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1. 发明授权

US07344752B2 Core-shell particles synthesized through controlled free radical polymerization 失效
标题翻译：通过控制自由基聚合合成的核 - 壳颗粒
公开(公告)号：US07344752B2
公开(公告)日：2008-03-18
申请号：US11023868
申请日：2004-12-27
申请人： Lei Zheng , John Thomas Lean , Eric Sean Castner , Thierry Florent Edme Materne , Dane Kenton Parker , Frank James Feher
发明人： Lei Zheng , John Thomas Lean , Eric Sean Castner , Thierry Florent Edme Materne , Dane Kenton Parker , Frank James Feher
IPC分类号： B01J13/02 , B01J13/14
CPC分类号： C08F279/02 , C08F257/02 , C08F291/00 , C08F2/38
摘要： The present invention discloses a process for producing a core-shell polymer that comprises: (1) preparing a monomer solution which is comprised of (a) at least one monomer, optional one crosslinking monomer (b) a conjugate acid of a surfactant with a pKa of less than 14, and (c) a controlled free radical polymerization agent; (2) preparing an aqueous medium which is comprised of (a) water, and (b) a conjugate base of a weak acid wherein the pKb of the base is less than 14; and (3) mixing the monomer solution with the aqueous medium under conditions that result in the in-situ formation of an emulsifier to produce a polymerization medium, and (4) initiating free radical polymerization within the polymerization medium to produce a core polymer, wherein the core contains a free radical control agents, (5) adding a second monomer to the polymerization medium containing the core polymer, and (6) allowing polymerization to proceed in the presence of the free radical control agent to produce the core-shell polymer.
摘要翻译：本发明公开了一种制备核 - 壳聚合物的方法，其包括：（1）制备单体溶液，该单体溶液由（a）至少一种单体，任选的一种交联单体（b）表面活性剂的共轭酸与 pKa小于14，（c）受控自由基聚合剂; （2）制备由（a）水和（b）弱酸的共轭碱组成的水性介质，其中碱的pKb小于14; 和（3）在导致乳化剂原位形成以产生聚合介质的条件下将单体溶液与水性介质混合，和（4）在聚合介质内引发自由基聚合以制备芯聚合物，其中核心包含自由基控制剂，（5）在含有核聚合物的聚合介质中加入第二单体，和（6）在自由基控制剂的存在下使聚合进行以制备核 - 壳聚合物。

2. 发明授权

US07825194B2 Hairy polymeric nanoparticles 有权
标题翻译：毛状聚合物纳米粒子
公开(公告)号：US07825194B2
公开(公告)日：2010-11-02
申请号：US12287426
申请日：2008-10-10
申请人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
发明人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
IPC分类号： C08F8/42 , C08F36/04 , C08F36/08 , C08F36/06
CPC分类号： C08F257/02 , C08C1/15 , C08F6/22 , C08F236/06 , C08L51/00
摘要： This invention discloses a process for synthesizing a hairy polymer particle which comprises the steps of (1) polymerizing a vinyl aromatic monomer by emulsion polymerization in an aqueous medium to produce core particles, (2) recovering the core particles from the aqueous medium, (3) dispersing the core particles in an organic solvent, (4) adding an organo-lithium compound to the dried core particles in the organic solvent to produce the hairless core initiator, and (5) utilizing the hairless core initiator to initiate the anionic polymerization of a conjugated diolefin monomer in an organic solvent to produce a solution of the hairy polymer particles. The hairy polymer nanoparticles can then be recovered from the organic solvent. These hairy polymer particles are comprised of (1) a core which is comprised of a polymer of a vinyl aromatic monomer and (2) hairs which are polymer chains of a conjugated diolefin monomer, wherein the hairs are covalently bonded to the core. The core is typically spherical in shape, has a diameter of less than 1000 nm, and is comprised of a crosslinked polymer of a vinyl aromatic monomer. The hairy polymer particles of this invention are useful as fillers in rubber compositions used in making articles of manufacture, such as tires, hoses, power transmission belts, windshield wiper blades, and the like.
摘要翻译：本发明公开了一种合成毛状聚合物颗粒的方法，其包括以下步骤：（1）通过乳液聚合在水性介质中聚合乙烯基芳族单体以产生核心颗粒，（2）从水介质中回收芯颗粒，（3 ）将核心颗粒分散在有机溶剂中，（4）将有机锂化合物加入到有机溶剂中的干燥芯颗粒中以制备无毛芯引发剂，和（5）利用无毛芯引发剂引发阴离子聚合共轭二烯单体在有机溶剂中以产生毛状聚合物颗粒的溶液。然后可以从有机溶剂中回收毛状聚合物纳米颗粒。这些毛发聚合物颗粒包括（1）由乙烯基芳族单体的聚合物组成的芯和（2）作为共轭二烯烃单体的聚合物链的毛发，其中毛发共价键合到芯上。芯通常为球形，直径小于1000nm，并且由乙烯基芳族单体的交联聚合物组成。本发明的毛发聚合物颗粒可用作用于制造制品的橡胶组合物中的填料，例如轮胎，软管，动力传动带，挡风玻璃刮水器等。

