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公开(公告)号：US06627715B2
公开(公告)日：2003-09-30
申请号：US10124006
申请日：2002-04-17
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas , John Robert Zuppo, III , Laurie Elizabeth Austin
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas , John Robert Zuppo, III , Laurie Elizabeth Austin
IPC分类号： C08F450
CPC分类号： B01J31/143 , B01J31/0212 , B01J31/04 , B01J31/122 , B01J31/128 , B01J31/14 , C08F36/04 , C08F297/04 , C08F297/06 , C08F4/52 , C08F4/44 , C08F4/54
摘要： The group IIa metal containing catalyst system of this invention can be utilized to synthesize rubbery polymers having a high trans microstructure by solution polymerization. Such rubbery polymers having a high trans microstructure content, such as polybutadiene rubber, styrene-isoprene-butadiene rubber, styrene-butadiene rubber, can be utilized in tire tread rubbers that exhibit improved wear and tear characteristics. This invention more specifically reveals a catalyst system which is comprised of (a) an organolithium compound, including organolithium functionalized compounds, (b) a group IIa metal salt selected from the group consisting of group IIa metal salts of di(alkylene glycol)alkylethers and group IIa metal salts of tri(alkylene glycol) alkylethers, and (c) an organoaluminum compound, and optionally an organomagnesium compound. The subject invention further discloses a process for synthesizing rubbery polymers having a high trans microstructure by a process that comprises polymerizing a conjugated diolefin monomer in an organic solvent in the presence of a catalyst system that is comprised of (a) an organolithium compound, (b) a group IIa metal salt selected from the group consisting of group IIa metal salts of amino glycols and group IIa metal salts of glycol ethers, and (c) an organoaluminum compound.
摘要翻译： 本发明的含IIa族金属的催化剂体系可用于通过溶液聚合合成具有高反相微观结构的橡胶状聚合物。 具有高反式显微组织含量的这种橡胶状聚合物，例如聚丁二烯橡胶，苯乙烯 - 异戊二烯 - 丁二烯橡胶，苯乙烯 - 丁二烯橡胶，可用于表现出改善的磨损和撕裂特性的轮胎胎面橡胶。 本发明更具体地揭示了一种催化剂体系，其包括（a）有机锂化合物，包括有机锂官能化化合物，（b）选自二（亚烷基二醇）烷基醚的IIa族金属盐和 三（亚烷基二醇）烷基醚的IIa族金属盐，和（c）有机铝化合物和任选的有机镁化合物。 本发明还公开了一种通过包括在（a）有机锂化合物（b）的催化剂体系存在下在有机溶剂中聚合共轭二烯烃单体的方法来合成具有高反向显微组织的橡胶状聚合物的方法， ）选自IIa族氨基二醇金属盐和IIa族二醇醚金属盐的IIa族金属盐，和（c）有机铝化合物。
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公开(公告)号：US07321017B1
公开(公告)日：2008-01-22
申请号：US11466920
申请日：2006-08-24
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas , John Robert Zuppo, III , Lauire Elizabeth Austin
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas , John Robert Zuppo, III , Lauire Elizabeth Austin
CPC分类号： C08F36/04 , B60C1/0016 , C08F4/52 , C08F4/50
摘要： The present invention is directed to an amine containing catalyst system for synthesizing rubbery polymers, such as polybutadiene rubber and styrene-butadiene rubber, having a high trans microstructure. The catalyst system, in one embodiment, includes (a) an organolithium compound, (b) a group IIa metal salt, (c) an organoaluminum compound, and (d) an amine compound which can be selected from (1) a heterocyclic aromatic compound which includes a ring structure with one or more nitrogen atoms as part of the ring; (2) a heterocyclic non-aromatic compound which includes a ring structure with two or more nitrogen atoms as part of the ring; (3) an aromatic compound including a ring structure substituted with at least one amine and at least one polar functionality containing group selected from a carboxyl group or a hydroxyl group; (4) a bicyclic chelating diamine compound; or (5) an aliphatic amine which includes a C5-C20 alkyl group.
