CN1048260C - 一种制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳的方法 - Google Patents
一种制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳的方法 Download PDFInfo
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- CN1048260C CN1048260C CN93119743A CN93119743A CN1048260C CN 1048260 C CN1048260 C CN 1048260C CN 93119743 A CN93119743 A CN 93119743A CN 93119743 A CN93119743 A CN 93119743A CN 1048260 C CN1048260 C CN 1048260C
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- latex
- hydrogen peroxide
- graft copolymer
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- monomer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/18—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种采用两段式乳液聚合法,以制备改进核壳间相结合的核一壳分散粒子型接枝共聚物胶乳,其中,利用过氧化氢于接枝之前的处理,使接枝主基的粒子表面上带有过氧化氢基。
Description
本发明涉及一种制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳所采用的两段式乳液聚合法、由该法制得的分散液与接枝共聚物及其使用。
借助两段式乳液聚合法以制备粒子型接枝共聚物的技术已被公开。在该方法中,第一阶段,借助乳液聚合作用,可制得一聚合物分散液,之后,第二阶段,经计量加入传统式引发剂及更多单体,可将另一种聚合物的壳接枝在该聚合物分散液上。同时,亦可用本发明的方法,使硬质单体与弹性体聚合物分散粒子(这些粒子的特征是:其玻璃化转变温度低于0℃)接枝。专利DE-A 3743142中曾述及这一步骤,即将氯乙烯接枝聚合在一种乙烯/醋酸乙烯橡胶上。由两段式合成法制备这些粒子接枝聚合物的过程中,主要问题在于接枝壳与接枝主基的结合。若相间结合度不够强,所制得模压制品的机械性能通常均欠佳。现有技术曾揭示许多方法用以改进相结合。
专利EP-A-231933 曾述及使用所谓的接枝连接单体(graft-linking monomers)。根据定义,这些单体为多官能单体,这些单体具有许多不同反应的C=C双键,并非全部在第一阶段的自由基聚合作用中发生反应,所以,在第二阶段,这些单体部分可与待接枝的单体结合。但其缺点是:在第一个聚合作用阶段,这些多官能单体亦起到交联剂的作用。此外,可经常发现,在第一个反应阶段,反应性稍弱的双键具有阻滞效果。所以,无法以所要求的数量,将这些接枝连接单体引入接枝主基内。
专利DE-A 4006643的权利要求范围内曾述及:在接枝主基内,使用羟烷基丙烯酸酯作为共聚单体,以改进接枝速率。但该方法的缺点是:由于其多种共聚合作用参数的影响,在第一阶段,所使用的羟烷基丙烯酸酯无法与所有乙烯基单体实施共聚合作用。
在许多专利文献(例如:专利DE-A 4135984及其引述的文献)中,曾多次述及有关可共聚合的过氧化物引发剂的使用,在第一阶段,这些引发剂可与接枝主基的单体实施共聚合作用,产生所谓的巨引发剂(macroinitiaror),在第二阶段,该巨引发剂可引发一接枝聚合作用而无需再添加引发剂。这些方法的缺点是:在第一阶段因产生巨引发剂对共聚合作用所造成的损失,所以,必须采取适当措施以确保过氧化物的功能不致遭受破坏。
