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1. 发明申请

US20050181935A1 Calcium-based catalyst system 失效
标题翻译：钙基催化剂体系
公开(公告)号：US20050181935A1
公开(公告)日：2005-08-18
申请号：US11106813
申请日：2005-04-15
申请人： Adel Halasa , Wen-Liang Hsu , John Zuppo
发明人： Adel Halasa , Wen-Liang Hsu , John Zuppo
IPC分类号： C08F136/08 , C08F236/10 , B01J31/00
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）。

2. 发明申请

US20070123631A1 Functionalized rubbery polymers 有权
标题翻译：官能化橡胶聚合物
公开(公告)号：US20070123631A1
公开(公告)日：2007-05-31
申请号：US11603719
申请日：2006-11-22
申请人： Adel Halasa , Wen-Liang Hsu , Jin-Ping Zhou , Teresa Martter
发明人： Adel Halasa , Wen-Liang Hsu , Jin-Ping Zhou , Teresa Martter
IPC分类号： C08K3/34
CPC分类号： C08F236/12 , B60C1/0016 , C07C211/27 , C07F7/10 , C08F212/08 , C08F212/14 , C08F236/10 , C08K3/36 , C08K5/548 , C08L21/00 , C08L97/00 , C08L15/00 , C08F236/06 , C08L2666/26
摘要： This invention discloses a process for the synthesis of a rubbery polymer by emulsion polymerization that comprised polymerizing (1) a conjugated diolefin monomer and (2) a functionalized monomer having the structural formula: wherein the R1 groups can be the same or different and represent hydrogen atoms or alkyl groups containing from 1 to about 8 carbon atoms, wherein R2 represents a hydrogen atom or an alkyl group containing from 1 to about 8 carbon atoms, wherein R3 represents a hydrogen atom or an alkyl group containing from 1 to about 8 carbon atoms, and wherein R4 represents a hydrogen atom or an alkyl group containing from 1 to about 8 carbon atoms, with the proviso that if R3 represent an alkyl group then R4 represents a hydrogen atom, and with the proviso that R4 represents an alkyl group then R3 represents a hydrogen atom, wherein said polymerization is conducted in an aqueous medium, and wherein said polymerization is initiated with a free radical initiator.
摘要翻译：本发明公开了一种通过乳液聚合合成橡胶状聚合物的方法，该方法包括聚合（1）共轭二烯单体和（2）具有以下结构式的官能化单体：其中R 1〜相同或不同，表示氢原子或含有1至约8个碳原子的烷基，其中R 2表示氢原子或含有1至约8个碳原子的烷基，其中R 代表氢原子或含有1至约8个碳原子的烷基，其中R 4表示氢原子或含有1至约8个碳原子的烷基碳原子，条件是如果R 3表示烷基，则R 4表示氢原子，条件是R 4' 表示烷基，则R 3表示氢原子，其中所述聚合在水性介质中进行， d，其中所述聚合由自由基引发剂引发。

3. 发明申请

US20070010629A1 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：US20070010629A1
公开(公告)日：2007-01-11
申请号：US11176457
申请日：2005-07-07
申请人： Adel Halasa , Wen-Liang Hsu , Chad Jasiunas
发明人： Adel Halasa , Wen-Liang Hsu , Chad Jasiunas
IPC分类号： C08F136/00
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，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，以产生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。

