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61. 发明授权

US06489415B2 Process for synthesizing trans-1,4-polybutadiene 失效
公开(公告)号：US06489415B2
公开(公告)日：2002-12-03
申请号：US09730257
申请日：2000-12-05
申请人： Wen-Liang Hsu , Adel Farhan Halasa
发明人： Wen-Liang Hsu , Adel Farhan Halasa
IPC分类号： C08F446
CPC分类号： C08F136/06 , C08F4/50 , C08F4/48
摘要： The process and catalyst system of this invention can be utilized to synthesize polybutadiene rubber having a high trans content and a low melting point by solution polymerization. The trans-polybutadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit outstanding wear characteristics. More importantly, the trans-polybutadiene rubber of this invention can be easily processed because of its low level of crystallinity. In fact, the trans-polybutadiene made by the process of this invention does not need to be heated in a “hot-house” before being used in making rubber compounds. This invention more specifically reveals a process for synthesizing trans-polybutadiene rubber which comprises polymerizing 1,3-butadiene in an organic solvent in the presence of a catalyst system which comprises (a) an organolithium compound, (b) a barium compound selected from the group consisting of (i) barium salts of cyclic alcohols, such as barium mentholate, and (ii) barium thymolate, and (c) an organoaluminum compound. The trans-polybutadiene made with the catalyst system of this invention typically has a glass transition temperature that is within the range of about -97° C. to about -90° C., a melting point that is within the range of about -30° C. to about 30° C., and a number average molecular weight that is within the range of about 50,000 to about 400,000.

62. 发明授权

US06348550B1 Molybdenum-based catalyst composition and process for controlling the characteristics of conjugated diene polymers 有权
标题翻译：钼基催化剂组合物和控制共轭二烯聚合物特性的方法
公开(公告)号：US06348550B1
公开(公告)日：2002-02-19
申请号：US09548556
申请日：2000-04-13
申请人： Steven Luo
发明人： Steven Luo
IPC分类号： C08F478
CPC分类号： C08F136/06 , C08F4/69
摘要： A catalyst composition that is the combination of or the reaction product of ingredients including (a) a molybdenum-containing compound, (b) a hydrogen phosphite, and (c) a blend of two or more sterically distinct organoaluminum compounds. This catalyst composition is particularly useful for polymerizing conjugated dienes. When this catalyst composition is used to polymerize 1,3-butadiene into syndiotactic 1,2-polybutadiene, the ratio of the organoaluminum compounds can be adjusted to vary the melting temperature and molecular weight of the polymer product.
摘要翻译：一种催化剂组合物，其为成分的组合或反应产物，包括（a）含钼化合物，（b）亚磷酸氢盐，和（c）两种或多种空间上不同的有机铝化合物的共混物。该催化剂组合物特别可用于聚合共轭二烯。当该催化剂组合物用于将1,3-丁二烯聚合成间规1,2-聚丁二烯时，可以调节有机铝化合物的比例以改变聚合物产物的熔融温度和分子量。

63. 发明申请

US20020016423A1 Process for controlling degree of branch of high 1,4-cis polybutadiene 失效
标题翻译：控制高1,4-顺式聚丁二烯分枝度的方法
公开(公告)号：US20020016423A1
公开(公告)日：2002-02-07
申请号：US09817997
申请日：2001-03-27
发明人： Young-Chan Jang , Pil-Sung Kim , Gwang-Hoon Kwag , A-Ju Kim , Seung-Hwon Lee
IPC分类号： C08F004/44
CPC分类号： C08F136/06 , C08F4/7098
摘要： Disclosed is a process of controlling the degree of branch of high 1,4-cis polybutadiene without any alternation in the 1,4-cis content and the polymerization yield, in which a dialkylzinc compound represented by the following formula I is added in a controlled amount as an agent for controlling the degree of branch of high 1,4-cis polybutadiene, thus guaranteeing the optimum processability and physical properties of polymer according to the use purpose. Formula IR1nullZnnullR2wherein R1 and R2 are same or different and include an alkyl group containing 1 to 5 carbon atoms.
摘要翻译：公开了一种控制高顺式1,4-顺式聚丁二烯的分支程度的方法，其中1,4-顺式含量和聚合产率没有任何变化，其中将下式I表示的二烷基锌化合物加入受控的作为控制高1,4-顺式聚丁二烯的分支度的试剂，从而根据用途保证聚合物的最佳加工性能和物理性能。其中R1和R2相同或不同并且包括含有1至5个碳原子的烷基，其中R 1和R 2都是相同或不同的。