摘要翻译： 本发明涉及一种用于合成橡胶状聚合物的胺类催化剂体系，如聚丁二烯橡胶和苯乙烯 - 丁二烯橡胶，具有高的反相微观结构。 在一个实施方案中，催化剂体系包括（a）有机锂化合物，（b）IIa族金属盐，（c）有机铝化合物和（d）胺化合物，其可以选自（1）杂环芳族 化合物，其包含具有一个或多个氮原子作为环的一部分的环结构; （2）包含具有两个以上氮原子的环结构作为环的一部分的杂环非芳族化合物; （3）包含被至少一个胺和至少一个选自羧基或羟基的极性官能团的基团取代的环结构的芳族化合物; （4）双环螯合二胺化合物; 或（5）包含C 5 -C 20烷基的脂族胺。
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公开(公告)号：US06583244B1
公开(公告)日：2003-06-24
申请号：US09999854
申请日：2001-10-31
IPC分类号： C08F446
摘要： Metal salts of cyclic alcohols can be used as modifiers in lithium initiated solution polymerizations of diene monomers into rubbery polymers having a low vinyl content. For instance, such initiator systems can be used in the copolymerization of styrene and isoprene to produce low vinyl styrene-isoprene rubber having a random distribution of repeat units that are derived from styrene. It is important for such polymerizations to be conducted in the absence of polar modifiers, such as Lewis bases. The subject invention more specifically discloses an initiator system which is comprised of (a) a lithium initiator and (b) a metal salt of a cyclic alcohol, wherein said initiator system is void of polar modifiers. The present invention also discloses a process for preparing a rubbery polymer having a low vinyl content which comprises: polymerizing at least one diene monomer with a lithium initiator at a temperature which is within the range of about 5° C. to about 100° C. in the presence of a metal salt of a cyclic alcohol, wherein the molar ratio of the metal salt of the cyclic alcohol to the lithium initiator is within the range of about 0.05:1 to about 10:1, and wherein the process is conducted in the absence of polar modifiers.
摘要翻译： 环醇的金属盐可以用作二烯单体的锂引发溶液聚合成具有低乙烯基含量的橡胶状聚合物中的改性剂。 例如，这种引发剂体系可以用于苯乙烯和异戊二烯的共聚合以制备具有衍生自苯乙烯的重复单元的随机分布的低乙烯基苯乙烯 - 异戊二烯橡胶。 在没有极性改性剂如路易斯碱的情况下进行这种聚合是重要的。 本发明更具体地公开了一种引发剂体系，其包括（a）锂引发剂和（b）环状醇的金属盐，其中所述引发剂体系没有极性改性剂。 本发明还公开了一种制备低乙烯基含量的橡胶状聚合物的方法，该方法包括：在约5℃至约100℃范围内的温度下，用锂引发剂聚合至少一种二烯单体。 在环醇的金属盐的存在下，其中环醇与锂引发剂的金属盐的摩尔比在约0.05:1至约10:1的范围内，并且其中所述方法在 没有极性改性剂。
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公开(公告)号：US06576728B1
公开(公告)日：2003-06-10
申请号：US10000738
申请日：2001-10-31
IPC分类号： C08F456
CPC分类号： C08F236/10 , C08F4/48
摘要： This invention is based upon the discovery of certain anionic initiator systems can be used to initiate the solution polymerization of conjugated diolefin monomers into rubbery polymers having a low vinyl content. For instance, such initiator systems can be used in the copolymerization of styrene and isoprene to produce low vinyl styrene-isoprene rubber having a random distribution of repeat units that are derived from styrene. These initiator systems are comprised of (a) a lithium initiator and (b) a member selected from the group consisting of (1) a sodium alkoxide, (2) a sodium salt of a sulfonic acid, and (3) a sodium salt of a glycol ether. It is important for the initiator system to be free of polar modifiers, such as Lewis bases. The subject invention more specifically discloses an initiator system which is comprised of (a) a lithium initiator and (b) a member selected from the group consisting of (1) a sodium alkoxide, (2) a sodium salt of a sulfonic acid, and (3) a sodium salt of a glycol ether, wherein said initiator system is void of polar modifiers. The present invention also discloses a process for preparing a rubbery polymer having a low vinyl content which comprises: polymerizing at least one diene monomer with a lithium initiator at a temperature which is within the range of about 5° C. to about 180° C. in the presence of a member selected from the group consisting of (1) a sodium alkoxide, (2) a sodium salt of a sulfonic acid, and (3) a sodium salt of a glycol ether, and wherein the process is conducted in the absence of polar modifiers.
