公开(公告)号：KR100453875B1

公开(公告)日：2004-10-20

申请号：KR1020000082794

申请日：2000-12-27

Applicant: 제일모직주식회사

Inventor： 박재범 ,  하두한 ,  임용환 ,  김경수

IPC: C08F279/04

CPC classification number: C08F285/00 ,  C08F279/04

Abstract: The present invention provides a method of preparing a graft copolymer with a high rubber content showing good mechanical properties, which comprises (i) a first step of preparing a first graft copolymer latex by graft-polymerizing a monomer mixture of styrene and acrylonitrile onto a rubber polymer using an oil-soluble initiator; and (ii) a second step of preparing a second graft copolymer latex by reacting said first graft copolymer latex using a redox catalyst system and an initiator and adding continuously a monomer mixture of styrene and acrylonitrile, a molecular weight controlling agent and an initiator over 2-6 hours.

Abstract translation: 本发明提供一种制备具有良好机械性能的高橡胶含量的接枝共聚物的方法，该方法包括（i）通过将苯乙烯和丙烯腈的单体混合物接枝聚合到橡胶上来制备第一接枝共聚物胶乳的第一步骤 使用油溶性引发剂的聚合物; （ii）通过使用氧化还原催化剂体系和引发剂使所述第一接枝共聚物胶乳反应并且连续添加苯乙烯和丙烯腈的单体混合物，分子量控制剂和引发剂来制备第二接枝共聚物胶乳的第二步骤 -6个小时。

公开(公告)号：KR1020030042626A

公开(公告)日：2003-06-02

申请号：KR1020010073352

申请日：2001-11-23

Applicant: 제일모직주식회사

Inventor： 박재범 ,  하두한 ,  임용환 ,  김경수

IPC: C08F279/04

CPC classification number: C08F279/04 ,  C08F212/10

Abstract: PURPOSE: A process for preparing a SAN(acrylonitrile-butadiene-styrene) graft copolymer of core-shell structure having excellent appearance and whiteness and high rubber content is provided. CONSTITUTION: The process for preparing a SAN graft copolymer comprises the steps of: introducing ion exchanged water into which a water soluble initiator is dissolved, and an emulsifier into a polybutadiene elastomeric polymer having an average particle diameter of 0.28 to 0.33 micrometers and gel content of 75 to 85 wt%; heating the mixture to 55 to 65 deg.C in order to swell the water soluble initiator into the elastomeric polymer and in order to decompose to form a radical gradually; introducing continuously an aromatic vinyl compound and an unsaturated nitrile compound which are the monomers to be grafted onto the elastomeric polymer, an emulsifier and a molecular weight modifier; heating the mixture to the final temperature of 75 to 85 deg.C and terminating the polymerization when the conversion is 95 to 98% and solid content is 40 to 44 wt% to obtain a SAN graft copolymer latex; and then introducing a solidifying agent consisting of an aqueous acid solution and aqueous salt solution to solidify the SAN graft copolymer resin.

Abstract translation: 目的：提供具有优异的外观和白度以及高橡胶含量的核 - 壳结构的SAN（丙烯腈 - 丁二烯 - 苯乙烯）接枝共聚物的方法。 构成：制备SAN接枝共聚物的方法包括以下步骤：引入溶解有水溶性引发剂的离子交换水，将乳化剂引入平均粒径为0.28至0.33微米的聚丁二烯弹性体聚合物中，并将凝胶含量 75〜85重量％ 将混合物加热至55至65℃以便将水溶性引发剂溶胀到弹性体聚合物中，并逐渐分解形成基团; 连续引入作为待接枝到弹性体聚合物上的单体的芳族乙烯基化合物和不饱和腈化合物，乳化剂和分子量调节剂; 将混合物加热至75〜85℃的最终温度，当转化率为95〜98％，固体成分为40〜44重量％时终止聚合，得到SAN接枝共聚物胶乳; 然后引入由酸水溶液和盐水溶液组成的固化剂以固化SAN接枝共聚物树脂。