64. 发明申请

US20010036899A1 Process and iron-based catalyst composition for the production of syndiotactic 1,2-polybutadiene 有权
公开(公告)号：US20010036899A1
公开(公告)日：2001-11-01
申请号：US09850240
申请日：2001-05-07
发明人： Steven Luo
IPC分类号： B01J031/00
CPC分类号： C08F4/70 , C08F136/06
摘要： A catalyst composition comprising (a) an iron-containing compound, (b) a dihydrocarbyl hydrogen phosphite, and (c) an organoaluminum compound is disclosed for polymerizing 1,3-butadiene into syndiotactic 1,2-polybutadiene. The use of the catalyst composition of this disclosure avoids the use of environmentally detrimental components such as carbon disulfide and halogenated solvents. The melting temperature of the syndiotactic 1,2-polybutadiene can be varied from about 100 to about 200null C. by variations in the catalyst components and the component ratios. The ability to vary the melting temperature over such a broad range with a single catalyst composition is very desirable. The syndiotactic 1,2-polybutadiene can be used as a plastic or as an additive for rubber compositions wherein it can crosslink with conventional rubbers using conventional crosslinking agents.

65. 发明授权

US6117956A Catalyst composition and polymerization process for producing syndiotactic 1,2-polybutadiene 失效
标题翻译：用于制备间规1,2-聚丁二烯的催化剂组合物和聚合方法
公开(公告)号：US6117956A
公开(公告)日：2000-09-12
申请号：US88611
申请日：1998-06-01
申请人： Steven Luo
发明人： Steven Luo
IPC分类号： C08F4/50 , C08F4/78 , C08F36/06 , C08F136/06 , C08F4/06 , B01J31/00 , C08F36/00
CPC分类号： C08F136/06
摘要： The instant invention teaches a method for forming a syndiotactic 1,2-polybutadiene product having a higher syndiotacticity and a higher melting temperature than syndiotactic 1,2-polybutadiene produced using chromium catalysts known in the prior art. The method includes polymerizing 1,3-butadiene in solution with a solvent, in the presence of catalytically effective amounts of: (a) a chromium compound; (b) an organomagnesium compound; and, (c) a cyclic hydrogen phosphite.
摘要翻译：本发明教导了一种形成间同立构1,2-聚丁二烯产物的方法，该产物具有比使用现有技术中已知的铬催化剂制备的间同立构1,2-聚丁二烯具有更高的间同立构规整度和较高的熔融温度。该方法包括在溶剂中将1,3-丁二烯与溶剂聚合，在催化有效量的存在下：（a）铬化合物; （b）有机镁化合物; 和（c）环状亚磷酸氢盐。

66. 发明授权

US6013746A Process for controlling the molecular weight distribution of high 1,4-cis polybutadiene 失效
标题翻译：控制高1,4-顺式聚丁二烯分子量分布的方法
公开(公告)号：US6013746A
公开(公告)日：2000-01-11
申请号：US93646
申请日：1998-06-09
申请人： Young-Chan Jang , Gwang-Hoon Kwag , Dong-Il Yoon , A-Ju Kim , Kyung-Nam Lim
发明人： Young-Chan Jang , Gwang-Hoon Kwag , Dong-Il Yoon , A-Ju Kim , Kyung-Nam Lim
IPC分类号： C08F36/06 , C08F4/609 , C08F136/06 , C08F236/06 , C08F4/80
CPC分类号： C08F136/06
摘要： This invention relates to a process for controlling the molecular weight distribution of high 1,4-cis polybutadiene and more particularly, to a process of easily controlling the molecular weight distribution of polybutadiene which is concerned directly with the physical properties such as processability, in such a manner that preparation of high 1,4-cis polybutadiene is made available via polymerization of 1,3-butadiene in the presence of Ziegler-Natta catalyst, adding carboxylic acid represented by following formula I for the controlling of the molecular weight distribution of polybutadiene based on the contents of carboxylic acid, may be easily controlled, without any alternation in the 1,4-cis contents. ##STR1## Wherein R is selected from the group consisting of alkyl, cycloalkyl and arylalkyl groups substituted or unsubstituted with at least one or more halogen atoms, or alkyl, cycloalkyl and arylalkyl groups with at least one or more double bonds containing from 5 to 20 carbon atoms.
摘要翻译：本发明涉及一种控制高1,4-顺式聚丁二烯的分子量分布的方法，更具体地说，涉及容易控制聚丁二烯的分子量分布的方法，其直接关系到诸如加工性的物理性质通过在齐格勒 - 纳塔催化剂存在下，通过1,3-丁二烯的聚合可得到制备高1,4-顺式聚丁二烯的方式，加入由下式I表示的羧酸以控制聚丁二烯的分子量分布基于羧酸的含量，可以容易地控制，而在1,4-顺式含量中没有任何变化。其中R选自被至少一个或多个卤素原子取代或未取代的烷基，环烷基和芳基烷基，或具有至少一个或多个含有5至20个碳原子的双键的烷基，环烷基和芳烷基。