摘要翻译： 本发明基于某些阴离子引发剂体系的发现，可用于引发共轭二烯烃单体溶液聚合成具有低乙烯基含量的橡胶状聚合物。 例如，这种引发剂体系可以用于苯乙烯和异戊二烯的共聚合以制备具有衍生自苯乙烯的重复单元的随机分布的低乙烯基苯乙烯 - 异戊二烯橡胶。 这些引发剂体系包括（a）锂引发剂和（b）选自（1）醇钠，（2）磺酸钠盐和（3）钠盐的钠盐 乙二醇醚。 引发剂体系不含极性改性剂如路易斯碱是重要的。 本发明更具体地公开了一种引发剂体系，其包括（a）锂引发剂和（b）选自（1）烷醇钠，（2）磺酸钠盐和 （3）二醇醚的钠盐，其中所述引发剂体系没有极性改性剂。 本发明还公开了一种制备低乙烯基含量的橡胶状聚合物的方法，该方法包括：在约5℃至约180℃的温度范围内使锂引发剂聚合至少一种二烯单体。 在选自（1）烷氧基钠，（2）磺酸钠盐和（3）二醇醚的钠盐中的成员的存在下，其中所述方法在 没有极性改性剂。
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5.发明授权Rubbery block polymers containing polylactone and rubber compounds including the same 失效含有聚内酯和包含它们的橡胶化合物的橡胶嵌段聚合物公开(公告)号：US07662883B2
公开(公告)日：2010-02-16
申请号：US11617342
申请日：2006-12-28
CPC分类号： C08F297/04 , C08F297/044 , C08K3/36 , C08K5/548 , C08L53/02 , Y10S152/905 , C08L2666/02 , C08L2666/14
摘要： The present invention is directed to rubbery block polymers containing a polylactone, such as polycaprolactone, methods of making the same, and to rubber compounds containing those block polymers. The rubbery block polymer is an anionically polymerized block polymer defined by A-B, wherein A includes at least one type of polymerized conjugated diene monomer, a polymerized vinyl aromatic monomer, or a mixture thereof and wherein B is a polylactone, such as polycaprolactone, which is hydroxy terminated. The rubbery block polymer may be compounded so to provide, for example, a tire tread with desirable properties for use in an automobile tire. Such rubber compound, for example, can include the rubbery block polymer, an organosilane coupling agent, such as a bis(trialkoxysilyl) alkane, bis(trialkoxysilylalkyl) polysulfide, or mixtures thereof, and silica filler in specified amounts.