4. 发明申请

US20050272852A1 Natural rubber-rich composition and tire with tread thereof 审中-公开
标题翻译：天然橡胶丰富的组合物和具有胎面的轮胎
公开(公告)号：US20050272852A1
公开(公告)日：2005-12-08
申请号：US10859524
申请日：2004-06-02
申请人： Paul Sandstrom , Adel Halasa , Wen-Liang Hsu , John Verthe , Chad Jasiunas
发明人： Paul Sandstrom , Adel Halasa , Wen-Liang Hsu , John Verthe , Chad Jasiunas
IPC分类号： B60C1/00 , C08F4/56 , C08K3/04 , C08K3/36 , C08L7/00 , C08L9/06 , C08L21/00
CPC分类号： C08L7/00 , B60C1/0016 , C08K3/04 , C08K3/36 , C08L9/06 , C08L21/00 , C08L2666/02 , C08L2666/08
摘要： This invention relates to a natural rubber-rich rubber composition and tire with tread thereof. A partial replacement of the natural rubber in the natural rubber-rich tire tread is accomplished by an inclusion of a specialized trans 1,4-styrene/butadiene copolymer rubber characterized by having a combination of bound styrene content and microstructure limitations. The tire tread rubber composition is comprised of a blend of the specialized trans 1,4-styrene/butadiene rubber and cis 1,4-polyisoprene natural rubber optionally together with at least one additional diene-based elastomer in which the natural rubber remains a major portion of the elastomers in the tread rubber composition. A significant aspect of the invention is a partial replacement of natural cis 1,4-polyisoprene rubber in the tread rubber composition. The specialized trans 1,4-styrene/butadiene rubber has a bound styrene content in a range of from about 15 to about 35 percent and a microstructure of its polybutadiene portion composed of from about 50 to about 80 percent trans 1,4-isomeric units, from about 10 to about 20 percent cis 1,4-isomeric units and from about 2 to about 10 percent vinyl 1,2-isomeric units; preferably a Mooney (ML1+4) at 100° C. viscosity value in a range of from about 50 to about 100, alternately from about 50 to about 85, and preferably a glass transition temperature (Tg) in a range of from about −60° C. to about −90° C.
摘要翻译：本发明涉及一种富含天然橡胶的橡胶组合物和具有胎面的轮胎。天然橡胶丰富的轮胎胎面中天然橡胶的部分替代是通过包含特征在于具有结合苯乙烯含量和微结构限制的组合的专用反式1,4-苯乙烯/丁二烯共聚物橡胶来实现的。轮胎胎面橡胶组合物由专门的反式1,4-苯乙烯/丁二烯橡胶和顺式1,4-聚异戊二烯天然橡胶的混合物组成，任选与至少一种另外的二烯基弹性体共混，其中天然橡胶保持主要橡胶组合物中的部分弹性体。本发明的一个重要方面是在胎面橡胶组合物中部分替代天然顺式1,4-聚异戊二烯橡胶。专用的反式1,4-苯乙烯/丁二烯橡胶具有约15至约35％范围内的结合苯乙烯含量，其聚丁二烯部分的显微组织由约50至约80％的反式1,4-异构体单元，约10至约20％的顺式1,4-异构体单元和约2至约10％的乙烯基1,2-异构体单元; 优选为100℃时的门尼（ML1 + 4），粘度值为约50至约100，交替为约50至约85，优选玻璃化转变温度（Tg）为约 - 60℃至约-90℃

5. 发明申请

US20050020753A1 Light weight rubber composition containing clay 失效
标题翻译：轻质橡胶组合物含有粘土
公开(公告)号：US20050020753A1
公开(公告)日：2005-01-27
申请号：US10923071
申请日：2004-08-20
申请人： Manoj Ajbani , Wen-Liang Hsu , Adel Halasa , Ginger Lee , Eric Castner
发明人： Manoj Ajbani , Wen-Liang Hsu , Adel Halasa , Ginger Lee , Eric Castner
IPC分类号： B60C1/00 , C08K3/04 , C08K3/34 , C08K5/54 , C08K7/00 , C08K9/04 , C08L21/00 , C08F36/14
CPC分类号： C08K3/346 , C08K9/04 , Y10S152/905 , C08L19/006
摘要： This invention relates to 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; wherein the tread is comprised of: (1) an amino group containing rubbery polymer, wherein said amino group containing rubbery polymer contains from about 0.1 weight percent to about 20 weight percent monomer units containing an amino group, (2) from 0.1 to about 25 phr of an organophilic 2:1 layered silicate clay selected from the group consisting of montmorillonite clays, bentonite clays, hectorite clays, saponite clays, nontronite clays, beidellite clays, fluorohectorite clays, stevensite clays, volkonskoite clays, sauconite clays, and laponite clays, and (3) a silica coupling agent.
摘要翻译：本发明涉及一种轮胎，该轮胎由具有外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以及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构成; 其中所述胎面适于与地面接触; 其中所述胎面由以下组成：（1）含氨基的橡胶状聚合物，其中所述含氨基的橡胶状聚合物含有约0.1重量％至约20重量％的含有氨基的单体单元，（2）0.1至约25 选自蒙脱石粘土，膨润土，锂蒙脱石粘土，皂石粘土，白云石粘土，贝得石粘土，氟代锂蒙脱石粘土，硬石榴石粘土，膨润土，粘土，松节油粘土等亲水性2:1层状硅酸盐粘土，和（3）二氧化硅偶联剂。

