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。

公开(公告)号：US07291687B1

公开(公告)日：2007-11-06

申请号：US11468921

申请日：2006-08-31

申请人： Adel Farhan Halasa ,  Laurie Elizabeth Austin ,  Wen-Liang Hsu

发明人： Adel Farhan Halasa ,  Laurie Elizabeth Austin ,  Wen-Liang Hsu

IPC分类号： C08F36/04 ,  C08F4/50

CPC分类号： C08F36/04 ,  C08F4/54

摘要： The present invention is directed to a 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) a barium salt of an alcohol that is soluble in a hydrocarbon solvent, and (b) an organomagnesium compound. In one example, the alcohol is a primary or secondary alcohol. The catalyst system can further optionally include an alkali metal alkoxide, an organolithium compound, an amine compound, or mixtures thereof.

摘要翻译： 本发明涉及一种用于合成橡胶状聚合物的催化剂体系，如聚丁二烯橡胶和苯乙烯 - 丁二烯橡胶，其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）可溶于烃溶剂的醇的钡盐和（b）有机镁化合物。 在一个实例中，醇是伯醇或仲醇。 催化剂体系还可任选地包括碱金属醇盐，有机锂化合物，胺化合物或其混合物。

公开(公告)号：US06608154B2

公开(公告)日：2003-08-19

申请号：US10178493

申请日：2002-06-24

申请人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Laurie Elizabeth Austin ,  Chad Aaron Jasiunas

发明人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Laurie Elizabeth Austin ,  Chad Aaron Jasiunas

IPC分类号： C08F450

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. The process and catalyst system of this invention can also be used in the synthesis of trans-styrene-butadiene rubber (SBR). 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 thymol, and (c) an organoaluminum compound.

公开(公告)号：US6103842A

公开(公告)日：2000-08-15

申请号：US72492

申请日：1998-05-04

申请人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Laurie Elizabeth Austin

发明人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Laurie Elizabeth Austin

IPC分类号： B60C1/00 ,  C08F4/54 ,  C08F4/56 ,  C08F236/10 ,  C08F4/50 ,  C08F36/06

CPC分类号： C08F236/10 ,  C08F4/565

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 exothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a barium 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 barium alkoxide and (c) a lithium alkoxide.

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一种用于放热聚合的催化剂体系，其基本上由（a）有机锂化合物，（b）烷氧基钡和（c）醇盐锂组成。 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）钡醇盐和（c）醇锂。

公开(公告)号：US06350807B1

公开(公告)日：2002-02-26

申请号：US09616270

申请日：2000-07-14

申请人： Edward John Blok ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa ,  John Joseph Andre Verthe ,  Raymond Robert DiRossi

发明人： Edward John Blok ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa ,  John Joseph Andre Verthe ,  Raymond Robert DiRossi

IPC分类号： C08K334

CPC分类号： C08L9/00 ,  B60C1/0016 ,  C08K3/04 ,  C08K3/36 ,  C08K5/0016 ,  C08L7/00 ,  C08L15/00 ,  Y02T10/862 ,  C08L2666/08

摘要： The present invention relates to a tire tread compound that is highly loaded with silica. This compound offers the advantages of silica compounding without the need for solution SBR. More specifically, the tire tread rubber formulations of this invention offer an excellent combination of traction, treadwear and rolling resistance characteristics. The subject invention 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; wherein the tread is comprised of (1) 5 phr to 40 phr of a polyisoprene rubber selected from the group consisting of natural rubber and synthetic polyisoprene, (2) 20 phr to 60 phr of high vinyl polybutadiene rubber having a glass transition temperature which is within the range of −40° C. to 10° C., (3) 20 phr to 60 phr of tin-coupled isoprene-butadiene rubber having a glass transition temperature which is within the range of −90° C. to −70° C., (4) 30 phr to 90 phr of silica, (5) 5 phr to 50 phr of carbon black, (6) 2 phr to 50 phr of processing oil and (7) 0.5 phr to 15 phr of a silica coupling agent.

摘要翻译： 本发明涉及高度负载二氧化硅的轮胎胎面胶。 该化合物具有二氧化硅复合的优点，无需溶液SBR。 更具体地，本发明的轮胎胎面橡胶配方提供牵引力，胎面磨损和滚动阻力特性的优异组合。 本发明公开了一种轮胎，其由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; 其中胎面由（1）5phr至40phr的选自天然橡胶和合成聚异戊二烯的聚异戊二烯橡胶，（2）20phr至60phr的玻璃化转变温度为20phr至60phr的高乙烯基聚丁二烯橡胶 在-40℃至10℃的范围内，（3）20phr至60phr的锡偶合异戊二烯 - 丁二烯橡胶，其玻璃化转变温度在-90℃至-70℃的范围内 （4）30phr至90phr的二氧化硅，（5）5phr至50phr的炭黑，（6）2phr至50phr的加工油和（7）0.5phr至15phr的二氧化硅 偶联剂。