3. 发明申请

US20090042719A1 Hairy polymeric nanoparticles 有权
标题翻译：毛状聚合物纳米粒子
公开(公告)号：US20090042719A1
公开(公告)日：2009-02-12
申请号：US12287426
申请日：2008-10-10
申请人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
发明人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
IPC分类号： B01J31/12
CPC分类号： C08F257/02 , C08C1/15 , C08F6/22 , C08F236/06 , C08L51/00
摘要： This invention discloses a process for synthesizing a hairy polymer particle which comprises the steps of (1) polymerizing a vinyl aromatic monomer by emulsion polymerization in an aqueous medium to produce core particles, (2) recovering the core particles from the aqueous medium, (3) dispersing the core particles in an organic solvent, (4) adding an organo-lithium compound to the dried core particles in the organic solvent to produce the hairless core initiator, and (5) utilizing the hairless core initiator to initiate the anionic polymerization of a conjugated diolefin monomer in an organic solvent to produce a solution of the hairy polymer particles. The hairy polymer nanoparticles can then be recovered from the organic solvent. These hairy polymer particles are comprised of (1) a core which is comprised of a polymer of a vinyl aromatic monomer and (2) hairs which are polymer chains of a conjugated diolefin monomer, wherein the hairs are covalently bonded to the core. The core is typically spherical in shape, has a diameter of less than 1000 nm, and is comprised of a crosslinked polymer of a vinyl aromatic monomer. The hairy polymer particles of this invention are useful as fillers in rubber compositions used in making articles of manufacture, such as tires, hoses, power transmission belts, windshield wiper blades, and the like.
摘要翻译：本发明公开了一种合成毛状聚合物颗粒的方法，其包括以下步骤：（1）通过乳液聚合在水性介质中聚合乙烯基芳族单体以产生核心颗粒，（2）从水介质中回收芯颗粒，（3 ）将核心颗粒分散在有机溶剂中，（4）将有机锂化合物加入到有机溶剂中的干燥芯颗粒中以制备无毛芯引发剂，和（5）利用无毛芯引发剂引发阴离子聚合共轭二烯单体在有机溶剂中以产生毛状聚合物颗粒的溶液。然后可以从有机溶剂中回收毛状聚合物纳米颗粒。这些毛发聚合物颗粒包括（1）由乙烯基芳族单体的聚合物组成的芯和（2）作为共轭二烯烃单体的聚合物链的毛发，其中毛发共价键合到芯上。芯通常为球形，直径小于1000nm，并且由乙烯基芳族单体的交联聚合物组成。本发明的毛发聚合物颗粒可用作用于制造制品的橡胶组合物中的填料，例如轮胎，软管，动力传动带，挡风玻璃刮水器等。

4. 发明授权

US07408005B2 Hairy polymeric nanoparticles 失效
公开(公告)号：US07408005B2
公开(公告)日：2008-08-05
申请号：US11072986
申请日：2005-03-05
申请人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
发明人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
IPC分类号： C08F279/02
CPC分类号： C08F257/02 , C08C1/15 , C08F6/22 , C08F236/06 , C08L51/00
摘要： This invention discloses a process for synthesizing a hairy polymer particle which comprises the steps of (1) polymerizing a vinyl aromatic monomer by emulsion polymerization in an aqueous medium to produce core particles, (2) recovering the core particles from the aqueous medium, (3) dispersing the core particles in an organic solvent, (4) adding an organo-lithium compound to the dried core particles in the organic solvent to produce the hairless core initiator, and (5) utilizing the hairless core initiator to initiate the anionic polymerization of a conjugated diolefin monomer in an organic solvent to produce a solution of the hairy polymer particles. The hairy polymer nanoparticles can then be recovered from the organic solvent. These hairy polymer particles are comprised of (1) a core which is comprised of a polymer of a vinyl aromatic monomer and (2) hairs which are polymer chains of a conjugated diolefin monomer, wherein the hairs are covalently bonded to the core. The core is typically spherical in shape, has a diameter of less than 1000 nm, and is comprised of a crosslinked polymer of a vinyl aromatic monomer. The hairy polymer particles of this invention are useful as fillers in rubber compositions used in making articles of manufacture, such as tires, hoses, power transmission belts, windshield wiper blades, and the like.

