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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：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：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Catalyst system for synthesizing amine functionalized rubbery polymers having a high trans microstructure 有权用于合成具有高反向显微组织的胺官能化橡胶状聚合物的催化剂体系公开(公告)号：US07943712B2
公开(公告)日：2011-05-17
申请号：US11617361
申请日：2006-12-28
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Laurie Elizabeth Austin , Chad Aaron Jasiunas , Steven Kristofer Henning
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Laurie Elizabeth Austin , Chad Aaron Jasiunas , Steven Kristofer Henning
摘要： The present invention is directed to a catalyst system for synthesizing rubbery polymers, such as polybutadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, or styrene-isoprene-butadiene rubber, that are amine functionalized and have a high trans microstructure. The catalyst system, in one embodiment, includes (a) an organolithium amine compound, (b) a group IIa metal salt of an amino glycol or a glycol ether, (c) an organoaluminum compound, and optionally (d) an amine compound. The amine functionalized rubbery polymers can be utilized in tire tread rubbers where the rubbery polymers may provide desirable wear properties without substantially sacrificing other performance characteristic(s), e.g., traction properties.
摘要翻译： 本发明涉及一种用于合成胺官能化并具有高反相微观结构的橡胶状聚合物如聚丁二烯橡胶，苯乙烯 - 丁二烯橡胶，异戊二烯 - 丁二烯橡胶或苯乙烯 - 异戊二烯 - 丁二烯橡胶的催化剂体系。 在一个实施方案中，催化剂体系包括（a）有机锂胺化合物，（b）氨基二醇或二醇醚的IIa族金属盐，（c）有机铝化合物和任选的（d）胺化合物。 胺官能化橡胶状聚合物可用于轮胎胎面橡胶中，其中橡胶状聚合物可提供期望的耐磨性，而基本上不会牺牲其它性能特征，例如牵引性能。
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6.发明授权公开(公告)号：US07714089B2
公开(公告)日：2010-05-11
申请号：US11955453
申请日：2007-12-13
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Leh-Yeh Hsu, legal representative , Shingo Futamura , Joe Zhou , Chad Aaron Jasiunas
IPC分类号： C08F236/14 , C08F226/06 , C08F230/02 , C07C323/25 , C07F7/10 , C08F2/22
CPC分类号： C08F236/14 , C07C323/25 , C07F7/1804 , C07F9/5004 , C07F9/5031 , C08L19/006
摘要： Rubbery polymers can be formed having the general formula: R1R2N—(CH2)n—X—CH2—CHR3R4 wherein R1 and R2 are independently selected from a group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, aryls, phenyls, heterocycles, acyls, and silanes, or R1 in combination with R2 forms a heterocyclic ring; n is an integer from 1 to 20; X is selected from a group consisting of sulfur, a phosphorus moiety, and a silicon moiety; R3 and R4 are one of hydrogen, alkyls, alkenyls, and at least one of which includes reactive unsaturation such as an alkenyl group. Moreover, this invention discloses a process of making functionalized rubbery polymers from the functionalized monomers.
摘要翻译： 可以形成具有以下通式的橡胶状聚合物：R1R2N-（CH2）n-X-CH2-CHR3R4，其中R1和R2独立地选自烷基，环烷基，烯基，环烯基，芳基，苯基，杂环，酰基， 和硅烷，或R 1与R 2组合形成杂环; n为1〜20的整数， X选自硫，磷部分和硅部分; R3和R4是氢，烷基，烯基之一，并且其中至少一个包括反应性不饱和键如烯基。 此外，本发明公开了一种由官能化单体制备官能化橡胶聚合物的方法。
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公开(公告)号：US07612147B2
公开(公告)日：2009-11-03
申请号：US11176457
申请日：2005-07-07
CPC分类号： C08C19/44 , B60C1/0016 , C08G83/003 , C08L15/00 , C08L101/005 , Y10T152/10 , Y10T152/10495
摘要： This invention discloses a process for synthesizing a dendrimer of a rubbery polymer comprising: (a) reacting a lithium terminated rubbery polymer with a halogenated silicon containing compound to produce a polymer which is terminated with halogenated silicon moieties, wherein the halogenated silicon contain compound has at least four halogen atoms which are bonded directly to silicon atoms, wherein the ratio of the lithium terminated rubbery polymer to halogen atoms in the halogenated silicon containing compound is within the range of 2:n to (n−1):n, wherein n represents the number of halogen atoms that are bonded directly to silicon atoms in the halogenated silicon containing compound, wherein the halogenated silicon containing compound contains at least three halogen atoms which are bonded directly to a silicon atom; (b) reacting the polymer which is terminated with halogenated silicon moieties with a molar excess of a tertiary alcohol to produce a polymer which is terminated with hydroxy silyl moieties; and (c) allowing the polymer which is terminated with the hydroxy silyl moieties to couple under conditions sufficient to produce a dendrimer containing siloxane linkages. It has also be found that similar dendrimers having improved processability can be make utilizing halogenated tin containing compounds in stead of the halogenated silicon containing compound.
