced molecular weight, regulated polymer macrostructure through branching and antidegradant protection). However, the utilization of alkylated diphenylamines, unlike para-styrenated diphenylamines, offers the additional advantage of being soluble in aliphatic solvents. By virtue of this increased level of solubility in aliphatic solvents, such as hexane, alkylated diphenylamines can be employed at greatly reduced levels of aromatic solvents. Likewise, when mixed catalyst streams containing alkylated diphenyl amines are combined precipitation is minimized compared to para-styrenated diphenylamine significantly improving issues related to fouling. The subject invention more specifically discloses a process for producing cis-1,4-polybutadiene having a reduced molecular weight and improved processability which comprises polymerizing 1,3-butadiene in the presence of (a) an organonickel compound, (b) an organoaluminum compound, (c) a fluorine containing compound, and (d) an alkylated diphenylamine; wherein the alkylated diphenylamine has alkyl groups that contain from 2 to 18 carbon atoms, and wherein the organoaluminum compound and the fluorine containing compound are brought together in the presence of the alkylated diphenylamine.

76. 发明授权

US06699813B2 Lanthanide-based catalyst composition for the manufacture of polydienes 有权
标题翻译：用于制造聚二烯的镧系元素的催化剂组合物
公开(公告)号：US06699813B2
公开(公告)日：2004-03-02
申请号：US10287205
申请日：2002-11-04
申请人： Steven Luo , Yoichi Ozawa , Koji Masaki , David Lawson
发明人： Steven Luo , Yoichi Ozawa , Koji Masaki , David Lawson
IPC分类号： B01D3100
CPC分类号： C08F36/04 , Y10S526/943 , C08F4/7098 , C08F4/545
摘要： A catalyst composition that is the combination of or the reaction product of ingredients comprising (a) an lanthanide compound, (b) an alkylating agent, (c) a nickel-containing compound, and optionally (d) a halogen-containing compound, with the proviso that the halogen-containing compound must be present where none of the lanthanide compound, the alkylating agent, and the nickel-containing compound contain a labile halogen atom.
摘要翻译：一种催化剂组合物，其是成分的组合或成分的反应产物，其包含（a）镧系元素化合物，（b）烷基化剂，（c）含镍化合物和任选（d）含卤素化合物与条件是必须存在镧系化合物，烷化剂和含镍化合物中不含有不稳定卤素原子的卤素化合物。

77. 发明授权

US06596825B1 Low gel high cis polydiene 有权
标题翻译：低凝胶高顺式聚二烯
公开(公告)号：US06596825B1
公开(公告)日：2003-07-22
申请号：US10208520
申请日：2002-07-30
申请人： H. Jerrold Miller
发明人： H. Jerrold Miller
IPC分类号： C08F242
CPC分类号： C08F36/04 , C08F4/7098 , C08F2/42
摘要： The present invention is directed to a process for forming a high-cis polydiene. The process includes catalyzing a diene polymerization, and terminating the polymerization with an amine-water termination mixture, preferably a TMEDA-water termination mixture. The catalyst system is a mixture of (a) organoaluminum compounds; (b) organonickel compounds; and (c) fluorine-containing compounds.
摘要翻译：本发明涉及形成高顺式聚二烯的方法。该方法包括催化二烯聚合，并用胺 - 水终止混合物，优选TMEDA-水终止混合物终止聚合。催化剂体系是（a）有机铝化合物的混合物; （b）有机锡化合物; 和（c）含氟化合物。

