公开(公告)号：US5057574A

公开(公告)日：1991-10-15

申请号：US523269

申请日：1990-05-14

申请人： Makoto Uchida ,  Yutaka Toyooka ,  Kazuo Kishida ,  Akira Nakata ,  Naoki Yamamoto

发明人： Makoto Uchida ,  Yutaka Toyooka ,  Kazuo Kishida ,  Akira Nakata ,  Naoki Yamamoto

IPC分类号： C08F212/12 ,  C08L25/16

CPC分类号： C08F212/12 ,  C08L25/16

摘要： A process for producing an .alpha.-alkyl-substituted aromatic vinyl copolymer constituted of 60 to 85 parts by weight of the .alpha.-alkyl-substituted aromatic vinyl monomer, 15 to 35 parts by weight of a vinyl cyanide monomer, and 0 to 40 parts by weight of another vinyl monomer copolymerizable with these monomers, which process is characterized in thatall the amount of the aromatic vinyl monomer necessary for the entire polymerization and such partial amounts of the vinyl cyanide monomer and another copolymerizable vinyl monomer as to give a predetermined copolymer composition with respect to the content of the aromatic vinyl monomer, are first charged and emulsified andthe emulsion polymerization is then initiated and carried out by adding dropwise continuously the residual amounts of the vinyl cyanide monomer and another copolymerizable vinyl monomer in such a manner that the range of change in the content of the aromatic vinyl monomer in the copolymer during the polymerization reaction will not vary more than 2% in the range of conversion of 0 to 90%; and a thermoplastic resin composition comprising[A] 50 to 90% by weight of a copolymer constituted of 60 to 85 parts by weight of an .alpha.-alkyl-substituted aromatic vinyl monomer, 15 to 35 parts by weight of a vinyl cyanide monomer, and 0 to 40 parts by weight of another vinyl monomer copolymerizable with these monomers, the copolymer being produced in such a manner that the range of change in the content of the aromatic vinyl monomer in the copolymer during the polymerization reaction will not vary more than 2% in the range of conversion of 0 to 90, and[B] 10 to 50% by weight of a graft copolymer constituted of 30 to 85 parts by weight of a rubber polymer and 15 to 70 parts by weight of a grafted polymer consisting of a monovinyl aromatic monomer, vinyl cyanide monomer, and another monomer copolymerizable with them in respective proportions of 85-40:0-40:0-80,where the total amount of polymers [A] and [B] is 100% by weight.

公开(公告)号：US4877844A

公开(公告)日：1989-10-31

申请号：US135470

申请日：1987-12-21

申请人： Kazuo Kishida ,  Yutaka Toyooka ,  Yoshiyuki Mikami

发明人： Kazuo Kishida ,  Yutaka Toyooka ,  Yoshiyuki Mikami

IPC分类号： C08F236/12 ,  C08F279/02

CPC分类号： C08F236/12 ,  C08F279/02

摘要： A process for producing a low gloss thermoplastic resin which comprises polymerizing in two steps from 20 to 70 parts by weight of a butadiene polymer, at least 70% by weight of which is constituted by butadiene, with from 30 to 80 parts by weight of a total of from 15 to 40% by weight of a vinyl cyanide monomer and from 60 to 85% by weight of an aromatic vinyl monomer, characterized in that for the polymerization of the first step, the butadiene polymer, the vinyl cyanide monomer and the aromatic vinyl monomer were charged in amounts corresponding to from 20 to 80% by weight of the entire butadiene polymer, from 20 to 80% by weight of the entire vinyl cyanide monomer and from 20 to 80% by weight of the entire aromatic vinyl monomer, respectively, and after the completion of the polymerization of the first step, the rest of the butadiene polymer, the vinyl cyanide monomer and the aromatic vinyl monomer were charged for the polymerization of the second step.