在专利DE-A 4000543的权利要求范围内,曾述及粒子表面可产生具有过氧化氢基的粒子巨引发剂。为达到此一目的,须以水溶性过氧化物及大气中的氧处理由乳化作用制得的接枝主基。依据该文献,过氧化氢基在粒子表面上形成,借助于还原剂,在第二阶段的接枝步骤中,这些基均可予以活化。最后作为接枝聚合物核的结合基。该方法缺点是氧分子的使用,由于氧分子的双基性,其在自由基反应中具有阻滞效果,所以,在后续接枝聚合作用之前,必须利用繁杂的步骤予以除去。
所以,本发明的目的在于开发一种制备粒子型接枝共聚物的方法,而该共聚物接枝主基与接枝壳间的结合可得到改进,使用此种方法可克服上述方法的缺点。
本发明涉及一种采用两段式乳化聚合法,以制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳的方法,制备该胶乳主要使用的一种或更多种单体,均选自一组单体,该组单体包括:由具有1至14个碳原子的醇所形成的(甲基)丙烯酸酯、由具有1至14个碳原子的饱和脂肪羧酸所形成的乙烯酯、烯烃、乙烯基芳香烃、囟代乙烯及/或第一阶段制得的乙烯醚,在该方法中,
a)将过氧化氢及一自由基引发剂(在添加过氧化氢时胶乳的温度下,该引发剂以半衰期大于48小时的速率分解成自由基)同时或依任何顺序添加于第一阶段的聚合物乳胶内,及
b)在第二阶段,将该混合物加热至某一温度,使自由基引发剂在该温度下以半衰期小于48小时的速率分解成自由基,和/或添加一还原剂及
c)添加接枝单体相(其中含有一种或更多种单体,这些单体形成均聚物,均聚物的玻璃化转变温度Tg>20℃),必要时连同另外的还原剂,胶乳聚合物即行接枝。
优选的主基单体,其选自一组单体,该组单体包括具有1至14个碳原子的醇所形成的丙烯酸甲酯或丙烯酸酯的单体,为:甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、甲基丙烯酸异丙酯、丙烯酸异丙酯、丙烯酸叔丁酯、丙烯酸正丁酯及丙烯酸乙基己酯。另有优选的单体,其选自一组单体,该组单体包括具有1至14个碳原子的饱和脂肪羧酯所形成的乙烯酯,为:醋酸乙烯酯、2-乙基己酸乙烯酯、乙酸异丙烯酯、丙酸乙烯酯、月桂酸乙烯酯及具有9至10个碳原子的维尔塞酸(Versatic acidR)乙烯酯(饱和α-分枝单羧酸的乙烯酯,市面上有售,壳牌公司生产)。此外,其他适意的单体为:选自包括烯烃的一组单体,乙烯、丙烯及1,3-丁二烯,选自包括囟代乙烯的一组单体,氯乙烯及属于乙烯基芳香烃的单体及苯乙烯。
必要时,本发明的共聚物可另外含有高达10%重量比(以共聚物为基准)的乙烯型不饱合、官能性共聚单体,作为主基单体。这些共聚单体的实例为:一或二元羧酸,例如:甲基丙烯酸、丙烯酸或反丁烯二酸及其酰胺类,具有羟官能基的单体,例如:丙烯酸羟乙酯、丙烯酸2-羟丙酯或N-羟甲基丙烯酰胺,具有磺酸酯官能基的单体,例如:磺酸乙烯酯或磺酸2-丙烯酰氨基-2-甲基丙酯,及聚合不饱和单体,例如:饱和或不饱和C4-或C10-二元羧酸的二乙烯基或二烯丙基酯,如:己二酸二乙烯酯或三聚氰酸三烯丙酯。
含有一个或更多个共聚单体的共聚物,其共聚单体为选自一组单体,该组单体包括:乙酸乙烯酯、乙酸异丙烯酯、丙酸乙烯酯、2-乙基己酯乙烯酯、十二酸乙烯酯、氯乙烯和/或乙烯的单体,或交联的聚丙烯酸丁酯共聚物更为优选。含有0至50重量%乙烯、50至100重量%醋酸乙烯酯的共聚物,尤其优选为经与0.01至5.0重量%的上述不饱和单体实施交联的共聚物,以上各重量%的和为100重量%。
该胶乳最好采用自由基乳液聚合法制备。在0至90℃温度范围内,以自由基引发剂引发聚合作用。在优选的乳液聚合法中,以水溶性自由基引发剂引发,这些引发剂的使用量为0.01至3.0重量%(以单体总重量为基准)。其实例是:过硫酸及过氧二硫酸的铵盐及钾盐,过氧化氢及偶氮化合物,例如:偶氮二异丁腈或偶氮二氰基戊酸。若采用加热引发方式,聚合作用优选地在70至90℃范围内实施。在较低温度(优选为在30至55℃)下,可借助于还原剂(例如:碱金属甲醛次硫酸盐、碱金属亚硫酸盐、亚硫酸氢盐及硫代硫酸盐及抗坏血酸)。