摘要翻译： 本发明涉及含有聚内酯如聚己酸内酯的橡胶嵌段聚合物，其制备方法以及含有这些嵌段聚合物的橡胶化合物。 橡胶嵌段聚合物是由AB定义的阴离子聚合的嵌段聚合物，其中A包括至少一种聚合的共轭二烯单体，聚合的乙烯基芳族单体或其混合物，其中B是聚内酯，例如聚己内酯， 羟基封端。 可以将橡胶状嵌段聚合物复合以提供例如具有用于汽车轮胎的期望性能的轮胎胎面。 例如，这种橡胶化合物可以包括橡胶嵌段聚合物，有机硅烷偶联剂，例如双（三烷氧基甲硅烷基）烷烃，双（三烷氧基甲硅烷基烷基）多硫化物或其混合物，以及指定量的二氧化硅填料。
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公开(公告)号：US06359088B1
公开(公告)日：2002-03-19
申请号：US09389507
申请日：1999-09-03
IPC分类号： C08F800
CPC分类号： C08F136/08 , C08F236/10 , C08F4/54
摘要： The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in isothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. An amine can also be added to the catalyst system to increase the molecular weight (Mooney viscosity) of the rubber.
摘要翻译： 本发明的方法和催化剂体系可用于通过溶液聚合合成具有高反式含量的高度无规的苯乙烯 - 丁二烯橡胶。 通过本发明方法制备的苯乙烯 - 丁二烯橡胶可用于表现出改善的磨损特性的轮胎胎面橡胶。 本发明更具体地揭示了用于等温聚合的催化剂体系，其基本上由（a）有机锂化合物，（b）醇盐和（c）醇锂组成。 本发明还公开了一种合成具有低乙烯基含量的无规苯乙烯 - 丁二烯橡胶的方法，该方法包括在等温条件下在有机溶剂中在催化剂体系存在下共聚苯乙烯和1,3-丁二烯的方法，所述催化剂体系基本上组成 （a）有机锂化合物，（b）烷氧基钙和（c）醇锂。 还可以向催化剂体系中加入胺以提高橡胶的分子量（门尼粘度）。
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公开(公告)号：US07825202B2
公开(公告)日：2010-11-02
申请号：US12248601
申请日：2008-10-09
申请人： John Robert Zuppo, III , Adel Farhan Halasa , Wen-Liang Hsu , Leh-Yeh Hsu, legal representative
CPC分类号： B60C1/0016 , C08F36/06 , C08F4/52
摘要： The present invention is directed to a catalyst system for synthesizing rubbery polymers, such as styrene-butadiene rubber, that can be utilized in tire tread rubbers. The catalyst system, in one embodiment, includes an organolithium compound and a potassium alkyl borohydride or potassium alkyl aluminum hydride defined by: (R)3A−(H)K+, wherein A is boron or aluminum, H is hydrogen, K is potassium, and R, which is the same or different, is either H, a C1-C10 alkyl, a C3-C10 cycloalkyl, phenyl, or phenyl substituted C1-C10 alkyl, or a C3-C10 cycloalkyl, with the proviso that at least one R is a C1-C10 alkyl, and further wherein any two R's may optionally be part of a carbocyclic ring. The rubbery polymers can have low to medium vinyl microstructure content, i.e., from about 10% to about 40%, and are useful in tire tread rubber compounds which can exhibit improved wear and tear characteristics.
摘要翻译： 本发明涉及可用于轮胎胎面橡胶中的用于合成橡胶状聚合物如丁苯橡胶的催化剂体系。 催化剂体系在一个实施方案中包括有机锂化合物和烷基硼氢化钾或烷基氢化铝钾，其定义为：（R）3A-（H）K +，其中A是硼或铝，H是氢，K是钾， 和R相同或不同，为H，C 1 -C 10烷基，C 3 -C 10环烷基，苯基或苯基取代的C 1 -C 10烷基或C 3 -C 10环烷基，条件是至少一个 R是C 1 -C 10烷基，并且其中任何两个R可以任选地是碳环的一部分。 橡胶状聚合物可以具有低至中等乙烯基微结构含量，即约10％至约40％，并且可用于可显示改善的磨损和撕裂特性的轮胎胎面橡胶化合物。
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公开(公告)号：US07087549B2
公开(公告)日：2006-08-08
申请号：US11106813
申请日：2005-04-15
IPC分类号： B01J31/00
CPC分类号： C08F136/08 , C08F236/10 , C08F4/54
摘要： This invention reveals a catalyst system for use in isothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. An amine can also be added to the catalyst system to increase the molecular weight (Mooney viscosity) of the rubber.
