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1. 发明授权

US4530967A Process for continuously polymerizing a block copolymer and the block copolymer mixture obtained therefrom 失效
标题翻译：用于连续聚合嵌段共聚物和由其获得的嵌段共聚物混合物的方法
公开(公告)号：US4530967A
公开(公告)日：1985-07-23
申请号：US509670
申请日：1983-06-30
申请人： Toshinori Shiraki , Akio Yamori , Hideo Morita
发明人： Toshinori Shiraki , Akio Yamori , Hideo Morita
IPC分类号： C08F297/04
CPC分类号： C08F297/04
摘要： A block copolymer containing two or more polymer blocks composed mainly of an aromatic vinyl hydrocarbon and one or more polymer blocks composed mainly of a conjugated diene having excellent mechanical properties can be advantageously prepared by (a) batchwise preparing the specified living polymer (i.e. prepolymer) of at least one aromatic vinyl hydrocarbon polymer block by using a portion of monomers, and, then, (b) continuously preparing the block copolymer for continuously polymerizing the remainder of the monomers by continuously supplying the prepolymer to the first polymerization vessel of a continuous polymerization zone and simultaneously supplying the remainder of the monomers in the form of a monomer composed mainly of the aromatic vinyl hydrocarbon and/or a monomer composed mainly of the conjugated diene continuously and separately to the subsequent polymerization vessel(s). Furthermore, a block copolymer mixture containing two or more polymer blocks composed mainly of an aromatic vinyl hydrocarbon and one or more polymer blocks composed mainly of a conjugated diene having a high mutual interaction between the block copolymers therein can be advantageously prepared by (a) batchwise preparing the prepolymer and, then, (b) continuously preparing the block copolymers having the aromatic vinyl hydrocarbon contents thereof substantially continuously changed with an increase in the molecular weight of the block copolymers by broadening the molecular-weight distribution of at least one polymer block formed in the continuous polymerization zone (b).

2. 发明授权

US4377665A Process for producing block copolymer resin 失效
标题翻译：制备嵌段共聚物树脂的方法
公开(公告)号：US4377665A
公开(公告)日：1983-03-22
申请号：US316420
申请日：1981-10-29
申请人： Toshinori Shiraki , Akio Yamori , Hideo Morita
发明人： Toshinori Shiraki , Akio Yamori , Hideo Morita
IPC分类号： C08F2/00 , C08F297/00 , C08F297/04
CPC分类号： C08F297/04
摘要： In producing a block copolymer resin having vinyl aromatic hydrocarbon polymer blocks such as of styrene and polymer blocks primarily composed of conjugated diene such as of butadiene successively through living polymers using an organolithium compound as a catalyst in an aliphatic solvent, the vinyl aromatic hydrocarbon monomer for forming the vinyl aromatic hydrocarbon polymer block is added at a controlled rate, at the stage when the vinyl aromatic hydrocarbon content in the polymer formed has reached a certain value, higher than the polymerization rate of the vinyl aromatic hydrocarbon monomer at the polymerization temperature but at a rate which can maintain the solubility parameter of the liquid phase portion in the polymerization system at 7.7 or less, whereby a block copolymer resin with good transparency and impact strength can be produced with good productivity.
摘要翻译：在通过使用有机锂化合物作为催化剂的活性聚合物在脂肪族溶剂中生产具有乙烯基芳族烃聚合物嵌段如苯乙烯和主要由共轭二烯如丁二烯组成的聚合物嵌段的嵌段共聚物树脂时，乙烯基芳族烃单体在所形成的聚合物中的乙烯基芳族烃含量达到一定值，高于乙烯基芳族烃单体在聚合温度下的聚合速率的时候，以可控制的速率加入形成乙烯基芳烃聚合物嵌段可以将聚合体系中的液相部分的溶解度参数保持在7.7以下的速度，从而可以以良好的生产率制造具有良好透明性和冲击强度的嵌段共聚物树脂。

