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1. 发明授权

US07884168B2 Heterogeneous rubbery polymers having random, tapered, and block portions therein and methods of making same 有权
标题翻译：具有随机，锥形和嵌段部分的非均相橡胶状聚合物及其制备方法
公开(公告)号：US07884168B2
公开(公告)日：2011-02-08
申请号：US12371122
申请日：2009-02-13
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Leh-Yeh Hsu, legal representative , Warren James Busch , David Michael Smith, Sr. , Jennifer Elizabeth Labbe , Scott Edwards Johnson
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Warren James Busch , David Michael Smith, Sr. , Jennifer Elizabeth Labbe , Scott Edwards Johnson
IPC分类号： C08F236/10 , C08F2/04 , C08F4/48
CPC分类号： B60C1/0016 , C08F212/08 , C08F236/10 , Y10S152/905 , C08F2/001
摘要： A heterogeneous rubbery polymer is provided that includes a polymer chain derived from a vinyl aromatic monomer and a conjugated diolefin monomer, wherein from greater than 20 weight percent to about 40 weight percent of units in the rubbery polymer are derived from the vinyl aromatic monomer and from about 60 weight percent to about 80 weight percent of units in the rubbery polymer are derived from the conjugated diolefin monomer. The polymer chain is further characterized by having greater than zero and less than about 30 weight percent of the vinyl aromatic units in sequences containing 1 vinyl aromatic unit, from about 5 weight percent to about 20 weight percent of the vinyl aromatic units in sequences containing 5 to 8 vinyl aromatic units, and greater than zero and less than about 5 weight percent of the vinyl aromatic units in sequences containing 9 or more vinyl aromatic units.
摘要翻译：提供了一种异相橡胶状聚合物，其包括衍生自乙烯基芳族单体和共轭二烯烃单体的聚合物链，其中橡胶状聚合物中大于20重量％至约40重量％的单元衍生自乙烯基芳族单体和橡胶状聚合物中约60重量％至约80重量％的单元衍生自共轭二烯单体。聚合物链的特征还在于具有大于零且小于约30重量％的含有乙烯基芳族单元的乙烯基芳族单元，约5重量％至约20重量％的乙烯基芳族单元，其序列包含5 至8个乙烯基芳族单元，并且大于零且小于约5重量％的含有9个或更多个乙烯基芳族单元的乙烯基芳族单元。

2. 发明申请

US20100206443A1 Heterogeneous Rubbery Polymers Having Random, Tapered, and Block Portions Therein and Methods of Making Same 有权
标题翻译：具有随机，锥形和块状部分的异质橡胶聚合物及其制造方法
公开(公告)号：US20100206443A1
公开(公告)日：2010-08-19
申请号：US12371122
申请日：2009-02-13
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Leh-Yeh Hsu , Warren James Busch , David Michael Smith, SR. , Jennifer Elizabeth Labbe , Scott Edwards Johnson
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Leh-Yeh Hsu , Warren James Busch , David Michael Smith, SR. , Jennifer Elizabeth Labbe , Scott Edwards Johnson
IPC分类号： B60C11/00 , C08F112/08 , C08F2/00
CPC分类号： B60C1/0016 , C08F212/08 , C08F236/10 , Y10S152/905 , C08F2/001
摘要： A heterogeneous rubbery polymer is provided that includes a polymer chain derived from a vinyl aromatic monomer and a conjugated diolefin monomer, wherein from greater than 20 weight percent to about 40 weight percent of units in the rubbery polymer are derived from the vinyl aromatic monomer and from about 60 weight percent to about 80 weight percent of units in the rubbery polymer are derived from the conjugated diolefin monomer. The polymer chain is further characterized by having greater than zero and less than about 30 weight percent of the vinyl aromatic units in sequences containing 1 vinyl aromatic unit, from about 5 weight percent to about 20 weight percent of the vinyl aromatic units in sequences containing 5 to 8 vinyl aromatic units, and greater than zero and less than about 5 weight percent of the vinyl aromatic units in sequences containing 9 or more vinyl aromatic units.
摘要翻译：提供了一种异相橡胶状聚合物，其包括衍生自乙烯基芳族单体和共轭二烯烃单体的聚合物链，其中橡胶状聚合物中大于20重量％至约40重量％的单元衍生自乙烯基芳族单体和橡胶状聚合物中约60重量％至约80重量％的单元衍生自共轭二烯单体。聚合物链的特征还在于具有大于零且小于约30重量％的含有乙烯基芳族单元的乙烯基芳族单元，约5重量％至约20重量％的乙烯基芳族单元，其序列包含5 至8个乙烯基芳族单元，并且大于零且小于约5重量％的含有9个或更多个乙烯基芳族单元的乙烯基芳族单元。