78. 发明授权

US3844974A Catalyst for the polymerization of conjugated diolefins 失效
标题翻译：用于聚合二烯的聚合的催化剂
公开(公告)号：US3844974A
公开(公告)日：1974-10-29
申请号：US32694073
申请日：1973-01-26
申请人： GOODYEAR TIRE & RUBBER
发明人： THROCKMORTON M
IPC分类号： C08F36/04 , B01J11/84
CPC分类号： C08F36/04 , C08F4/7098
摘要： There is disclosed a method for the polymerization of butadiene or butadiene in mixture with other diolefins such as isoprene, 2ethyl butadiene, 2,3-dimethyl butadiene and the like, with a catalyst system comprising (1) an organometallic compound in which the metal is from Groups I, II and III of the Periodic System, (2) a nickel compound from the group of carboxylic acid salts of nickel, organic complex compounds of nickel or nickel carbonyls, (3) a fluorine containing compound from the group of boron trifluoride, metal fluorides and complexes thereof and (4) a compound containing a hydroperoxide group. The polymers contain a high proportion of cis 1,4 content and find use as synthetic rubbers in such products as tires and tire treads.
摘要翻译：公开了一种与其它二烯烃如异戊二烯，2-乙基丁二烯，2,3-二甲基丁二烯等混合聚合丁二烯或丁二烯的方法，催化剂体系包括（1）有机金属化合物，其中金属来自周期性系统的I，II和III族，（2）由镍的羧酸盐，镍或镍羰基的有机络合物组成的镍化合物，（3）一组含氟化合物三氟化硼，金属氟化物及其络合物和（4）含有氢过氧化物基团的化合物。这些聚合物含有高比例的顺式1,4含量，并且可用作诸如轮胎和轮胎胎面的产品中的合成橡胶。

79. 发明授权

US3652529A Method for producing solid polybutadiene containing more than 60 percent 1 2-microstructure 失效
标题翻译：生产含多于60％1 2-微结构的固体聚丁二烯的方法
公开(公告)号：US3652529A
公开(公告)日：1972-03-28
申请号：US3652529D
申请日：1970-04-23
申请人： GOODYEAR TIRE & RUBBER
发明人： JUDY WILLIAM A , THROCKMORTON MORFORD C
IPC分类号： C08F136/06 , C08D1/14 , C08D3/06
CPC分类号： C08F136/06 , C08F4/7098
摘要： A METHOD IS DISCLOSED TO PRODUCE A POLYBUTADIENE CONTAINING MORE THAN 60 PERCENT OF THE POLYMER IN A 1,2 MICROSTRUCTURE WHICH COMPRISES POLYMERIZING BUTADIENE UNDER SOLUTION POLYMERIZATION CONDITIONS, WITH A CATALYST COMPRISING (1) AN ORGANOALUMINUM COMPOUND, (2) TUNGSTEN OXYCHLORIDE AND (3) A NICKEL SALT OF A CARBOXYLIC ACID OR AN ORGANO COMPLEX COMPOUND OF NICKEL IN WHICH THE MOLE RATIO OF ALUMINUM TO TUNGSTEN IS EQUAL TO OR GREATER THAN 1.5/1.

80. 发明授权

US3577395A Novel catalyst for the polymerization of conjugated dienes 失效
标题翻译：用于聚合二烯的聚合的新催化剂
公开(公告)号：US3577395A
公开(公告)日：1971-05-04
申请号：US3577395D
申请日：1969-04-09
申请人： GOODYEAR TIRE & RUBBER
发明人： LAL JOGINDER , THROCKMORTON MORFORD C
IPC分类号： C08F36/04 , C08D3/06
CPC分类号： C08F36/04 , C08F4/7098
摘要： THERE IS DISCLOSED A PROCESS OF THE POLYMERIZATION OF BUTADIENE AND BUTADIENE IN MIXTURE WITH OTHER CONJUGATED DIOLEFINS TO FORM POLYMERS CONTAINING A HIGH PORTION OF BUTADIENE UNITS IN THE CIS 1,4 CONGIGURATION COMPRISING CONTACTING AT LEAST ONE DIOLEFIN WITH A CATALYST COMPRISING (A) AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSITING OF ORGANOMETALLIC COMPOUNDS WHEREIN THE METAL IS SELECTED FROM GROUPS I, II AND III OF THE PERIODIC TABLE AND HYDRIDES OF METALS OF GROUPS II AND III OF THE PERIODIC TABLE AND THEIR MONOMERIC OR POLYMERIC HALIDE DERIVATIVES, AMINE DERIVATIVES AND COMPLEXES OF THESE HYDRIDES WITH AMINES, ETHERS OR OTHER MOLECULES CAPABLE OF FORMING COMPLEX COMPOUNDS WITH THESE HYDRIDES, (B) AT LEAST ONE ORGANONICKEL COMPOUND AND (C) AT LEAST ONE ORGANIC FLUORO-CHEMICAL COMPOUND.

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