5. 发明授权

US07812092B2 Hairy polymeric nanoparticles 有权
公开(公告)号：US07812092B2
公开(公告)日：2010-10-12
申请号：US12157237
申请日：2008-06-10
申请人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
发明人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
IPC分类号： C08F279/02
CPC分类号： C08F257/02 , C08C1/15 , C08F6/22 , C08F236/06 , C08L51/00
摘要： This invention discloses a process for synthesizing a hairy polymer particle which comprises the steps of (1) polymerizing a vinyl aromatic monomer by emulsion polymerization in an aqueous medium to produce core particles, (2) recovering the core particles from the aqueous medium, (3) dispersing the core particles in an organic solvent, (4) adding an organo-lithium compound to the dried core particles in the organic solvent to produce the hairless core initiator, and (5) utilizing the hairless core initiator to initiate the anionic polymerization of a conjugated diolefin monomer in an organic solvent to produce a solution of the hairy polymer particles. The hairy polymer nanoparticles can then be recovered from the organic solvent. These hairy polymer particles are comprised of (1) a core which is comprised of a polymer of a vinyl aromatic monomer and (2) hairs which are polymer chains of a conjugated diolefin monomer, wherein the hairs are covalently bonded to the core. The core is typically spherical in shape, has a diameter of less than 1000 nm, and is comprised of a crosslinked polymer of a vinyl aromatic monomer. The hairy polymer particles of this invention are useful as fillers in rubber compositions used in making articles of manufacture, such as tires, hoses, power transmission belts, windshield wiper blades, and the like.

6. 发明申请

US20080242813A1 Hairy polymeric nanoparticles 有权
标题翻译：毛状聚合物纳米粒子
公开(公告)号：US20080242813A1
公开(公告)日：2008-10-02
申请号：US12157237
申请日：2008-06-10
申请人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
发明人： Lei Zheng , Eric Sean Castner , Thierry Florent Edme Materne
IPC分类号： C08F36/06 , C08F36/08 , C08F12/08 , C08F4/34
CPC分类号： C08F257/02 , C08C1/15 , C08F6/22 , C08F236/06 , C08L51/00
摘要： This invention discloses a process for synthesizing a hairy polymer particle which comprises the steps of (1) polymerizing a vinyl aromatic monomer by emulsion polymerization in an aqueous medium to produce core particles, (2) recovering the core particles from the aqueous medium, (3) dispersing the core particles in an organic solvent, (4) adding an organo-lithium compound to the dried core particles in the organic solvent to produce the hairless core initiator, and (5) utilizing the hairless core initiator to initiate the anionic polymerization of a conjugated diolefin monomer in an organic solvent to produce a solution of the hairy polymer particles. The hairy polymer nanoparticles can then be recovered from the organic solvent. These hairy polymer particles are comprised of (1) a core which is comprised of a polymer of a vinyl aromatic monomer and (2) hairs which are polymer chains of a conjugated diolefin monomer, wherein the hairs are covalently bonded to the core. The core is typically spherical in shape, has a diameter of less than 1000 nm, and is comprised of a crosslinked polymer of a vinyl aromatic monomer. The hairy polymer particles of this invention are useful as fillers in rubber compositions used in making articles of manufacture, such as tires, hoses, power transmission belts, windshield wiper blades, and the like.
摘要翻译：本发明公开了一种合成毛状聚合物颗粒的方法，其包括以下步骤：（1）通过乳液聚合在水性介质中聚合乙烯基芳族单体以产生核心颗粒，（2）从水介质中回收芯颗粒，（3 ）将核心颗粒分散在有机溶剂中，（4）将有机锂化合物加入到有机溶剂中的干燥芯颗粒中以制备无毛芯引发剂，和（5）利用无毛芯引发剂引发阴离子聚合共轭二烯单体在有机溶剂中以产生毛状聚合物颗粒的溶液。然后可以从有机溶剂中回收毛状聚合物纳米颗粒。这些毛发聚合物颗粒包括（1）由乙烯基芳族单体的聚合物组成的芯和（2）作为共轭二烯烃单体的聚合物链的毛发，其中毛发共价键合到芯上。芯通常为球形，直径小于1000nm，并且由乙烯基芳族单体的交联聚合物组成。本发明的毛发聚合物颗粒可用作用于制造制品的橡胶组合物中的填料，例如轮胎，软管，动力传动带，挡风玻璃刮水器等。