6. 发明申请

US20060247360A1 Rubber composition containing an alkoxysilane coupled in-chain functionalized elastomer and tire with component thereof 有权
标题翻译：含有烷氧基硅烷的链烷基官能化弹性体和轮胎与其组分的橡胶组合物
公开(公告)号：US20060247360A1
公开(公告)日：2006-11-02
申请号：US11110025
申请日：2005-04-20
申请人： Adel Halasa , Wen-Liang Hsu , Kenneth Bates , David Benko , Shingo Futamura , Kuo-Chih Hua
发明人： Adel Halasa , Wen-Liang Hsu , Kenneth Bates , David Benko , Shingo Futamura , Kuo-Chih Hua
IPC分类号： B60C1/00
CPC分类号： B60C1/0016 , C08C19/25 , C08C19/44 , C08L15/00 , C08L19/006 , C08L21/00 , C08L2666/08
摘要： This invention relates to a precipitated silica reinforced conjugated diene-based elastomer composition containing an alkoxysilane coupled, in-chain functionalized, conjugated diene-based elastomer and to a tire having at least one component thereof. Said in-chain functionalized conjugated diene-based elastomer is a conjugated diene-based elastomer which contains a plurality of at least one of in-chain p- and m-(2-pyrrolidinoethyl) styrene (PES) and m-(2-pyrrolidino-1-methylethyl) alpha-methylstyrene (PAMS) groups.
摘要翻译：本发明涉及一种沉淀二氧化硅增强共轭二烯系弹性体组合物，其含有烷氧基硅烷偶联，链内官能化共轭二烯类弹性体和具有至少一种组分的轮胎。所述的链内官能化共轭二烯系弹性体是共轭二烯系弹性体，其含有多个至少一种链内对称和间 - （2-吡咯烷基乙基）苯乙烯（PES）和间 - （2-吡咯烷子基） -1-甲基乙基）α-甲基苯乙烯（PAMS）基团。

7. 发明申请

US20060074207A1 Synthetic polyisoprene rubber 有权
标题翻译：合成聚异戊二烯橡胶
公开(公告)号：US20060074207A1
公开(公告)日：2006-04-06
申请号：US11287562
申请日：2005-11-23
申请人： Adel Halasa , Wen-Liang Hsu , Aaron Ryba , Jin-Ping Zhou , Chad Jasiunas , Paul Sandstrom
发明人： Adel Halasa , Wen-Liang Hsu , Aaron Ryba , Jin-Ping Zhou , Chad Jasiunas , Paul Sandstrom
IPC分类号： C08F4/44
CPC分类号： B01J31/143 , B01J31/04 , B60C1/0016 , C08F36/04 , C08L9/00 , C08L21/00 , C08F4/545 , C08F4/44 , C08L2666/08
摘要： The neodymium catalyst system prepared by the technique of this invention can be used in the polymerization of isoprene monomer into synthetic polyisoprene rubber having an extremely high cis-microstructure content and high stereo regularity. This polyisoprene rubber will crystallize under strain and can be compounded into rubber formulations in a manner similar to natural rubber. This invention more specifically discloses a process for the synthesis of polyisoprene rubber which comprises polymerizing isoprene monomer in the presence of a neodymium catalyst system, wherein the neodymium catalyst system is prepared by a process that comprises (1) reacting a neodymium carboxylate with an organoaluminum compound in an organic solvent to produce neodymium-aluminum catalyst component, and (2) subsequently reacting the neodymium-aluminum catalyst component with an elemental halogen to produce the neodymium catalyst system, wherein the neodymium catalyst system is void of nickel-containing compounds.
摘要翻译：通过本发明技术制备的钕催化剂体系可用于将异戊二烯单体聚合成具有非常高的顺式微结构含量和高立体规律性的合成聚异戊二烯橡胶。该聚异戊二烯橡胶将在应变下结晶，并且可以以与天然橡胶相似的方式配合成橡胶制剂。本发明更具体地公开了一种用于合成聚异戊二烯橡胶的方法，其包括在钕催化剂体系存在下聚合异戊二烯单体，其中所述钕催化剂体系通过以下方法制备，所述方法包括：（1）使羧酸钕与有机铝化合物在有机溶剂中制备钕 - 铝催化剂组分，和（2）随后使钕 - 铝催化剂组分与元素卤素反应以产生钕催化剂体系，其中钕催化剂体系不含含镍化合物。