所有阴离子及非离子乳化剂,其在传统乳液聚合作用中使用时,亦可用作分散剂。以单体总重量为基准,乳化剂的最佳使用量为1至6重量%。例如,阴离子表面活性剂中,诸如:链长为8到18个碳原子的硫酸烷基酯、具有8至18个碳原子的疏水基及高达40个环氧乙烷或环氧丙烷单元的烷基及烷芳基醚硫酸酯、具有8至18个碳原子的烷基或烷芳基磺酸酯,磺基琥珀酸与一元醇或烷基酚所形成的酯或半酯较为适当。例如,非离子表面活性剂中,以具有8至40个环氧乙烷单元的烷基聚乙二醇醚或烷芳基聚乙二醇醚较为适当。
聚合作用pH值所要求的范围,通常为2.5至10,优选为3至8,可经由已知的酸、碱或传统式缓冲盐类(例如:碱金属的磷酸盐或碱金属的碳酸盐)获得。于聚合作用期间,添加已知的调节剂,例如:硫醇、醛类及含氯烃等,可提高分子量。
聚合作用可采取分批式或连续式,使用或不使用粒胶、反应混合物的全部或个别成分均于开始时一次加入、或反应混合物的全部或个别成分于开始时部分加入,随后陆续计量加入,或开始时不添加,全部采用计量加入。所有计量加入的速度因特定成分而异。
制备前述含有乙烯及乙烯酯的优选共聚物胶乳所用的优选程序中,于聚合作用开始前,乙烯的绝对压力必须达到10×105至90×105帕,且随后继续加入乙烯以保持压力不变。开始时,乙烯酯的添加量优选为5至20%重量比,其余部分则于聚合作用过程中计量加入。乙烯型不饱和、官能共聚单体可全部计量加入或开始时部分加入,其余部分于聚合作用进行中计量加入。乳化剂可依照任何程序添加;优选为:若干乳化剂于开始时添加,其余部分则于聚合作用过程中计量加入。
胶乳聚合作用实施方式,以胶乳的总重量为基准,单体的残余量将低于1重量%,固体含量则可高达20至65重量%。
为改进接枝主基与接枝聚合物外壳间的相结合,根据本发明的方法,以过氧化氢处理胶乳聚合物,胶乳粒子的粒子表面可产生过氧化氢基。因此,可同时或以任何顺序,将过氧化氢及自由基引发剂(该引发剂在作过氧化氢处理时,在胶乳的温度下,以半衰期大于48小时的速率分解成自由基)加入。
在每种情况下,以第一阶段胶乳聚合物的重量为基准,添加的过氧化氢,优选为0.1至20重量%,尤其优选为0.1至10重量%。添加胶乳时的温度优选为20至40℃,添加过氧化氢之后,在上述温度范围内,最好使该混合物继续静置或加以搅拌,该过程历时30分钟至12小时。在一尤其优选的具体实例中,与过氧化氢一起加入,添加重金属盐类催化剂的量(以胶乳聚合物为基准,优选为0.001至0.01%重量比)这些重金属盐可能具有多种氧化态的盐类,例如:硫酸铁(II)。
在对过氧化氢进行处理后,将该混合物加热至某一温度,在该温度下,自由基引发剂以半衰期低于48小时的速率分解成自由基。另外一种方式,无需进一步加热,仅添加还原剂,亦可产生自由基引发作用。
适于引发接枝反应的自由基引发剂,其实例是:水溶性自由基引发剂,例如:过硫酸铵、过硫酸钾、过氧化二硫酸铵、过氧化二硫酸钾或水溶性偶氮化合物,例如:偶氮二异丁腈或偶氮二氰戊酸。适当的还原剂是氧化还原引发剂体系内常用的还原剂,例如:碱金属甲醛次硫酸盐类(雕白粉brueggolite)、碱金属亚硫酸盐、亚硫酸氢盐及硫化硫酸盐与抗坏血酸。以接枝单体相为基准,还原剂和/或水溶性自由基引发剂的作用量,优选为0.01至3.0重量%。
在对过氧化氢进行处理后,必要时,于温度达到平衡后,将待接枝的单体计量加入,必要时可连同还原剂一起加入。接枝单体相含有一种或更多种单体,这些单体所形成的均聚物,其玻璃化转变温度Tg>20℃。苯乙烯、乙烯基甲苯、甲基丙烯酸甲酯、氯乙烯或这些单体的混合物是优选的待接枝聚合物。以接枝共聚物为基准,接枝单体的添加量必须适当,即在接枝的聚合物壳中所占比例应为5至95重量%。
因所选择的引发剂体系不同,接枝聚合是在30至90℃的温度下进行。必要时为完成接枝,以接枝共聚物总重量为基准,亦可添加0.1至5.0重量%的上述非离子或阴离子乳化剂。在一优选的具体实例中,于结束添加接枝单体后,继续计量加入还原剂,直至残余单体含量低于1重量%(以胶乳的总重量为基准)。根据本发明方法制备的接枝共聚物分散液,其固体含量为20至65重量%,为达到此固体含量,于进行过氧化氢处理前,亦可用水将胶乳加以适度的稀释。