摘要翻译： 一种低光泽性热塑性树脂的制造方法，其特征在于，将20〜70重量份的丁二烯聚合物，其中至少70重量％由丁二烯构成，其中20〜70重量份， 总计为15至40重量％的乙烯基氰单体和60至85重量％的芳族乙烯基单体，其特征在于，对于第一步骤的聚合，丁二烯聚合物，乙烯基氰单体和芳族化合物 乙烯基单体的量相当于整个丁二烯聚合物的20至80重量％，全部乙烯基氰单体的20至80重量％和芳族乙烯基单体总量的20至80重量％ ，在第一步聚合完成后，加入其余的丁二烯聚合物，乙烯基氰单体和芳族乙烯基单体进行第二步的聚合反应。

公开(公告)号：US4912162A

公开(公告)日：1990-03-27

申请号：US10426

申请日：1987-02-03

申请人： Kazuo Kishida ,  Yutaka Toyooka ,  Haruyoshi Kitahara

发明人： Kazuo Kishida ,  Yutaka Toyooka ,  Haruyoshi Kitahara

IPC分类号： C08F285/00 ,  C08L51/00

CPC分类号： C08L51/00 ,  Y10S525/902

摘要： Disclosed is a graft copolymer resin prepared by graft polymerizing a vinyl compound onto a composite-structured acrylic rubber whose particles are composed of a core consisting of a diene rubber enlarged by treatment with an acid group-containing copolymer latex, and an outer layer consisting of an acrylate polymer having a crosslinked structure formed by the combined use of a graft-linking agent and a cross-linking agent. This graft copolymer resin may be blended with a rigid thermoplastic resin in a specific proportion. This resin composition imparts a good gloss to the molded articles formed therefrom, while retaining excellent impact resistance and weather resistance.

摘要翻译： 公开了通过将乙烯基化合物接枝聚合到复合结构的丙烯酸橡胶上而制备的接枝共聚物树脂，该复合结构的丙烯酸橡胶的颗粒由通过用含酸基的共聚物胶乳处理而扩大的二烯橡胶组成的芯和由 具有通过组合使用接枝交联剂和交联剂形成的交联结构的丙烯酸酯聚合物。 该接枝共聚物树脂可以与特定比例的刚性热塑性树脂共混。 该树脂组合物对由其形成的模塑制品赋予良好的光泽，同时保持优异的耐冲击性和耐候性。

公开(公告)号：US4804706A

公开(公告)日：1989-02-14

申请号：US25628

申请日：1987-03-02

申请人： Kazuo Kishida ,  Yutaka Toyooka ,  Atsushi Kimura

发明人： Kazuo Kishida ,  Yutaka Toyooka ,  Atsushi Kimura

IPC分类号： C08F212/04 ,  C08F222/40 ,  C08L25/02 ,  C08L51/04 ,  C08L77/00 ,  C08L51/00

CPC分类号： C08F222/40

摘要： The present invention provides a process for the preparation of maleimide copolymers by emulsion polymerization of an aromatic vinyl monomer, a vinyl cyanide monomer and a maleimide monomer in specific proportions wherein the polymerization is carried out by charging not less than a specific proportion of the aromatic vinyl monomer and optionally not more than a specific proportion of the vinyl cyanide monomer into the polymerization system before initiation of the polymerization; adding, continuously or dividedly, a mixture composed of the total amount of the maleimide monomer and the remainder of the other monomers to the polymerization system after initiation of the polymerization; maintaining the pH of the aqueous phase of the polymerization system in the range of 3 to 9 at the initiation of said polymerization; and using a redox catalyst containing an oil-soluble organic peroxide. According to this polymerization process, maleimide copolymers having excellent thermal resistance and resistance to thermal decomposition can be prepared in high yield.The present invention also provides a resin composition having excellent thermal resistance, resistance to thermal decomposition, and impact resistance which is formed by blending, in a specific proportion, a maleimide copolymer prepared by the aforesaid process with a rubber-reinforced resin obtained by grafting a vinyl cyanide monomer or the like onto a specific elastomer; and optionally blending the resulting thermoplastic resin composition with a thermoplastic resin that is hard at room temperature.

摘要翻译： 本发明提供了一种通过芳香族乙烯基单体，乙烯基氰单体和马来酰亚胺单体以特定比例的乳液聚合制备马来酰亚胺共聚物的方法，其中聚合通过将不少于特定比例的芳族乙烯基 单体，并且任选地不超过特定比例的乙烯基氰单体在聚合开始之前进入聚合体系; 在聚合开始后，向马来酰亚胺单体和剩余的其它单体组成的混合物连续地或分开地加入到聚合体系中; 在所述聚合开始时，将聚合体系的水相的pH保持在3〜9的范围内; 并使用含有油溶性有机过氧化物的氧化还原催化剂。 根据该聚合方法，可以高产率制备具有优异的耐热性和耐热分解性的马来酰亚胺共聚物。 本发明还提供一种具有优异的耐热性，耐热分解性和耐冲击性的树脂组合物，其通过以特定比例将通过上述方法制备的马来酰亚胺共聚物与通过将上述方法获得的橡胶增强树脂 乙烯基氰单体等涂覆在特定的弹性体上; 任选地将得到的热塑性树脂组合物与在室温下硬的热塑性树脂共混。