7. 发明授权

US06313220B1 Preparation of reinforced elastomer, elastomer composite, and tire having component thereof 失效
标题翻译：增强弹性体，弹性体复合材料和具有其组分的轮胎的制备
公开(公告)号：US06313220B1
公开(公告)日：2001-11-06
申请号：US09518570
申请日：2000-03-03
申请人： Thierry Florent Edme Materne , Daniel Edward Bowen, III , Francois Kayser , Eric Sean Castner
发明人： Thierry Florent Edme Materne , Daniel Edward Bowen, III , Francois Kayser , Eric Sean Castner
IPC分类号： C08L8304
CPC分类号： C08L83/04 , B60C1/00 , B60C1/0016 , C08G77/16 , C08G77/18 , C08K5/54 , C08L9/00 , C08L9/06 , C08L21/00 , C08L2666/14 , C08L2666/44 , C08L2666/52 , C08L2666/04
摘要： This invention relates to the preparation of an elastomer which contains a dispersion of a reinforcing system formed in situ within an elastomer host by the interaction of a telechelic hydroxy and/or alkoxy terminated polysiloxane and a reticulating agent having a moiety comprised of at least two alkoxy groups. The invention further includes a rubber composition of at least two elastomers wherein one of said elastomers is a pre-formed composite of elastomer and the in situ formed reinforcement system. A tire having a component of such rubber composition, particularly a tire tread, is specifically contemplated.
摘要翻译：本发明涉及弹性体的制备，该弹性体含有通过遥爪羟基和/或烷氧基封端的聚硅氧烷与具有至少两个烷氧基的部分组成的网状物的相互作用的弹性体主体内原位形成的增强体系的分散体团体本发明还包括至少两种弹性体的橡胶组合物，其中所述弹性体之一是弹性体的预形成复合材料和原位形成的增强体系。特别考虑了具有这种橡胶组合物的组分，特别是轮胎胎面的轮胎。

8. 发明授权

US07244783B2 Thermoplastic elastomer composition 有权
标题翻译：热塑性弹性体组合物
公开(公告)号：US07244783B2
公开(公告)日：2007-07-17
申请号：US10875413
申请日：2004-06-24
申请人： John Thomas Lean , Manoj Ajbani , Eric Sean Castner , Lei Zheng , Christopher Kiehl
发明人： John Thomas Lean , Manoj Ajbani , Eric Sean Castner , Lei Zheng , Christopher Kiehl
IPC分类号： C08L53/00
CPC分类号： C08L51/003 , C08F257/00 , C08L23/10 , C08L53/025 , C08L2205/03 , C08F236/04 , C08L2666/02
摘要： A thermoplastic elastomer composition comprised of (a) a thermoplastic resin selected from the group consisting of polyphenylene ether, polypropylene, polyethylene, and polystyrene, (b) a block copolymer selected from the group consisting of styrene-ethylene butylene-styrene, styrene-ethylene propylene-styrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-isoprene random copolymer, styrene-ethylene propylene block copolymer, styrene-ethylene ethylene propylene-styrene and hydrogenated styrene-butadiene random copolymers, (c) a core-shell polymer comprised of a polymeric core and a polymeric shell with the proviso that the polymeric core and/or the polymeric shell may be crosslinked, and (d) an oil.
摘要翻译：一种热塑性弹性体组合物，其包含（a）选自聚苯醚，聚丙烯，聚乙烯和聚苯乙烯的热塑性树脂，（b）嵌段共聚物，其选自苯乙烯 - 乙烯 - 丁烯 - 苯乙烯，苯乙烯 - 乙烯丙烯 - 苯乙烯，氢化聚丁二烯，氢化聚异戊二烯，氢化苯乙烯 - 异戊二烯无规共聚物，苯乙烯 - 乙烯丙烯嵌段共聚物，苯乙烯 - 乙烯乙烯丙烯 - 苯乙烯和氢化苯乙烯 - 丁二烯无规共聚物，（c）聚合物芯和聚合物壳，条件是聚合物芯和/或聚合物壳可以是交联的，和（d）油。