摘要翻译： 本发明公开了一种用于合成橡胶状聚合物树枝状聚合物的方法，其包括：（a）使锂封端的橡胶状聚合物与含卤化硅的化合物反应以制备用卤化硅部分封端的聚合物，其中卤化硅含有化合物在 至少四个与硅原子直接键合的卤素原子，其中锂封端的橡胶状聚合物与含卤化硅化合物中的卤素原子的比例在2：n至（n-1）：n的范围内，其中n表示 与卤代硅化合物中的硅原子直接键合的卤素原子数，其中含卤化硅的化合物含有至少三个与硅原子直接键合的卤素原子; （b）将用卤代硅部分封端的聚合物与摩尔过量的叔醇反应，以产生用羟基甲硅烷基部分封端的聚合物; 和（c）使在羟基甲硅烷基部分封端的聚合物在足以产生含有硅氧烷键的树枝状聚合物的条件下偶联。 还可以发现，具有改进加工性能的类似树枝状大分子可以利用含卤化锡的化合物代替含卤化硅的化合物。
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公开(公告)号：US07189792B2
公开(公告)日：2007-03-13
申请号：US11311495
申请日：2005-12-19
摘要： The process and catalyst of this invention can be utilized to synthesize homo and copolymers of conjugated diene monomers and vinyl aromatic monomers having high trans contents of greater than 60% with low melting points. These homo and copolymers of conjugated diene monomers and vinyl aromatic monomers can be utilized in tire tread and sidewall rubbers that exhibit outstanding wear and tear characteristics in the tread and excellent flexing properties in the sidewall. The rubber polymers of this invention are made utilizing an improved catalyst system. This catalyst system is comprised of (a) organo aluminum compounds, (b) organo lithium compounds, (c) a barium compound selected from barium salts of (i) di(ethylene glycol) ethyl ether, (ii) di(ethylene glycol) propyl ether, (iii) di(ethylene glycol) hexyl ether, (iv) di(N,N-dimethyl amino glycol) ethyl ether, (v) menthol and thymol in the presence of polar modifier consisting of water, alcohols, amines, thiols, phosphates and phosphites. The trans polymers and copolymers of this invention made with the above catalyst system typically have a glass transition temperature ranging from −97° C. to −40° C., a melt temperature ranging from −30° C. to +30° C., and a number average molecular weight from 20,000 to 250,000. The inclusion of such polar modifiers in the barium catalyst system results in a high styrene content in copolymerization, a high trans content, and high molecular weight. Copolymers of conjugated diolefin monomers and vinyl aromatic monomers made with the catalyst system of this invention also have a tapered macrostructure.
摘要翻译： 本发明的方法和催化剂可用于合成共轭二烯单体和具有高反式含量大于60％的低熔点的乙烯基芳族单体的均聚物和共聚物。 共轭二烯单体和乙烯基芳族单体的这些均聚物和共聚物可以用于轮胎胎面和侧壁橡胶，其在胎面中表现出优异的耐磨性和优异的弯曲性能。 使用改进的催化剂体系制备本发明的橡胶聚合物。 该催化剂体系包括（a）有机铝化合物，（b）有机锂化合物，（c）选自（i）二（乙二醇）乙醚的钡盐，（ii）二（乙二醇） 丙基醚，（iii）二（乙二醇）己基醚，（iv）二（N，N-二甲基氨基乙二醇）乙醚，（v）薄荷醇和百里酚在由水，醇，胺， 硫醇，磷酸盐和亚磷酸盐。 用上述催化剂体系制备的本发明的反式聚合物和共聚物通常具有-97℃至-40℃的熔融温度范围为-30℃至+ 30℃的玻璃化转变温度。 ，数均分子量为20,000〜250,000。 在钡催化剂体系中包含这种极性改性剂导致共聚反应中苯乙烯含量高，反式含量高，分子量高。 用本发明的催化剂体系制得的共轭二烯烃单体和乙烯基芳族单体的共聚物也具有锥形宏观结构。
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公开(公告)号：US07153805B2
公开(公告)日：2006-12-26
申请号：US11240862
申请日：2005-09-30
IPC分类号： C08F4/52 , C08F236/06 , C08F236/08
CPC分类号： C08F36/04 , C08F136/06 , C08F136/08 , C08F4/58 , C08F4/545 , C08F236/06 , C08F236/08
摘要： The subject invention relates to a process for preparing a catalyst system that comprises the sequential steps of (I) reacting an organometalic compound that contains a metal from Group III-B of the Periodic System with an organoaluminum compound at a temperature which is within the range of 50° C. to 100° C. to produce an aluminum modified Group III-B metal containing catalyst component, and (II) mixing the aluminum modified Group III-B metal containing catalyst component with a halogen containing compound to produce the Group III-B metal containing catalyst system, wherein the catalyst system is void of compounds selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols, aliphatic thiols, cycloaliphatic thiols, trialkyl silanols, and triaryl silanols, wherein the organometalic compound that contains a metal from Group III-B of the Periodic System is reacted with the organoaluminum compound in the absence of conjugated diene monomers, and wherein the catalyst system is prepared in the absence of compounds that contain labile halogen atoms.
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公开(公告)号：US06995224B2
公开(公告)日：2006-02-07
申请号：US11043589
申请日：2005-01-26
IPC分类号： C08F126/06
CPC分类号： C08F236/14 , C08C19/44 , C08F236/10
摘要： This invention discloses a process for synthesizing an amine functionalized monomer that comprises (1) reacting a secondary amine with a 2,3-dihalopropene to produce a vinyl halide containing secondary amine having a structural formula selected from the group consisting of wherein R and R′ can be the same or different and represent allyl, alkoxyl or alkyl groups containing from 1 to about 10 carbon atoms, and wherein X represents a halogen atom, and wherein m represents an integer from 4 to about 10, and wherein X represents a halogen atom; and (2) reacting the vinyl halide containing secondary amine with a vinyl magnesium halide to produce the monomer having a structural formula wherein R and R′ can be the same or different and represent alkyl, allyl or alkoxyl groups containing from 1 to about 10 carbon atoms, and wherein m represents an integer from about 4 to about 10.
摘要翻译： 本发明公开了一种用于合成胺官能化单体的方法，其包括（1）使仲胺与2,3-二卤代丙烯反应以制备含有仲胺的乙烯基卤化物，所述仲胺具有选自以下的结构式：化学式id =“ CHEM-US-00001“num =”000
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