例如,为将接枝共聚物分离出来,可采用喷雾干燥法、滚筒干燥法或后续干燥凝固法。
另外,本发明涉及接枝共聚物胶乳及接枝共聚物,这些共聚物是由本发明的方法制得的,并具有一核(该核内含有一个或更多个单体,这些单体为选自一组的单体,这组单体包括:具有1至14个碳原子的醇所形成的(甲基)丙烯酸酯、具有1至14个碳原子的饱和脂肪羧酸所形成的乙烯酯、烯烃、乙烯基芳香烃、囟代乙烯和/或乙烯基醚)及一壳(该壳包括一个或更多个单体),这些单体所形成的均聚合物,其玻璃化转变温度Tg<20℃。核/壳分散粒子,其核优选为由玻璃化转变温度Tg<20℃的交联弹性体聚合物所组成。接枝共聚物,其交联的核含有醋酸乙烯酯及乙烯或其交联的核尤其优选为含有丙烯酸丁酯的核,壳则由苯乙烯、甲基丙烯酸甲酯和/或氯乙烯组成。
本发明更涉及使用本发明制备的接枝共聚物胶乳,作为织物及乳化油漆的含水结合剂及硬膏剂(plaster)的粘合剂。分散作用完成后所制得的接枝共聚物,适合用作:生产柔韧的至柔软的模压制品(热塑弹性体)的热塑性模压材料、用于改进或赋予聚合物合金的相间相容性的添加剂及作为不饱和聚酯树脂的″低糙度″(low-profile)添加剂。
在本发明的步骤中,利用过氧化氢处理,可使接枝主基的粒子表面上产生过氧化氢基。以加热或还原使这些过氧化氢基活化,随后则发生接枝反应。由于粒子表面上形成许多自由基,接枝的效果必然很高,因而所制得的模压制品,其机械性能得以按比例得到改进。与现有技术的步骤相比,本方法的优点是:接枝主基的制备(与接枝-连接单体的共聚合作用相比)及接枝步骤(与巨引发剂的共聚合作用相比)并不困难,而且(与用大气氧处理相比)亦不产生阻滞效果。
下列各实施例可对本发明作进一步的说明:
实施例1:
制备一交联的乙烯/醋酸乙烯酯分散液作为接枝主基
首先制备四种溶液:
引发剂溶液I:将0.25重量份的过硫酸钾溶解于5.5重量份的水中。
引发剂溶液II:将0.45重量份的过硫酸钾溶解于14.6重量份的水中。
单体溶液:将0.45重量份的己二酸二乙烯酯溶解于90重量份的醋酸乙烯酯中。
初始乳化液:将0.8重量份的2-丙烯酰胺基-2-甲基丙烯磺酸钠及2.2重量份的磺基琥珀酸二异酯(Aerosol MA 80,氰氨公司生产)乳化于42重量份的水中。于一搅拌高压釜内,将9.75重量份的醋酸乙烯酯、0.25重量份的磺酸乙烯酯及0.515重量份的磺基琥珀酸二异己酯(Aerosol MA80,氰氨公司生产)加热至75℃,并通入80×105帕压力的乙烯。待温度达到平衡后,将上述引发剂溶液I徐徐加入,历时10分钟,其他三种液体则计量加入。有关计量加入速率的选定,单体溶液及初始乳化液的计量加入时间为5小时,引发剂溶液II的计量加入时间为6小时。
所得匀细分散液,其固体含量为50.2重量%,粒径分布形式单一化,平均粒径为172纳米。该共聚物的乙烯含量为41重量%,该聚合物树脂的玻璃化转变温度(由差示扫描量热法测定)为-26.5℃;其K值(于四氢呋喃内)为42.1。
实施例2:
以5重量%的过氧化氢作预处理后的接枝聚合作用
首先将1,070克实施例1中制得的乙烯/醋酸乙烯酯分散液、61.6克35%浓度的H2O2溶液及2.08克过硫酸钾置于一3升玻璃圆锥烧瓶(该烧瓶附有内温度计、回流冷凝器及搅拌器)内,并在室温下搅拌2小时。之后,将该混合物加热至65℃。待温度达到平衡后,将1.65克羟甲亚磺酸的钠盐(Brueggolite)(溶解于108毫升水中)及由180克苯乙烯、2.88克Aerosol MA 80及125毫升水所组成的初始乳化液,计量加入,历时3小时。在65℃温度下搅拌1小时,完成反应。
所得匀细分散液,其固体含量为43.3%重量比,粒径分布形式单一化,平均粒径为192纳米。该粒子接枝聚合物有两相,其玻璃化转变温度(由差示扫描量热法测定)分别为-25.1℃及+101.8℃;其K值(于四氢呋喃内)为42.1。经测定残留单体含量为0.88重量%。
实施例3:
以10重量%的过氧化氢作预处理后的接枝聚合作用
实施步骤与实施例2的步骤相同,但搅拌加入的初始混合物是123克35%浓度的H2O2溶液。