公开(公告)号：US5994448A

公开(公告)日：1999-11-30

申请号：US133503

申请日：1998-08-12

申请人： Edward John Blok ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

发明人： Edward John Blok ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

IPC分类号： B60C1/00 ,  C08C19/44 ,  C08L9/00 ,  C08K3/00

CPC分类号： C08C19/44 ,  B60C1/0016 ,  C08L9/00 ,  C08K3/36 ,  C08L7/00 ,  C08L9/06

摘要： This invention relates to a tire tread compound that can be used in manufacturing tires having outstanding traction characteristics without compromising treadwear and rolling resistance. The tire tread compounds of this invention are made utilizing an isoprene-butadiene rubber having a high glass transition temperature and having SnR.sub.3 end groups, wherein R represents an alkyl group, such as a tertiary-butyl group. These isoprene-butadiene rubbers are made by reacting an isoprene-butadiene rubber having a glass transition temperature which is within the range of about -50.degree. C. to about 0.degree. C. with a tin compound of the formula SnR.sub.3 X, wherein R represents an alkyl group and wherein X represents a halogen. This invention more specifically discloses a tire tread rubber composition which is comprised of (1) about 60 phr to about 95 phr of an isoprene-butadiene rubber having a glass transition temperature which is within the range of about -50.degree. C. to about 0.degree. C. and having --SnR.sub.3 end groups, (2) about 5 phr to about 30 phr of natural rubber and (3) up to about 25 phr of a rubbery polymer having a low glass transition temperature which is within the range of about -85.degree. C. to about -55.degree. C., with the proviso that the total amount of the natural rubber and the rubbery polymer having a low glass transition temperature does not exceed about 40 phr. The rubbery polymer having a low glass transition temperature will typically be high cis-1,4-polybutadiene, isoprene-butadiene rubber, styrene-butadiene rubber or styrene-isoprene-butadiene rubber.

摘要翻译： 本发明涉及一种轮胎胎面胶，其可用于制造具有优异牵引特性的轮胎，而不损害胎面和滚动阻力。 本发明的轮胎胎面胶料采用高玻璃化转变温度的异戊二烯 - 丁二烯橡胶制成，并具有SnR 3端基，其中R表示烷基，如叔丁基。 这些异戊二烯 - 丁二烯橡胶通过使玻璃化转变温度在约-50℃至约0℃范围内的异戊二烯 - 丁二烯橡胶与式SnR 3 X的锡化合物反应制备，其中R表示 烷基，其中X表示卤素。 本发明更具体地公开了一种轮胎胎面橡胶组合物，其包含（1）约60phr至约95phr的玻璃化转变温度在约-50℃至约0的范围内的异戊二烯 - 丁二烯橡胶 具有-SnR 3端基，（2）约5phr至约30phr的天然橡胶和（3）至多约25phr的玻璃化转变温度低于约 - 约25phr的橡胶状聚合物， 85℃至约-55℃，条件是具有低玻璃化转变温度的天然橡胶和橡胶状聚合物的总量不超过约40phr。 具有低玻璃化转变温度的橡胶状聚合物通常是高顺式-1,4-聚丁二烯，异戊二烯 - 丁二烯橡胶，苯乙烯 - 丁二烯橡胶或苯乙烯 - 异戊二烯 - 丁二烯橡胶。

公开(公告)号：US07199201B2

公开(公告)日：2007-04-03

申请号：US11287562

申请日：2005-11-23

申请人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Aaron Michael Ryba ,  Jin-Ping Zhou ,  Chad Aaron Jasiunas ,  Paul Harry Sandstrom

发明人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Aaron Michael Ryba ,  Jin-Ping Zhou ,  Chad Aaron Jasiunas ,  Paul Harry Sandstrom

IPC分类号： C08F36/08 ,  C08F136/08

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。

公开(公告)号：US07091150B2

公开(公告)日：2006-08-15

申请号：US10942517

申请日：2004-09-16

申请人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Aaron Michael Ryba ,  Jin-Ping Zhou ,  Chad Aaron Jasiunas ,  Paul Harry Sandstrom

发明人： Adel Farhan Halasa ,  Wen-Liang Hsu ,  Aaron Michael Ryba ,  Jin-Ping Zhou ,  Chad Aaron Jasiunas ,  Paul Harry Sandstrom

IPC分类号： B01J31/04 ,  B01J37/04

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 preparing a neodymium catalyst system which 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. The present invention further discloses a synthetic polyisoprene rubber which is comprised of repeat units that are derived from isoprene, wherein the synthetic polyisoprene rubber has a cis-microstructure content which is within the range of 98.0% to 99.5%, a 3,4-microstructure content which is within the range of 0.5% to 2.0%, and a trans-microstructure content which is within the range of 0.0% to 0.5%.