公开(公告)号：US5064906A

公开(公告)日：1991-11-12

申请号：US405428

申请日：1989-08-28

申请人： Kazuo Kishida ,  Yutaka Toyooka ,  Haruyoshi Kitahara

发明人： Kazuo Kishida ,  Yutaka Toyooka ,  Haruyoshi Kitahara

IPC分类号： C08F285/00 ,  C08L51/00

CPC分类号： C08L51/00 ,  Y10S525/902

摘要： Disclosed is a graft copolymer resin prepared by graft polymerizing a vinyl compound onto a composite-structured acrylic rubber whose particles are composed of a core consisting of a diene rubber enlarged by treatment with an acid group-containing copolymer latex, and an outer layer consisting of an acrylate polymer having a crosslinked structure formed by the combined use of a graft-linking agent and a cross-linking agent. This graft copolymer resin may be blended with a rigid thermoplastic resin in a specific proportion. This resin composition imparts a good gloss to the molded articles formed therefrom, while retaining excellent impact resistance and weather resistance.

公开(公告)号：US4757109A

公开(公告)日：1988-07-12

申请号：US928279

申请日：1986-10-14

申请人： Kazuo Kishida ,  Yutaka Toyooka ,  Atsushi Kimura

发明人： Kazuo Kishida ,  Yutaka Toyooka ,  Atsushi Kimura

IPC分类号： C08F212/04 ,  C08F222/40 ,  C08L25/02 ,  C08L51/04 ,  C08L39/04 ,  C08L51/00

CPC分类号： C08F222/40

摘要： A process for the preparation of maleimide copolymers by emulsion polymerization of 50 to 80% by weight of an aromatic vinyl monomer, 10 to 30% by weight of a vinyl cyanide monomer, and 5 to 40% by weight of a maleimide monomer comprising a three step polymerization process wherein the remaining vinyl cyanide monomer is separately added in the third step of said process.

摘要翻译： PCT No.PCT / JP86 / 00252 Sec。 一九八六年十月十四日 102（e）1986年10月14日PCT PCT日期：1986年5月16日PCT公布。 出版物WO86 / 06732 日本公报1986年11月20日。一种通过乳液聚合制备马来酰亚胺共聚物的方法，其通过50至80重量％的芳族乙烯基单体，10至30重量％的乙烯基氰单体和5至40重量％ 的包含三步聚合方法的马来酰亚胺单体，其中在所述方法的第三步中分离加入剩余的乙烯基氰单体。

公开(公告)号：US4556692A

公开(公告)日：1985-12-03

申请号：US676810

申请日：1984-11-30

申请人： Kazuo Kishida ,  Naoki Yamamoto ,  Yasumasa Sato

发明人： Kazuo Kishida ,  Naoki Yamamoto ,  Yasumasa Sato

IPC分类号： C08L25/16 ,  C08L51/00 ,  C08L51/04 ,  C08F265/02

CPC分类号： C08L25/16 ,  C08L51/003 ,  C08L51/04

摘要： A thermoplastic resin composition having excellent impact resistance and heat resistance which comprises 5 to 95% by weight of a graft copolymer (I) obtained by polymerizing 93 to 30 parts by weight of a monomer or a monomer mixture for grafting comprising 30 to 100% by weight of at least one monomer selected from the group consisting of styrene, .alpha.-methylstyrene, acrylonitrile and methyl methacrylate and 0 to 70% by weight of at least one copolymerizable monomer having CH.sub.2 .dbd.C