3. 发明授权

US4530966A Process for continuously polymerizing a block copolymer and the block copolymer mixture obtained therefrom 失效
标题翻译：用于连续聚合嵌段共聚物和由其获得的嵌段共聚物混合物的方法
公开(公告)号：US4530966A
公开(公告)日：1985-07-23
申请号：US509666
申请日：1983-06-30
申请人： Toshinori Shiraki , Akio Yamori , Hideo Morita
发明人： Toshinori Shiraki , Akio Yamori , Hideo Morita
IPC分类号： C08F297/04
CPC分类号： C08F297/04
摘要： A block copolymer containing two or more polymer blocks composed mainly of an aromatic vinyl hydrocarbon and one or more polymer blocks composed mainly of a conjugated diene having excellent mechanical properties can be advantageously prepared by (a) batchwise preparing the specified living polymer (i.e. prepolymer) of at least one aromatic vinyl hydrocarbon polymer block by using a portion of monomers, and, then, (b) continuously preparing the block copolymer for continuously polymerizing the remainder of the monomers by continuously supplying the prepolymer to the first polymerization vessel of a continuous polymerization zone and simultaneously supplying the remainder of the monomers in the form of a monomer composed mainly of the aromatic vinyl hydrocarbon and/or a monomer composed mainly of the conjugated diene continuously and separately to the subsequent polymerization vessel(s). Furthermore, a block copolymer mixture containing two or more polymer blocks composed mainly of an aromatic vinyl hydrocarbon and one or more polymer blocks composed mainly of a conjugated diene having a high mutual interaction between the block copolymers therein can be advantageously prepared by (a) batchwise preparing the prepolymer and, then, (b) continuously preparing the block copolymers having the aromatic vinyl hydrocarbon contents thereof substantially continuously changed with an increase in the molecular weight of the block copolymers by broadening the molecular-weight distribution of at least one polymer block formed in the continuous polymerization zone (b).
摘要翻译：含有两个以上主要由芳族乙烯基烃组成的聚合物嵌段和主要由共轭二烯组成的聚合物嵌段的嵌段共聚物的嵌段共聚物可以有利地通过（a）分批制备规定的活性聚合物（即预聚物）的至少一种芳香族乙烯基烃聚合物嵌段，然后（b）连续地制备嵌段共聚物，以通过连续地向第一聚合容器提供连续聚合的连续聚合剩余的单体同时将主要由芳族乙烯基烃和/或主要由共轭二烯组成的单体的单体形式的剩余单体连续和分别供给到随后的聚合反应器中。此外，通过（a）分批地制备含有主要由芳族乙烯基烃构成的两种或更多种聚合物嵌段和主要由共轭二烯组成的共轭二烯的嵌段共聚物混合物的嵌段共聚物混合物，制备预聚物，然后（b）通过扩大形成的至少一个聚合物嵌段的分子量分布，连续制备具有芳族乙烯基烃含量的嵌段共聚物基本上随嵌段共聚物分子量的增加而变化在连续聚合区（b）中。

4. 发明授权

US4657971A Modified block copolymer composition 失效
公开(公告)号：US4657971A
公开(公告)日：1987-04-14
申请号：US769466
申请日：1985-08-26
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00 , C08L51/04 , C08L51/06 , C08L53/02
CPC分类号： C08F287/00 , C08F8/04 , C08F8/46 , C08L51/006 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, abrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

5. 发明授权

US5272209A Modified block copolymer composition 失效
公开(公告)号：US5272209A
公开(公告)日：1993-12-21
申请号：US825788
申请日：1992-01-21
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00 , C08L53/02
CPC分类号： C08F287/00 , C08F8/04 , C08L51/006 , C08L77/00 , C08F2810/20 , Y10S525/94
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, adrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

6. 发明授权

US5183857A Modified block copolymer and a process for producing the same 失效
标题翻译：改性嵌段共聚物及其制备方法
公开(公告)号：US5183857A
公开(公告)日：1993-02-02
申请号：US443188
申请日：1989-11-30
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00
CPC分类号： C08F287/00 , C08F8/04 , C08F8/46 , C08L51/006 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, adrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