公开(公告)号：KR1020020054103A

公开(公告)日：2002-07-06

申请号：KR1020000082794

申请日：2000-12-27

Applicant: 제일모직주식회사

Inventor： 박재범 ,  하두한 ,  임용환 ,  김경수

IPC: C08F279/04

CPC classification number: C08F285/00 ,  C08F279/04

Abstract: PURPOSE: Provided is a method for preparing a novel graft copolymer having high rubber content and improved natural color, as well as excellent in impact resistance and fluidity. CONSTITUTION: The method comprises the steps of (i) mixing 10-30 wt% of graft monomer mixture with fat-soluble thermal decomposition initiator with stirring, introducing the mixture into rubbery polymer, introducing molecular weight controlling agent and ion exchange water, elevating the temperature with stirring, and continuously stirring within 10 minutes when the temperature reaches 55-65 deg.C to swell most of the introduced graft monomer and polymerization initiator into rubber particles, and introducing an emulsifier and elevating a temperature of reactor to initiate a polymerization, thereby the first copolymer latex being produced; and (ii) introducing redox based catalyst mixture and polymerization initiator in a reactor in the presence of the first graft copolymer latex, stirring the mixture for 5-10 minutes, mixing 90-70 wt% of residual graft monomer mixture and molecular weight controlling agent with stirring, and continuously introducing the latter mixture over 2-5 hours and polymerization initiator at the same time for 2-5 hours to graft react the trace graft monomer and the polymerization initiator, thereby the second copolymer latex being produced.

Abstract translation: 目的：提供一种具有高橡胶含量和改进的自然色，以及耐冲击性和流动性优异的新型接枝共聚物的方法。 方法：该方法包括以下步骤：（i）将10-30重量％的接枝单体混合物与脂溶性热分解引发剂搅拌混合，将混合物引入橡胶状聚合物，引入分子量控制剂和离子交换水， 在温度达到55-65摄氏度的10分钟内连续搅拌，将大多数引入的接枝单体和聚合引发剂溶胀到橡胶颗粒中，并引入乳化剂并升高反应器的温度以引发聚合反应， 从而产生第一共聚物胶乳; 和（ii）在反应器中在第一接枝共聚物胶乳存在下引入氧化还原型催化剂混合物和聚合引发剂，将混合物搅拌5-10分钟，混合90-70重量％的残余接枝单体混合物和分子量控制剂 在2-5小时内连续引入后者混合物，同时将聚合引发剂同时进行2-5小时，以使接枝单体和聚合引发剂接枝反应，从而制备第二共聚物胶乳。

公开(公告)号：KR100402281B1

公开(公告)日：2003-10-22

申请号：KR1020000083860

申请日：2000-12-28

Applicant: 제일모직주식회사

Inventor： 하두한 ,  김경수 ,  임용환

IPC: C08F220/18

Abstract: PURPOSE: Provided is a thermoplastic resin composition excellent in impact-resistance, gloss, and weather-resistance, which is produced by mixing an acryl-based graft copolymer latex and a graft ABS copolymer latex. CONSTITUTION: The thermoplastic resin composition is produced by mixing 70-100pts.wt. of the acryl-based graft copolymer latex and 30-0pts.wt. of the graft ABS copolymer latex with a graft rate of 40-60% and coagulating by using a coagulant and dehydrating and drying, wherein the graft ABS copolymer latex is produced by using a polybutadiene rubber with an average particle diameter of 0.3-0.45 micrometer. And the acryl-based graft copolymer latex is produced from a crosslinked acryl-based rubber latex with a polymerization rate of 95-99%, an average particle size of 0.15-25 micrometer, the gel content of 85-95wt%, and a solid component of 39-44%.

Abstract translation: 目的：提供一种通过将丙烯酸类接枝共聚物胶乳和接枝ABS共聚物胶乳混合而制得的耐冲击性，光泽度和耐候性优异的热塑性树脂组合物。 构成：热塑性树脂组合物通过混合70-100pts.wt。 的丙烯酸类接枝共聚物胶乳和30-0pts.wt。 的接枝率为40-60％的接枝ABS共聚物胶乳，并通过使用凝固剂和脱水干燥而凝固，其中接枝ABS共聚物胶乳是通过使用平均粒径为0.3-0.45微米的聚丁二烯橡胶制备的。 并且丙烯酸基接枝共聚物胶乳由交联丙烯酰基橡胶胶乳制备，聚合率为95-99％，平均粒径为0.15-25微米，凝胶含量为85-95重量％，固体 组分39-44％。