所得匀细分散液,其固体含量为44.3%重量比,粒径分布形式单一化,平均粒径为181纳米。该粒子接枝聚合物有两相,其玻璃化转变温度(由差示扫描量热法测定)分别为-26.0℃及+102.3℃;其K值(于四氢呋喃内)为38.9。经测定残留单体含量为0.57重量%。
比较例1:
不用过氧化氢作预处理的接枝聚合作用
实施步骤与实施例2及3的步骤相同,但接枝反应前不添加过氧化氢。
所得匀细分散液,其固体含量为43.1%重量比,粒径分布形式单一化,平均粒径为180纳米。该粒子接枝聚合物有两相,其玻璃化转变温度(由差示扫描量热法测定)分别为-25.1℃及+100.1℃;其K值(于四氢呋喃内)为36.9。经测定残余单体含量为0.98重量%。
性能测试:
试样的制备:
为测试产品质量及加工性能,于分散液内添加一10%浓度的氯化钙(CaCl2)溶液使其凝固,将所得凝块加以过滤、清洗及烘干,制得一白色、可自由流动的粉末。
首先,在170℃温度下,在实验室用辊筒辗磨机将该粉末加以研磨,之后,在温度170℃及压力10兆帕斯卡(MPa)的情况下,将其压成1毫米厚的薄片。
测试方法:
按照工业标准DIN 53505测定这些薄片的肖耳A硬度、按照DIN 53504测定其抗张强度及断裂伸长率及按照DIM 53515测定其撕裂扩大强度。
测试结果如表1所示:
如表1所示,经用过氧化氢处理所得的模压制品,其抗张强度增加约20%,裂断伸长率也同样增加约20%。撕裂扩大强度的提高幅度高达75%。表1:
实施例 | 肖耳A硬度 | 抗张强度[牛顿/毫米2] | 裂断伸长率% | 撕裂扩大强度[牛顿/毫米2] |
比较例1 | 46 | 5.55 | 216 | 6.26 |
实施例2 | 56 | 6.27 | 239 | 7.76 |
实施例3 | 57 | 6.50 | 259 | 10.90 |
Claims (10)
1、一种制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳的方法,该方法是采用两段式乳液聚合法,制备该胶乳使用一种或多种选自下述一组的单体,该组单体包括:由具有1至14个碳原子的醇所形成的(甲基)丙烯酸酯、由具有1至14个碳原子的饱和脂肪羧酸所形成的乙烯酯、烯烃、乙烯基芳香烃、卤代乙烯和/或第一阶段制得的乙烯醚,在该方法中,
a)将过氧化氢及一自由基引发剂同时或依任何顺序添加于第一阶段的聚合物胶乳内,在添加过氧化氢时胶乳的温度下,该引发剂以半衰期大于48小时的速率分解成自由基,及
b)在第二阶段,将该混合物加热至某一温度,使自由基引发剂在该温度下以半衰期小于48小时的速率分解成自由基,和/或添加一还原剂及
c)添加接枝单体相,该单体相中含有一种或多种乙烯基不饱和单体,这些单体形成均聚物,均聚物的玻璃化转变温度Tg>20℃,胶乳聚合物非必要地用另外的还原剂进行接枝。
2、如权利要求1所述的方法,其中,以第一阶段胶乳聚合物的重量为基准,添加0.1至20重量%的过氧化氢。
3、如权利要求1或2所述的方法,其中,是在胶乳温度为20至40℃的情况下添加过氧化氢。
4、如权利要求1所述的方法,其中,在添加过氧化氢后,在上述温度范围内,将该混合物静置或搅拌30分钟至12小时。
5、如权利要求1所述的方法,其中,与过氧化氢一起添加重金属盐类的催化剂,这些重金属可以具有多种氧化态。
6、如权利要求1的方法,其中,与过氧化氢一起,以胶乳聚合物为基准,添加0.001至0.01重量%的铁盐。
7、如权利要求6的方法,其中所述的铁盐是硫酸铁(II)。
8、如权利要求1所述的方法所制备的接枝共聚物胶乳,其核是由交联的弹性体聚合物所组成,这些聚合物含有醋酸乙烯酯及乙烯或丙烯酸丁酯,其壳是由苯乙烯、甲基丙烯酸甲酯和/或氯乙烯组成。
9、如权利要求8的接枝共聚物胶乳作为织物及乳化油漆的含水结合剂及硬膏剂的粘合剂的应用。
10、由权利要求8所述的接枝共聚物胶乳制得的接枝共聚物作为热塑性模压材料在生产柔韧至柔软的模压制品中的应用,和作为改善或赋予聚合物合金相间相容性的添加剂以及作为不饱和聚酯树脂的″低糙度″添加剂的应用。
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DEP4240744.2 | 1992-12-03 | ||