3. 发明授权

US07064171B1 Non-random styrene-butadiene rubber 失效
标题翻译：无规丁苯橡胶
公开(公告)号：US07064171B1
公开(公告)日：2006-06-20
申请号：US11232685
申请日：2005-09-22
申请人： Adel Farhan Halasa , Wen-Liang Hsu , David Michael Smith, Sr. , Warren James Busch , John Joseph Andre Verthe , Scott Edwards Johnson
发明人： Adel Farhan Halasa , Wen-Liang Hsu , David Michael Smith, Sr. , Warren James Busch , John Joseph Andre Verthe , Scott Edwards Johnson
IPC分类号： C08F236/10
CPC分类号： C08L9/06 , B60C1/0016 , C08F236/10 , C08L7/00 , C08L9/00 , C08L97/005 , Y10S152/905 , C08L2666/02 , C08L2666/08
摘要： The present invention reveals a tire having a tread that is comprised of (1) 30 phr to 80 phr of a non-random styrene-butadiene rubber comprised of polymer chains that are derived from styrene and 1,3-butadiene, wherein from about 10 weight percent to about 50 weight percent of the repeat units in the styrene-butadiene rubber are derived from styrene, wherein from about 60 weight percent to about 90 weight percent of the repeat units in the styrene-butadiene rubber are derived from 1,3-butadiene, wherein from about 30 weight percent to about 50 weight percent of the styrene repeat units are in sequences containing 5 to 20 styrene repeat units, wherein the bound styrene content found in the first half of the polymer chains differs from the bound styrene content found in the second half of the polymer chains by at least 5 weight percent, wherein the styrene-butadiene rubber has a 1,2-vinyl content which is within the range of about 8 percent to about 20 percent, wherein the styrene-butadiene rubber has a number average molecular weight which is within the range of 200,000 to 475,000, and wherein the styrene-butadiene rubber has a glass transition temperature which is within the range of −82° C. to −50° C. and (2) 20 phr to 70 phr of polybutadiene. The tire tread formulation can optionally contain silica and lignin.
摘要翻译：本发明揭示了具有胎面的轮胎，该胎面由（1）30phr至80phr由衍生自苯乙烯和1,3-丁二烯的聚合物链组成的非无规丁苯橡胶组成，其中约10 苯乙烯 - 丁二烯橡胶中重复单元的重量百分比至约50重量％衍生自苯乙烯，其中苯乙烯 - 丁二烯橡胶中重复单元的约60重量％至约90重量％丁二烯，其中约30重量％至约50重量％的苯乙烯重复单元是含有5至20个苯乙烯重复单元的序列，其中在聚合物链的前半部分中发现的结合苯乙烯含量与发现的结合的苯乙烯含量不同在所述聚合物链的后半部分中至少5重量％，其中所述苯乙烯 - 丁二烯橡胶具有在约8％至约20％范围内的1,2-乙烯基含量，其中所述苯乙烯 - 丁二烯 iene橡胶的数均分子量在200,000至475,000的范围内，其中丁苯橡胶的玻璃化转变温度在-82℃至-50℃的范围内，（2 ）20phr至70phr的聚丁二烯。轮胎胎面配方可任选地含有二氧化硅和木质素。

4. 发明授权

US07825202B2 Potassium based catalyst systems for synthesizing rubbery polymers 有权
标题翻译：用于合成橡胶状聚合物的钾基催化剂体系
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
发明人： John Robert Zuppo, III , Adel Farhan Halasa , Wen-Liang Hsu
IPC分类号： C08F4/44 , C08F4/56 , C08F4/52 , B01J31/14
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。

5. 发明授权

US07714089B2 Functionalized monomers and functionalized rubbery polymers made therewith 有权
标题翻译：官能化单体和由其制备的官能化橡胶聚合物
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
发明人： Adel Farhan Halasa , Wen-Liang Hsu , 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。

6. 发明授权

US07943712B2 Catalyst system for synthesizing amine functionalized rubbery polymers having a high trans microstructure 有权
标题翻译：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
IPC分类号： C08F4/50 , C08F2/06 , C07F7/08
CPC分类号： C08F36/04 , C08F4/48 , C08F4/54
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。