摘要翻译： 本发明揭示了用于等温聚合的催化剂体系，其基本上由（a）有机锂化合物，（b）醇盐和（c）醇锂组成。 本发明还公开了一种合成具有低乙烯基含量的无规苯乙烯 - 丁二烯橡胶的方法，该方法包括在等温条件下在有机溶剂中在催化剂体系存在下共聚苯乙烯和1,3-丁二烯的方法，所述催化剂体系基本上组成 （a）有机锂化合物，（b）烷氧基钙和（c）醇锂。 还可以向催化剂体系中加入胺以提高橡胶的分子量（门尼粘度）。
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公开(公告)号：US20100093960A1
公开(公告)日：2010-04-15
申请号：US12248601
申请日：2008-10-09
CPC分类号： B60C1/0016 , C08F36/06 , C08F4/52
摘要： The present invention is directed to a catalyst system for synthesizing rubbery polymers, such as styrene-butadiene rubber, that can be utilized in tire tread rubbers. The catalyst system, in one embodiment, includes an organolithium compound and a potassium alkyl borohydride or potassium alkyl aluminum hydride defined by: (R)3A−(H)K+, wherein A is boron or aluminum, H is hydrogen, K is potassium, and R, which is the same or different, is either H, a C1-C10 alkyl, a C3-C10 cycloalkyl, phenyl, or phenyl substituted C1-C10 alkyl, or a C3-C10 cycloalkyl, with the proviso that at least one R is a C1-C10 alkyl, and further wherein any two R's may optionally be part of a carbocyclic ring. The rubbery polymers can have low to medium vinyl microstructure content, i.e., from about 10% to about 40%, and are useful in tire tread rubber compounds which can exhibit improved wear and tear characteristics.
摘要翻译： 本发明涉及可用于轮胎胎面橡胶中的用于合成橡胶状聚合物如丁苯橡胶的催化剂体系。 催化剂体系在一个实施方案中包括有机锂化合物和烷基硼氢化钾或烷基氢化铝钾，其定义为：（R）3A-（H）K +，其中A是硼或铝，H是氢，K是钾， 和R相同或不同，为H，C 1 -C 10烷基，C 3 -C 10环烷基，苯基或苯基取代的C 1 -C 10烷基或C 3 -C 10环烷基，条件是至少一个 R是C 1 -C 10烷基，并且其中任何两个R可以任选地是碳环的一部分。 橡胶状聚合物可以具有低至中等乙烯基微结构含量，即约10％至约40％，并且可用于可显示改善的磨损和撕裂特性的轮胎胎面橡胶化合物。
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10.发明授权Pneumatic tire having a component containing high trans styrene-isoprene-butadiene rubber 失效具有含有高反式苯乙烯 - 异戊二烯 - 丁二烯橡胶的组分的气动轮胎公开(公告)号：US06686420B1
公开(公告)日：2004-02-03
申请号：US10324438
申请日：2002-12-19
IPC分类号： C08F23610
CPC分类号： C08L9/06 , C08L21/00 , C08L2666/08
摘要： The invention is directed to a pneumatic tire having at least one component comprising a vulcanizable rubber composition, wherein the vulcanizable rubber composition comprises, based on 100 parts by weight of elastomer (phr), from about 30 to 100 phr of high trans random SIBR, and from about zero to about 70 phr of at least one additional elastomer, wherein the high trans random SIBR comprises from about 3 to about 30 percent by weight of styrene.
摘要翻译： 本发明涉及具有至少一种包含可硫化橡胶组合物的组分的充气轮胎，其中所述可硫化橡胶组合物基于100重量份的弹性体（phr），约30至100phr的高反式随机SIBR， 和约0至约70phr的至少一种另外的弹性体，其中高反式随机SIBR包含约3至约30重量％的苯乙烯。
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