67. 发明授权

US5945485A Viscosity modifier polybutadiene polymers 失效
标题翻译：粘度调节剂聚丁二烯聚合物
公开(公告)号：US5945485A
公开(公告)日：1999-08-31
申请号：US618052
申请日：1996-03-25
申请人： Mark Joseph Struglinski , Gary William VerStrate , Lewis J. Fetters
发明人： Mark Joseph Struglinski , Gary William VerStrate , Lewis J. Fetters
IPC分类号： C08C19/02 , C08F8/04 , C08F36/00 , C08F36/04 , C08F136/06 , C08F297/02 , C08F297/04 , C08L53/00 , C10M143/12 , C10N20/04 , C10N20/06 , C10N30/02 , C10N40/04
CPC分类号： C10M143/12 , C08C19/02 , C08F136/06 , C08F297/02 , C08F297/048 , C08F8/04 , C08L53/005 , C10M2205/06
摘要： The present invention relates to hydrogenated polybutadiene comprising monomeric units of 1,4-butadiene and 1,2-butadiene addition products. The copolymer is hydrogenated and comprises at least 10% by weight of at least one crystallizable segment and at least one low crystallinity segment.
摘要翻译：本发明涉及包含1,4-丁二烯和1,2-丁二烯加成产物的单体单元的氢化聚丁二烯。共聚物被氢化并且包含至少10重量％的至少一个可结晶链段和至少一个低结晶度链段。

68. 发明授权

US5652304A Vapor phase synthesis of rubbery polymers 失效
标题翻译：橡胶状聚合物的气相合成
公开(公告)号：US5652304A
公开(公告)日：1997-07-29
申请号：US663803
申请日：1996-06-28
申请人： Nissim Calderon , Kenneth Floyd Castner , Howard Allen Colvin , Joel Muse, Jr.
发明人： Nissim Calderon , Kenneth Floyd Castner , Howard Allen Colvin , Joel Muse, Jr.
IPC分类号： B01J8/10 , B01J8/24 , B01J8/36 , C08F2/06 , C08F2/34 , C08F4/64 , C08F4/70 , C08F36/04 , C08F136/04 , C08F136/06 , C08F136/08 , G09F13/28 , G09F21/06
CPC分类号： B01J8/1827 , B01J8/10 , B01J8/24 , B01J8/36 , C08F136/04 , C08F136/06 , C08F136/08 , C08F36/04 , G09F13/28 , G09F21/06 , B01J2208/00256 , B01J2208/00274 , B01J2219/00108 , B01J2219/182 , Y10S526/901 , Y10S526/903
摘要： By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.; and(3) withdrawing said cis-1,4-polyisoprene from said reaction zone. It has been determined that gel formation can be reduced by conducting the polymerization of isoprene monomer in the presence of a diarylamine, such as para-styrenated diphenylamine.
摘要翻译：通过利用本发明的气相聚合技术，实现了许多显着和非常有益的优点。例如，具有一致和可控分子量的顺式-1,4-聚异戊二烯橡胶和高顺式-1,4-聚丁二烯橡胶可以在不使用溶剂的情况下容易且实际地制备。本发明更具体地公开了一种将异戊二烯气相聚合成顺式-1,4-聚异戊二烯的方法，包括以下步骤：（1）将反应区中的所述异戊二烯和预制的催化剂体系装入反应区，有机铝化合物与四氯化钛，优选在至少一种醚存在下进行; 其中所述异戊二烯通过温度和压力的适当组合保持在所述反应区中的气相中; （2）允许所述异戊二烯在约35℃至约70℃的温度范围内聚合成顺式-1,4-聚异戊二烯; 和（3）从所述反应区中取出所述顺式-1,4-聚异戊二烯。已经确定通过在二芳基胺如对苯二甲酸二苯胺存在下进行异戊二烯单体的聚合可以降低凝胶形成。