DE4240744A DE4240744A1 (de) | 1992-12-03 | 1992-12-03 | Verfahren zur Herstellung eines Pfropfcopolymerlatex von Kern-Schale-Dispersionsteilchen mit verbesserter Phasenanbindung zwischen Kern und Schale |
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US (1) | US5399621A (zh) |
EP (1) | EP0600478B1 (zh) |
JP (1) | JP2676672B2 (zh) |
KR (1) | KR0133971B1 (zh) |
CN (1) | CN1048260C (zh) |
CA (1) | CA2110673A1 (zh) |
DE (2) | DE4240744A1 (zh) |
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US5900311A (en) * | 1994-03-23 | 1999-05-04 | Cook Composites And Polymers Co. | Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance |
EP0725092A3 (de) * | 1995-02-06 | 1997-08-27 | Chemie Linz Gmbh | Redispergierbare, pulverförmige Kern-Mantel-Polymere, deren Herstellung und Verwendung |
US5731035A (en) * | 1995-09-22 | 1998-03-24 | Cook Composites And Polymers | Process for making a paintable polymer article |
CN1154671C (zh) | 1996-09-09 | 2004-06-23 | 巴斯福股份公司 | 聚合物水分散体的制备方法 |
ID20459A (id) | 1997-06-24 | 1998-12-24 | Denki Kagaku Kogyo Kk | Komposisi resin yang bisa mengawetkan, komposisi perekat, produk dan susunan yang diawetkan |
KR100380016B1 (ko) * | 1998-03-20 | 2003-09-19 | 주식회사 엘지화학 | 소구경고무라텍스제조방법 |
KR100584285B1 (ko) * | 1998-12-31 | 2006-12-15 | 주식회사 케이씨씨 | 아크릴계 코아쉘 유화중합체를 함유하는 마이크로겔 수용성도료 조성물 |
JP3538574B2 (ja) | 1999-09-27 | 2004-06-14 | 株式会社リンレイ | 可剥離性被覆組成物 |
JP4379998B2 (ja) * | 1999-09-30 | 2009-12-09 | 住友化学株式会社 | エチレン−酢酸ビニル系共重合体水性エマルジョンの製造方法 |
DE19958820B4 (de) * | 1999-12-07 | 2010-04-01 | Vestolit Gmbh & Co. Kg | Verfahren zur Herstellung thermoplastischer Formmassen, nach diesem Verfahren hergestellte Formmassen und deren Verwendung |