摘要翻译： 具有优异的耐冲击性和耐热性的热塑性树脂组合物包含5至95重量％的通过将93至30重量份的单体或用于接枝的单体混合物聚合而获得的接枝共聚物（I），其包含30至100％ 至少一种选自苯乙烯，α-甲基苯乙烯，丙烯腈和甲基丙烯酸甲酯的单体的重量和0-70％重量的至少一种可共聚的单体，其中R 2为C < 通过加入0.1至5重量份（以固体计）含酸基共聚物（B）胶乳获得的粒径为至少0.2μm的附聚颗粒的橡胶胶乳的重量（以固体计） 得自3至30重量％的含酸基单体，97至35重量％的至少一种在烷基中具有1至12个碳原子的丙烯酸烷基酯和0至48重量％的至少一种 单乙烯基单体可共聚 （100重量％）相对于100重量份（以固体计）的100重量份（重量）固体成分的100〜50重量％ 丁二烯和0至50重量％的其它可共聚的CH 2 = C <基团的单体（总共100重量％）; 95〜5重量％的通过聚合α-甲基苯乙烯和至少一种其它可共聚的CH 2 = C <基团的单体获得的热塑性树脂（II）; 和0〜50重量％的不含α-甲基苯乙烯单元的其它热塑性树脂（III），所述组分（I），（II）和（III）配混以使所述丁二烯橡胶（A）的含量在 整个组合物的总重量为3〜40重量％，α-甲基苯乙烯单元的含量为10〜75重量％。

公开(公告)号：US4558099A

公开(公告)日：1985-12-10

申请号：US675232

申请日：1984-11-27

申请人： Kazuo Kishida ,  Naoki Yamamoto ,  Yasumasa Sato

发明人： Kazuo Kishida ,  Naoki Yamamoto ,  Yasumasa Sato

IPC分类号： C08C1/07 ,  C08F279/02 ,  C08F279/04 ,  C08F265/02

CPC分类号： C08F279/04 ,  C08C1/07 ,  C08F279/02

摘要： A thermoplastic resin having excellent impact resistance and heat resistance obtainable by polymerizing 93 to 30 parts by weight of a monomer mixture comprising 20 to 90% by weight of at least one .alpha.-alkylaromatic vinyl monomer, 10 to 40% by weight of at least one vinyl cyanide monomer and 0 to 60% by weight of at least one vinyl monomer copolymerizable therewith (100% by weight in total) in the presence of 7 to 70 parts by weight (in terms of solid) of a rubber latex of a large particle size having a particle diameter of at least 0.2 .mu.m obtained by adding 0.1 to 5 parts by weight (in terms of solid) of an acid-group containing copolymer (B) latex obtained from 3 to 30% by weight of an acid-group containing monomer, 97 to 35% by weight of at least one alkyl acrylate having 1 to 12 carbon atoms in the alkyl group, and 0 to 48% by weight of at least one vinyl monomer copolymerizable therewith (100% by weight in total) to 100 parts by weight (in terms of solid) of a rubber (A) latex of a small particle size having a pH of 7 or higher obtained from 100 to 50% by weight of 1,3-butadiene and 0 to 50% by weight of a monomer having CH.sub.2 .dbd.C

摘要翻译： 具有优异抗冲击性和耐热性的热塑性树脂可通过聚合93至30重量份的包含20至90重量％的至少一种α-烷基芳族乙烯基单体，10至40重量％的至少一种 乙烯基氰单体和0至60重量％的至少一种可与其共聚的乙烯基单体（总共100重量％），在7至70重量份（以固体计）的大颗粒的橡胶胶乳的存在下 通过加入0.1至5重量份（以固体计）含有酸的基团的共聚物（B）得到的粒径至少为0.2μm的粒径为3至30重量％的酸基 至少一种在烷基中具有1-12个碳原子的丙烯酸烷基酯和至少一种可与其共聚的至少一种乙烯基单体（总共100重量％）至少至少一个至少一个 橡胶（A）胶乳100重量份（以固体计） 得到100〜50重量％的1,3-丁二烯和0〜50重量％的具有CH 2 = C <基团且可与其共聚的单体（100重量％）的pH为7以上的小粒径 总共）。

公开(公告)号：US4513111A

公开(公告)日：1985-04-23

申请号：US473369

申请日：1983-03-08

申请人： Kazuo Kishida ,  Naoki Yamamoto ,  Kozi Nishida ,  Toshihito Narita ,  Yasumasa Sato

发明人： Kazuo Kishida ,  Naoki Yamamoto ,  Kozi Nishida ,  Toshihito Narita ,  Yasumasa Sato