69. 发明授权

US5596053A High trans-1,4-polybutadiene and catalyst and process for preparing crystalline high trans-1,4-poly-butadiene 失效
标题翻译：高反式1,4-聚丁二烯及其催化剂及制备结晶高反式1,4-聚丁二烯的方法
公开(公告)号：US5596053A
公开(公告)日：1997-01-21
申请号：US455772
申请日：1995-05-31
申请人： Jung W. Kang , Jason T. Poulton
发明人： Jung W. Kang , Jason T. Poulton
IPC分类号： C08F4/70 , C08F136/06
CPC分类号： C08F4/7098 , C08F136/06
摘要： Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 50.degree. C. and 70.degree. C. to 130.degree. C. are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated nickel oxy borate compound; (b) an orKanoaluminum compound; (c) a triaryloxy phosphorus compound and (d) a carboxylic acid preferably a fluorinated carboxylic acid. The resultant polymers are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.
摘要翻译：具有高反式-1,4-加成含量的二烯聚合物和30℃至50℃和70℃至130℃范围内的两个不同的熔点通过聚合1,3-二二烯单体在烃溶剂中，在催化剂组合物存在下，包含（a）羧化的含硼酸镍化合物; （b）一种或二种铝化合物; （c）三芳氧基磷化合物和（d）羧酸，优选氟化羧酸。所得到的聚合物可用作轮胎橡胶的添加剂，以通过降低化合物门尼粘度和降低各种化合物料的收缩来提高加工性能。

70. 发明授权

US5548045A Process for producing polybutadiene 失效
标题翻译：生产聚丁二烯的方法
公开(公告)号：US5548045A
公开(公告)日：1996-08-20
申请号：US302958
申请日：1994-09-12
申请人： Kohei Goto , Iwakazu Hattori , Shoji Ogasahara , Masahiro Shibata , Yoshiyuki Michino , Kazuo Soga , Takeshi Shiono
发明人： Kohei Goto , Iwakazu Hattori , Shoji Ogasahara , Masahiro Shibata , Yoshiyuki Michino , Kazuo Soga , Takeshi Shiono
IPC分类号： C08F4/60 , C08F4/70 , C08F36/06 , C08F136/06
CPC分类号： C08F136/06
摘要： A process for producing a polybutadiene, which comprises polymerizing 1,3-butadiene in an inert organic solvent with a catalyst comprising (A) a cobalt compound, (B) an organoaluminum compound consisting essentially of an aluminoxane and, if necessary, (C) a tertiary phosphine compound, (D) at least one compound selected from the group consisting of an ester compound, an alcohol compound, a phenolic compound, a sulfoxide compound, a nitrogen-containing heterocyclic compound, water and a tertiary amine compound and (E) at least one compound selected from the group consisting of carbon disulfide, a xanthogen compound and a thioisocyanide. By this process, there can be produced, as desired, a cis-1,4-polybutadiene, a 1,2-polybutadiene having a desired vinyl content, a crystalline 1,2-polybutadiene or a polybutadiene containing crystalline 1,2-polybutadiene segments.
摘要翻译：一种生产聚丁二烯的方法，其包括在惰性有机溶剂中使用包含（A）钴化合物的催化剂聚合1,3-丁二烯，（B）主要由铝氧烷组成的有机铝化合物，如果需要，（C）叔膦化合物，（D）至少一种选自酯化合物，醇化合物，酚类化合物，亚砜化合物，含氮杂环化合物，水和叔胺化合物的化合物和（E ）至少一种选自二硫化碳，黄原酸化合物和硫代茜素的化合物。通过该方法，可以根据需要制备顺式-1,4-聚丁二烯，具有所需乙烯基含量的1,2-聚丁二烯，结晶1,2-聚丁二烯或含有结晶1,2-聚丁二烯的聚丁二烯细分。

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