7. 发明授权

US07906682B2 Synthesis of soluble functionalized lithium initiators 有权
标题翻译：可溶性官能化锂引发剂的合成
公开(公告)号：US07906682B2
公开(公告)日：2011-03-15
申请号：US12686768
申请日：2010-01-13
申请人： Adel Farhan Halasa , Wen-Liang Hsu
发明人： Adel Farhan Halasa , Wen-Liang Hsu
IPC分类号： C07C221/00 , C07C225/00 , C08F8/00 , C08F32/00 , C08F132/00 , C08F232/00
CPC分类号： B60C1/0016 , C07F1/005 , C07F1/02 , C08C19/44 , C08F36/04 , C08F4/488
摘要： This invention discloses a process for making dilithium initiators in high purity. This process can be conducted in the absence of amines which is desirable since amines can act as modifiers for anionic polymerizations. The dilithium compounds made are highly desirable because they are soluble in aromatic solvents. The present invention also discloses a tire which is comprised of a generally toroidal-shaped carcass with an outer circumferential tread, two spaced beads, at least one ply extending from bead to bead and sidewalls extending radially from and connecting said tread to said beads, wherein said tread is adapted to be ground-contacting, and wherein said tread is a cured the rubber formulation which is comprised of (a) at least one rubbery polymer containing functional groups of the structural formula: wherein R, R′ and R″ can be the same or different, wherein R is selected from the group consisting of hydrogen atoms, alkyl groups, aryl groups, alkaryl groups, and amino aryl groups, and wherein R′ and R″ represent alkyl groups alkyl groups that contain from 1 to 8 carbon atoms, and (b) at least one member selected from the group consisting of carbon black and silica.
摘要翻译：本发明公开了一种制备高纯度二锂引发剂的方法。该方法可以在不存在胺的情况下进行，因为胺可以用作阴离子聚合的改性剂。所制备的二锂化合物是非常需要的，因为它们可溶于芳族溶剂。本发明还公开了一种轮胎，其包括具有外圆周胎面的大致环形胎体，两个间隔开的胎圈，从胎圈到胎圈延伸的至少一个帘布层和从所述胎面径向延伸并将所述胎面连接到所述胎圈的侧壁，其中所述胎面适于与地面接触，并且其中所述胎面是固化的橡胶配方，其由（a）至少一种含有以下结构式的官能团的橡胶状聚合物组成：其中R，R'和R“可以是相同或不同，其中R选自氢原子，烷基，芳基，烷芳基和氨基芳基，其中R'和R“表示含有1至8个碳的烷基基团原子，和（b）选自碳黑和二氧化硅中的至少一种。

8. 发明授权

US07612147B2 Dendrimers of rubbery polymers 失效
标题翻译：橡胶聚合物的树枝状聚合物
公开(公告)号：US07612147B2
公开(公告)日：2009-11-03
申请号：US11176457
申请日：2005-07-07
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Chad Aaron Jasiunas
IPC分类号： C08C19/25 , C08F8/18 , C08F36/04 , C08J3/24
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。

9. 发明申请

US20080161519A1 Catalyst System for Synthesizing Amine Functionalized Rubbery Polymers 有权
标题翻译：用于合成胺官能化橡胶聚合物的催化剂体系
公开(公告)号：US20080161519A1
公开(公告)日：2008-07-03
申请号：US11616986
申请日：2006-12-28
申请人： Adel Farhan Halasa , Wen-Liang Hsu
发明人： Adel Farhan Halasa , Wen-Liang Hsu
IPC分类号： C08F2/00
CPC分类号： C08F36/04 , C08F4/48 , C08F4/54
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 or high vinyl microstructure. The catalyst system, in one embodiment, includes an organolithium amine compound, and one or more of (a) a group IIa metal salt of an amino glycol or a glycol ether, (b) an organoaluminum compound, or (c) 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：本发明涉及用于合成胺官能化并具有高反式或高乙烯基显微组织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，催化剂体系包括有机锂化合物和（a）氨基二醇或二醇醚的IIa族金属盐，（b）有机铝化合物或（c）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。

10. 发明授权

US07222650B2 Tire with a tread comprising a rubbery polymer of a functionalized monomer 有权
标题翻译：具有包含官能化单体的橡胶状聚合物的胎面的轮胎
公开(公告)号：US07222650B2
公开(公告)日：2007-05-29
申请号：US10429382
申请日：2003-05-05
申请人： Adel Farhan Halasa , Wen-Liang Hsu , Kenneth Allen Bates , Shingo Futamura
发明人： Adel Farhan Halasa , Wen-Liang Hsu , Kenneth Allen Bates , Shingo Futamura
IPC分类号： B60C1/00 , C08F26/06
CPC分类号： B60C1/0016 , C08K3/013 , Y10S152/905 , C08L19/006
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 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，所述仲胺具有选自下组的结构式：其中R和R' 可以相同或不同，表示含有1至约10个碳原子的烯丙基，烷氧基或烷基，其中X表示卤素原子，其中m表示4至约10的整数，并且其中X表示卤素原子 ; 和（2）使含有乙烯基卤的仲胺与乙烯基卤化镁反应以制备具有结构的单体，其中R和R'可以相同或不同并且表示含有1至约10个碳原子的烷基，烯丙基或烷氧基，并且其中m表示约4至约10的整数。

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