7. 发明授权

US4657970A Modified block copolymer composition 失效
公开(公告)号：US4657970A
公开(公告)日：1987-04-14
申请号：US769506
申请日：1985-08-26
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00 , C08L51/04 , C08L53/02 , C08L69/00
CPC分类号： C08F287/00 , C08F8/04 , C08F8/46 , C08L51/006 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, adrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

8. 发明授权

US5272208A Modified block copolymer composition 失效
标题翻译：改性嵌段共聚物组成
公开(公告)号：US5272208A
公开(公告)日：1993-12-21
申请号：US819636
申请日：1992-01-10
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00 , C08L53/02
CPC分类号： C08L51/006 , C08F287/00 , C08F8/04 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, adrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.
摘要翻译：一种改性嵌段共聚物组合物，其包含热塑性聚合物和基本上由单乙烯基取代的芳族烃聚合物嵌段的基础嵌段共聚物和烯属不饱和度不超过20％的烯烃化合物聚合物嵌段组成的改性嵌段共聚物，所述嵌段共聚物具有含有羧酸基团和/或其衍生基团的分子单元接枝到其上。本发明的改性嵌段共聚物组合物是耐冲击性，粘合性，涂料粘合性，耐候性，耐热劣化性，透明性和光泽性优异的耐热性，耐侵蚀性，耐压缩性优异的橡胶状或皮革状组合物的树脂组合物耐电阻性，粘合性，透明性，耐油性，耐候性和耐热老化性。

9. 发明授权

US4927889A Modified block copolymer and a process for producing the same 失效
标题翻译：改性嵌段共聚物及其制备方法
公开(公告)号：US4927889A
公开(公告)日：1990-05-22
申请号：US113238
申请日：1987-10-27
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00
CPC分类号： C08F287/00 , C08F8/04 , C08F8/46 , C08L51/006 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, abrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.

10. 发明授权

US4628072A Modified block copolymer composition 失效
标题翻译：改性嵌段共聚物组成
公开(公告)号：US4628072A
公开(公告)日：1986-12-09
申请号：US432923
申请日：1982-09-30
申请人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
发明人： Toshinori Shiraki , Fusakazu Hayano , Hideo Morita
IPC分类号： C08F8/46 , C08F287/00 , C08L51/00 , C08L77/00 , C08L53/00 , C08L53/02
CPC分类号： C08F287/00 , C08F8/04 , C08F8/46 , C08L51/006 , C08L77/00 , C08F2810/20
摘要： A modified block copolymer composition comprising a thermoplastic polymer and a modified block copolymer consisting essentially of a base block copolymer of a monovinyl substituted aromatic hydrocarbon polymer block and an olefin compound polymer block having an ethylenic unsaturation degree not exceeding 20%, the base block copolymer having a molecular unit containing a carboxylic acid group and/or a group derived therefrom grafted thereto. The modified block copolymer composition of the present invention is a resinous composition excellent in impact resistance, adhesion, paint adhesion, weatherability, resistance to thermal deterioration, transparency and gloss or a rubbery or leather-like composition excellent in heat resistance, abrasion resistance, compression set resistance, adhesion, transparency, oil resistance, weatherability and resistance to heat aging.
摘要翻译： PCT No.PCT / JP82 / 00316 Sec。 371日期1982年9月30日 102（e）1982年9月30日PCT申请1982年8月13日PCT公布。公开号WO83 / 日本1983年2月17日。一种改性嵌段共聚物组合物，其包含热塑性聚合物和改性嵌段共聚物，其基本上由单乙烯基取代的芳族烃聚合物嵌段与烯属不饱和度不超过20的烯烃化合物聚合物嵌段％，具有含有羧酸基和/或其衍生基团的分子单元的基础嵌段共聚物接枝到其上。本发明的改性嵌段共聚物组合物是耐冲击性，粘合性，涂料粘附性，耐候性，耐热劣化性，透明性和光泽性优异的耐热性，耐磨性，压缩性优异的橡胶状或皮革状组合物的树脂组合物耐电阻性，粘合性，透明性，耐油性，耐候性和耐热老化性。

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