IPC分类号： C08F2/16 ,  C08F2/18 ,  C08F2/22 ,  C08F279/02 ,  C08F285/00 ,  C08L9/04 ,  C08L9/08 ,  C08L9/10

CPC分类号： C08F279/02 ,  C08F285/00

摘要： In a process comprising adding an ethylenic monomer or monomer mixture (B) to a rubbery polymer (A) latex, emulsion-polymerizing it to produce a graft copolymer (C) latex, then adding an acidic substance or an electrolyte to said graft copolymer (C) latex to partially coagulate the latex, thereafter either first adding an ethylenic monomer or monomer mixture (D) and then adding a suspension polymerization stabilizer or simultaneously adding an ethylenic monomer or monomer mixture (D) and a suspension polymerization stabilizer, and carrying out suspension polymerization to obtain a graft copolymer (E) in the form of beads, a process for producing an impact-resistant resin wherein:(1) said rubbery polymer (A) contains at least 60% by weight of a diene monomer component and has a degree of swelling of 10-35, a gel content of 70% by weight or more and a weight average particle diameter of 0.2-0.5.mu. and the major part of the particles has a particle diameter ranging from 0.03.mu. to 1.0.mu.;(2) said ethylenic monomer or monomer mixture of (B) and (D) independently comprises 50-100% by weight of an aromatic vinyl monomer and 50-0% by weight of a vinyl monomer copolymerizable therewith; and;(3) said graft copolymer (C) has a free polymer rate of 10% or higher and a reduced viscosity (.eta..sub.sp /C), determined by dissolving 0.1 g of its acetone-soluble fraction into 100 ml of N,N-dimethylformamide and measuring the viscosity at 25.degree. C., of 0.3-1.0 dl/g.

摘要翻译： 在包括向橡胶状聚合物（A）胶乳中加入乙烯性单体或单体混合物（B）的方法中，将其乳液聚合以产生接枝共聚物（C）胶乳，然后向所述接枝共聚物中加入酸性物质或电解质 C）将胶乳部分凝固，然后首先加入乙烯性单体或单体混合物（D），然后加入悬浮聚合稳定剂或同时加入乙烯性单体或单体混合物（D）和悬浮聚合稳定剂，并进行 悬浮聚合以得到珠粒形式的接枝共聚物（E），一种制备耐冲击树脂的方法，其中：（1）所述橡胶状聚合物（A）含有至少60重量％的二烯单体组分，并且具有 溶胀度为10-35，凝胶含量为70重量％以上，重均粒径为0.2〜0.5μm，主要部分的粒径为0.03〜1.0μm ; （2）所述乙烯单体或（B）和（D）的单体混合物独立地包含50-100重量％的芳族乙烯基单体和50-0重量％的可与其共聚的乙烯基单体; 和; （3）所述接枝共聚物（C）具有10％以上的游离聚合物比例和通过将0.1克丙酮可溶成分溶解在100ml N，N-二甲基甲酰胺中而确定的比浓粘度（eta sp /℃） 并测量25℃下的粘度为0.3-1.0dl / g。

公开(公告)号：US5055529A

公开(公告)日：1991-10-08

申请号：US329872

申请日：1989-03-28

申请人： Kazuo Kishida ,  Kiyokazu Kitai ,  Masahiro Kaneda ,  Kenji Okano

发明人： Kazuo Kishida ,  Kiyokazu Kitai ,  Masahiro Kaneda ,  Kenji Okano

IPC分类号： C08F2/24 ,  C08F2/44 ,  C08F220/00 ,  C08F220/14 ,  C08F220/18 ,  C08F265/06 ,  C08L27/06 ,  C08L33/10 ,  C08L51/00 ,  C08L101/00

CPC分类号： C08L27/06 ,  C08F265/06 ,  C08L101/00 ,  C08L51/003

摘要： A processing aid for a thermoplastic resin is disclosed, which is a two-stage polymer obtained by polymerizing (B) 5 to 50 parts by weight of a monomer or monomer mixture composed mainly of methyl methacrylate in the presence of (A) 50 to 95 parts by weight of a polymer comprising 100 to 50% by weight of units of a methacrylic acid ester other than methyl methacrylate and 0 to 50% by weight of units of other monomer copolymerizable with the methacrylic acid ester and having a reduced viscosity .eta.sp/C not larger than 2.0 dl/g, so that the total amount of the components (A) and (B) is 100 parts by weight and the reduced viscosity .eta.sp of the final polymer is not larger than 2.0 dl/g. A thermoplastic resin having the processing aid incorporated therein has an improved shaping processability, and a shaped article mode therefrom has good surface characteristics.