8. 发明申请

US20060252861A1 Synthesis of soluble functionalized lithium initiators 失效
标题翻译：可溶性官能化锂引发剂的合成
公开(公告)号：US20060252861A1
公开(公告)日：2006-11-09
申请号：US11479717
申请日：2006-06-30
申请人： Adel Halasa , Wen-Liang Hsu
发明人： Adel Halasa , Wen-Liang Hsu
IPC分类号： C08G63/685
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“表示烷基，其含有1至 8个碳原子，和（b）选自碳黑和二氧化硅中的至少一种。

9. 发明申请

US20060183831A1 Preparation of silica reinforced polyisoprene-rich rubber composition and tire with component thereof 失效
公开(公告)号：US20060183831A1
公开(公告)日：2006-08-17
申请号：US11058531
申请日：2005-02-15
申请人： Wen-Liang Hsu , Shingo Futamura , Kenneth Bates , Adel Halasa , Kuo-Chih Hua , Bruce Hahn
发明人： Wen-Liang Hsu , Shingo Futamura , Kenneth Bates , Adel Halasa , Kuo-Chih Hua , Bruce Hahn
IPC分类号： B60C1/00
CPC分类号： B60C1/0016
摘要： This invention relates to the preparation of a cis 1,4-polyisoprene rubber-rich rubber composition containing precipitated silica which has been pre-treated with a fatty alcohol and/or epoxidized soybean oil together with an organosilane containing polysulfide coupling agent and to tires having at least one component comprised of such rubber composition. The invention particularly relates to a process of (a) preparing a natural rubber-rich rubber composition comprised of pre-treating precipitated silica aggregates prior to blending with, or in the presence of, dry natural rubber with a fatty alcohol and/or epoxidized soybean oil to the exclusion of sulfur curative for the natural rubber, mixing an organalkoxysiloxane based polysulfide coupling agent with said dry natural rubber coincidentally with or subsequent to said precipitated silica aggregate fatty alcohol and/or epoxidized soybean oil pre-treatment to form a composite thereof, to the exclusion of sulfur curative, followed by (b) mixing the resulting rubber mixture with sulfur curative and (c) curing the resulting rubber composition.

10. 发明申请

US20060149010A1 Catalyst for synthesizing high trans polymers 失效
标题翻译：用于合成高反式聚合物的催化剂
公开(公告)号：US20060149010A1
公开(公告)日：2006-07-06
申请号：US11311495
申请日：2005-12-19
申请人： Adel Halasa , Wen-Liang Hsu , Chad Jasiunas , Laurie Austin
发明人： Adel Halasa , Wen-Liang Hsu , Chad Jasiunas , Laurie Austin
IPC分类号： C08F4/56
CPC分类号： C08F36/06 , C08F4/484 , C08F4/52 , C08F4/48 , C08F4/50
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用于轮胎胎面和侧壁橡胶，其在胎面中表现出优异的耐磨损性能和优异的侧壁弯曲性能。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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