JP2002348339A (ja) * | 2001-05-24 | 2002-12-04 | Sumitomo Chem Co Ltd | エチレン・ビニルエステル共重合体含有水性エマルジョンならびに該エマルジョンと多価イソシアネート化合物とを含有する接着剤 |
JP2004067789A (ja) * | 2002-08-05 | 2004-03-04 | Sumitomo Chem Co Ltd | 耐衝撃性メタクリル樹脂キャスト成形体の製造方法 |
KR100512367B1 (ko) * | 2003-08-05 | 2005-09-05 | 주식회사 엘지화학 | 그라프트 공중합체 라텍스 및 그의 건조 분말 제조방법 |
CN100396741C (zh) * | 2003-12-17 | 2008-06-25 | 陈良 | 一种低挥发性水性涂料用树脂组合物及其生产方法 |
CN100447170C (zh) * | 2006-06-01 | 2008-12-31 | 北京化工大学 | 一种提高丙烯酸酯核/壳结构乳胶粒子接枝效率的方法 |
CN100554294C (zh) * | 2007-08-10 | 2009-10-28 | 上海东升新材料有限公司 | 一种用于制造可再分散乳胶粉的乳液及其制备方法 |
CN102061621B (zh) * | 2010-11-23 | 2012-07-04 | 海安县银桥纺织品有限公司 | 一种原位聚合微胶囊喷胶棉保暖材料的生产方法 |
CN103936932B (zh) * | 2014-05-15 | 2016-09-14 | 齐齐哈尔大学 | 一种表层含羟基核壳乳胶粒子合成方法 |
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- 1993-10-30 CN CN93119743A patent/CN1048260C/zh not_active Expired - Fee Related
- 1993-11-29 KR KR1019930025717A patent/KR0133971B1/ko not_active IP Right Cessation
- 1993-12-02 ES ES93119426T patent/ES2084437T3/es not_active Expired - Lifetime
- 1993-12-02 EP EP93119426A patent/EP0600478B1/de not_active Expired - Lifetime
- 1993-12-02 JP JP5329560A patent/JP2676672B2/ja not_active Expired - Lifetime
- 1993-12-02 DE DE59301795T patent/DE59301795D1/de not_active Expired - Fee Related
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JP2676672B2 (ja) | 1997-11-17 |
EP0600478A1 (de) | 1994-06-08 |
KR940014472A (ko) | 1994-07-18 |
CN1087646A (zh) | 1994-06-08 |
EP0600478B1 (de) | 1996-03-06 |
ES2084437T3 (es) | 1996-05-01 |
TW287180B (zh) | 1996-10-01 |
DE59301795D1 (de) | 1996-04-11 |
CA2110673A1 (en) | 1994-06-08 |
DE4240744A1 (de) | 1994-06-09 |
US5399621A (en) | 1995-03-21 |
JPH06206950A (ja) | 1994-07-26 |
KR0133971B1 (ko) | 1998-04-20 |
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