9. 发明授权

US06777500B2 Core-shell polymer particles 失效
公开(公告)号：US06777500B2
公开(公告)日：2004-08-17
申请号：US10334574
申请日：2002-12-31
申请人： John Thomas Lean , Eric Sean Castner
发明人： John Thomas Lean , Eric Sean Castner
IPC分类号： C08L906
CPC分类号： C08F257/02 , C08L9/06 , C08L51/00 , C08L53/00 , Y10S525/902 , C08F236/04 , C08L2666/24
摘要： A core-shell particle for use as filler in rubber compositions. In one embodiment, the particle comprises a crosslinked core having repeat aromatic vinyl units. During an emulsion polymerization, a crosslinked shell comprising of conjugated diene units is grafted onto the core through residual vinyl units. The polymeric shell provides for better interaction and dispersion of the styrene core in an otherwise immiscible polymer matrix, particularly diene-based polymers. In another embodiment, the core has repeat units of (i) about 0% to about 25% by weight of a conjugated diene unit, (ii) about 70% to about 85% by weight of an aromatic vinyl unit, and (iii) about 15% to about 30% by weight of a crosslinking monomer unit.

10. 发明授权

US07638574B2 Tire tread containing core-shell particles 有权
标题翻译：包含核 - 壳颗粒的轮胎胎面
公开(公告)号：US07638574B2
公开(公告)日：2009-12-29
申请号：US11170912
申请日：2005-06-30
申请人： Ping Zhang , Lei Zheng , Feng Anne Xie , Eric Sean Castner
发明人： Ping Zhang , Lei Zheng , Feng Anne Xie , Eric Sean Castner
IPC分类号： C08K3/04 , C08L51/04 , C08L9/00 , C08F36/00 , C08F12/02
CPC分类号： C08F279/02 , B60C1/0016 , C08K3/04 , C08L9/06 , C08L51/04 , C08L2666/24 , C08L2666/02 , C08L2666/04
摘要： This invention is based upon the discovered that crosslinked core-shell particles can be used as a filler in low cost emulsion styrene-butadiene rubber (ESBR) with excellent results being attained. In fact, such core-shell particle filled ESBR exhibits performance similar to silica filled solution styrene-butadiene rubber (SSBR) in terms of dynamic response, Payne effect, rebound and tan δ at 0° C. and 100° C. The utilization of such crosslinked core-shell particles in rubber compounds offers the additional advantage of weight reduction since the core-shell particles are significantly less dense than carbon black or silica fillers. The use of the crosslinked core-shell polymers of this invention in rubber formulations in place of silica also offers the advantage of not needing any expensive silane coupling agents to attain required levels of polymer/filler interaction. Accordingly, no silane coupling agent is used in the rubber compounds of this invention which leads to reduced cost. Cost can be further reduced by virtue of the fact that compound mixing conditions can be substantially relaxed as compared to mixing silica containing rubber formulations. The present invention more specifically discloses A rubbery composition which is comprised of (1) an emulsion styrene-butadiene rubber, (2) carbon black, and (3) core-shell particles, wherein the core-shell particles are comprised of (a) a crosslinked elastomeric core comprised of repeat units that are derived from at least one diolefin monomer, and (b) a polymeric shell which is derived from at least one vinyl aromatic monomer.
摘要翻译：本发明基于发现交联的核 - 壳颗粒可以用作低成本乳液丁苯橡胶（ESBR）中的填料，并获得优异的结果。事实上，这种核 - 壳颗粒填充的ESBR在0°C和100°C的动态响应，Payne效应，回弹和tanδ方面表现出与二氧化硅填充溶液苯乙烯 - 丁二烯橡胶（SSBR）相似的性能。橡胶化合物中的这种交联的核 - 壳颗粒提供了减轻重量的另外的优点，因为核 - 壳颗粒比炭黑或二氧化硅填料密度明显更低。在橡胶配方中使用本发明的交联的核 - 壳聚合物代替二氧化硅也提供了不需要任何昂贵的硅烷偶联剂来获得所需水平的聚合物/填料相互作用的优点。因此，本发明的橡胶化合物中不使用硅烷偶联剂，导致成本降低。与混合含二氧化硅的橡胶配方相比，由于化合物混合条件可以基本上松弛，所以可以进一步降低成本。本发明更具体地公开了一种橡胶组合物，其包含（1）乳液丁苯橡胶，（2）炭黑和（3）核 - 壳颗粒，其中核 - 壳颗粒由（a）组成，由衍生自至少一种二烯单体的重复单元组成的交联弹性芯，和（b）衍生自至少一种乙烯基芳族单体的聚合物壳。

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