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制备钕催化剂体系的方法，其包括：（1）使羧酸钕与有机铝化合物在有机溶剂中反应以制备钕 - 铝催化剂组分，和（2）随后使钕 - 铝催化剂组分 用元素卤素制备钕催化剂体系。 本发明还公开了一种合成聚异戊二烯橡胶，其由衍生自异戊二烯的重复单元组成，其中合成聚异戊二烯橡胶的顺式微结构含量在98.0％至99.5％的范围内，3,4-微结构 含量在0.5％至2.0％的范围内，反式微结构含量在0.0％至0.5％的范围内。

公开(公告)号：US06562895B2

公开(公告)日：2003-05-13

申请号：US09727175

申请日：2000-11-30

申请人： Edward John Blok ,  Mark Leslie Kralevich, Jr. ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

发明人： Edward John Blok ,  Mark Leslie Kralevich, Jr. ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

IPC分类号： C08J2700

CPC分类号： C08F236/08 ,  B60C1/0016 ,  C08F236/06 ,  C08L21/00 ,  Y10T152/10495 ,  C08L2666/08

摘要： The subject invention discloses a liquid isoprene-butadiene rubber (IBR) which is particularly valuable for use in making treads for high performance automobile tires, including race tires, that exhibit superior dry traction characteristics and durability. The isoprene-butadiene rubber of this invention is a liquid at room temperature and is comprised of repeat units which are derived from about 5 weight percent to about 95 weight percent isoprene and from about 5 weight percent to about 95 weight percent 1,3-butadiene, wherein the repeat units derived from isoprene and 1,3-butadiene are in essentially random order. The IBR of this invention also has a low number average molecular weight which is within the range of about 3,000 to about 50,000 and has a glass transition temperature which is within the range of about −50° C. to about 20° C. This invention more specifically discloses a tire tread compound which is comprised of (a) a rubbery elastomer, (b) about 20 phr to about 80 phr of an aromatic process oil, (c) about 35 phr to about 130 phr of a filler and (d) about 4 phr to about 40 phr of a liquid isoprene-butadiene rubber having a number average molecular weight which is within the range of about 3,000 to about 50,000, a glass transition temperature which is within the range of about −50° C. to about 20° C., and wherein the liquid isoprene-butadiene polymer exhibits only one glass transition temperature.

摘要翻译： 本发明公开了一种特别有价值的液体异戊二烯 - 丁二烯橡胶（IBR），其用于制造具有优异的干牵引特性和耐久性的高性能汽车轮胎（包括赛车轮胎）的胎面。 本发明的异戊二烯 - 丁二烯橡胶在室温下为液体，并由衍生自约5重量％至约95重量％的异戊二烯和约5重量％至约95重量％的1,3-丁二烯的重复单元 ，其中衍生自异戊二烯和1,3-丁二烯的重复单元基本上是随机的。 本发明的IBR还具有低于约3,000至约50,000的数均分子量，玻璃化转变温度在约-50℃至约20℃的范围内。本发明 更具体地公开了一种轮胎胎面胶，其由（a）橡胶弹性体，（b）约20phr至约80phr的芳族加工油，（c）约35phr至约130phr的填料和（d ）约4phr至约40phr的数均分子量在约3,000至约50,000范围内的液体异戊二烯 - 丁二烯橡胶，玻璃化转变温度在约-50℃至 约20℃，并且其中液体异戊二烯 - 丁二烯聚合物仅显示一个玻璃化转变温度。

公开(公告)号：US06410624B1

公开(公告)日：2002-06-25

申请号：US09395446

申请日：1999-09-14

申请人： Neil Arthur Maly ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

发明人： Neil Arthur Maly ,  Paul Harry Sandstrom ,  Wen-Liang Hsu ,  Adel Farhan Halasa

IPC分类号： C08K524

CPC分类号： C08K5/548 ,  B60C1/0016 ,  C08K3/04 ,  C08L9/00 ,  C08L9/06 ,  C08L2205/02 ,  Y02T10/862 ,  C08L21/00 ,  C08L2666/08

摘要： Rubber compositions comprised of novel blends of segmented styrene-rich styrene/isoprene/butadiene terpolymer elastomer and at least one additional elastomer and tires with treads comprised of such rubber composition. Such tires may exhibit increased traction and reduced rolling resistance.

摘要翻译： 橡胶组合物由分段富含苯乙烯的苯乙烯/异戊二烯/丁二烯三元共聚物弹性体的新共混物和至少一种另外的弹性体和具有由这种橡胶组合物构成的胎面的轮胎组成。 这种轮胎可能表现出增加的牵引力和降低的滚动阻力。