公开(公告)号：KR1020020054691A

公开(公告)日：2002-07-08

申请号：KR1020000083860

申请日：2000-12-28

Applicant: 제일모직주식회사

Inventor： 하두한 ,  김경수 ,  임용환

IPC: C08F220/18

CPC classification number: C08F265/06 ,  C08F2/26 ,  C08F212/08 ,  C08F212/12 ,  C08F220/44 ,  C08L9/10

Abstract: PURPOSE: Provided is a thermoplastic resin composition excellent in impact-resistance, gloss, and weather-resistance, which is produced by mixing an acryl-based graft copolymer latex and a graft ABS copolymer latex. CONSTITUTION: The thermoplastic resin composition is produced by mixing 70-100pts.wt. of the acryl-based graft copolymer latex and 30-0pts.wt. of the graft ABS copolymer latex with a graft rate of 40-60% and coagulating by using a coagulant and dehydrating and drying, wherein the graft ABS copolymer latex is produced by using a polybutadiene rubber with an average particle diameter of 0.3-0.45 micrometer. And the acryl-based graft copolymer latex is produced from a crosslinked acryl-based rubber latex with a polymerization rate of 95-99%, an average particle size of 0.15-25 micrometer, the gel content of 85-95wt%, and a solid component of 39-44%.

Abstract translation: 目的：提供通过混合丙烯酸系接枝共聚物胶乳和接枝ABS共聚物胶乳而制成的耐冲击性，光泽，耐候性优异的热塑性树脂组合物。 构成：热塑性树脂组合物通过混合70-100pts.wt。 的丙烯酰基接枝共聚物胶乳和30-0pts.wt。 的接枝率为40-60％的接枝ABS共聚物胶乳，并通过使用凝结剂进行凝结和脱水干燥，其中通过使用平均粒径为0.3-0.45微米的聚丁二烯橡胶制备接枝ABS共聚物胶乳。 丙烯酰基接枝共聚物胶乳由聚合率95-99％，平均粒度为0.15-25微米，凝胶含量为85-95重量％的交联丙烯酸系橡胶胶乳制成，固体 成分为39-44％。

公开(公告)号：KR100455101B1

公开(公告)日：2004-11-06

申请号：KR1020010073352

申请日：2001-11-23

Applicant: 제일모직주식회사

Inventor： 박재범 ,  하두한 ,  임용환 ,  김경수

IPC: C08F279/04

Abstract: PURPOSE: A process for preparing a SAN(acrylonitrile-butadiene-styrene) graft copolymer of core-shell structure having excellent appearance and whiteness and high rubber content is provided. CONSTITUTION: The process for preparing a SAN graft copolymer comprises the steps of: introducing ion exchanged water into which a water soluble initiator is dissolved, and an emulsifier into a polybutadiene elastomeric polymer having an average particle diameter of 0.28 to 0.33 micrometers and gel content of 75 to 85 wt%; heating the mixture to 55 to 65 deg.C in order to swell the water soluble initiator into the elastomeric polymer and in order to decompose to form a radical gradually; introducing continuously an aromatic vinyl compound and an unsaturated nitrile compound which are the monomers to be grafted onto the elastomeric polymer, an emulsifier and a molecular weight modifier; heating the mixture to the final temperature of 75 to 85 deg.C and terminating the polymerization when the conversion is 95 to 98% and solid content is 40 to 44 wt% to obtain a SAN graft copolymer latex; and then introducing a solidifying agent consisting of an aqueous acid solution and aqueous salt solution to solidify the SAN graft copolymer resin.

Abstract translation: 目的：提供一种制备具有优异外观和白度以及高橡胶含量的核 - 壳结构的SAN（丙烯腈 - 丁二烯 - 苯乙烯）接枝共聚物的方法。 构成：用于制备SAN接枝共聚物的方法包括以下步骤：将溶解有水溶性引发剂的离子交换水和乳化剂引入平均粒径为0.28-0.33微米的聚丁二烯弹性体聚合物中， 75至85重量％; 加热混合物至55-65℃以使水溶性引发剂溶胀到弹性体聚合物中并逐渐分解形成自由基; 将作为待接枝单体的芳族乙烯基化合物和不饱和腈化合物连续引入弹性体聚合物，乳化剂和分子量调节剂; 加热至75〜85℃的最终温度，当转化率为95〜98％，固含量为40〜44wt％时，终止聚合，得到SAN接枝共聚物胶乳; 然后引入由酸水溶液和盐水溶液组成的固化剂以固化SAN接枝共聚物树脂。