CN105968315B - 一种基于聚甲基丙烯酸甲酯相容剂的制备方法 - Google Patents
一种基于聚甲基丙烯酸甲酯相容剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种基于聚甲基丙烯酸甲酯相容剂的制备方法,包括步骤:端羟基聚丙烯酸酯的制备、含羟基聚甲基丙烯酸甲酯的制备和聚甲基丙烯酸甲酯‑g‑聚丙烯酸酯相容剂的制备。本发明的有益效果是:相容剂制备方法相对简单,接枝链链长可控,接枝密度可调。
Description
技术领域
本发明属于高分子材料领域,涉及一种基于聚甲基丙烯酸甲酯相容剂的制备方法。
背景技术
相容剂又称增容剂,是指借助于分子间的键合力,促使不相容的两种聚合物(一般是极性相差较大的材料)结合在一体,进而得到稳定的共混物的助剂。相容剂在热力学本质上可以理解为界面活性剂,在不相容的高分子体系中添加相容剂并在一定温度下经混合混炼后,相容剂将被局限在两种高分子之间的界面上,起到降低界面张力、增加界面层厚度、降低分散粒子尺寸的作用,使体系最终形成具有宏观均匀微观相分离特征的热力学稳定的相态结构。
聚甲基丙烯酸甲酯(PMMA)是一种高强度、高透光率的热塑性材料,硬度较好,具有一定的抗寒性和耐腐蚀性,在聚合物光纤、汽车车灯、电脑导光板等方面有着良好的应用。但是,PMMA韧性较差,常温抗冲击性能不佳,这些缺点限制了其应用领域的扩展。
丙烯酸酯橡胶(ACM)是以丙烯酸酯为主要组成的共聚物,由于主链结构完全饱和,是一种耐热、耐油、耐寒性能优良且成本适中的特种橡胶,广泛应用于汽车工业中的橡胶制品。ACM橡胶韧性好,与PMMA混炼能改善PMMA韧性差,常温抗冲击性能不佳的缺点。
PMMA的改性方法有多种,包括共聚增韧、共混增韧、形态控制增韧等,其中共混增韧即有机弹性体与之共混增韧是一种常见方法。为了进一步提高共混组分之间的相容性提高两相间结合力,需要用到相容剂。相容剂包括反应型和非反应型,从制备方法上又分为嵌段、接枝等。例如专利CN 103073838A介绍了一种相容剂的制备方法,其由ABS接枝马来酸酐及SEBS接枝马来酸酐复配,但该方法存在接枝率较低的缺点。
发明内容
本发明要解决的技术问题是:基于上述问题,本发明提供一种基于聚甲基丙烯酸甲酯相容剂的制备方法。
本发明解决其技术问题所采用的一个技术方案是:一种基于聚甲基丙烯酸甲酯相容剂的制备方法,包括以下步骤:
(1)端羟基聚丙烯酸酯的制备:将引发剂Ⅰ、单体Ⅰ、络合液、还原剂和溶剂Ⅰ加入到反应容器中,将反应体系抽真空充氮气,50~100℃反应2~10小时,制得端羟基聚丙烯酸酯;
(2)含羟基聚甲基丙烯酸甲酯的制备:将引发剂Ⅱ、单体Ⅱ、甲基丙烯酸甲酯缓慢滴加到装有溶剂Ⅱ的反应容器中,60~100℃反应3~10小时,制得含羟基聚甲基丙烯酸甲酯;
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸酯相容剂的制备:将步骤(1)制得的端羟基聚丙烯酸酯与二异氰酸酯在催化剂作用下,40~80℃反应0.5~6小时,再加入步骤(2)制得的聚甲基丙烯酸甲酯,80~100℃反应1~10小时,得到相容剂聚甲基丙烯酸甲酯-g-聚丙烯酸酯。
进一步地,步骤(1)中引发剂Ⅰ为一个端基为羟基的有机卤代化合物,具体为α-溴代异丁酸羟乙酯、α-氯代异丁酸羟乙酯、α-溴代异丁酸羟丁酯、α-氯代异丁酸羟丁酯或2-溴-N-(2-羟乙基)-2-甲基丙酰胺中的一种;单体Ⅰ为丙烯酸酯类,具体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯或丙烯酸-2-乙基己酯中的一种或几种;络合液为氧化态的过渡金属卤化物、配体和乙醇在常温下搅拌均匀而得,氧化态的过渡金属卤化物为CuCl2、CuBr2、FeCl3或FeBr3中的一种或几种,配体为五甲基二乙烯基三胺、三-(N,N-二甲氨基乙基)胺或1,1,4,7,10,10-六甲基三亚乙基四胺中的一种或几种;还原剂为辛酸亚锡、抗坏血酸或葡萄糖中的一种或几种。
进一步地,步骤(1)中单体Ⅰ:引发剂的摩尔比为10:1~100:1,氧化态的过渡金属卤化物:单体Ⅰ的摩尔比为0.00005:1~0.0005:1,氧化态的过渡金属卤化物:还原剂Ⅰ的摩尔比为1:10~1:25,氧化态的过渡金属卤化物:配体的摩尔比为1:10~1:30,溶剂Ⅰ用量为单体Ⅰ质量的10~100%。
进一步地,步骤(2)中引发剂Ⅱ为自由基引发剂,具体为偶氮二异丁氰或过氧化二苯甲酰中的一种或两种;单体Ⅱ为(甲基)丙烯酸羟乙酯或(甲基)丙烯酸羟丙酯类。
进一步地,步骤(2)中单体Ⅱ的质量为单体Ⅱ与甲基丙烯酸甲酯总质量的5~25%,引发剂Ⅱ的质量为单体Ⅱ与甲基丙烯酸甲酯总质量的1~5‰。
进一步地,步骤(3)中二异氰酸酯具体为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1,5-二异氰酸酯、2,6-二异氰酸酯己酸甲酯或六甲基二异氰酸酯中的一种,催化剂为二月桂酸二丁基锡、三乙醇胺或辛酸亚锡中的一种或几种。
进一步地,步骤(3)中二异氰酸酯与端羟基聚丙烯酸酯的NCO/OH为2.0/1~3.0/1,端羟基聚丙烯酸酯与聚甲基丙烯酸甲酯的质量比为1:0.5~1:10。
本发明的有益效果是:相容剂制备方法相对简单,接枝链链长可控,接枝密度可调。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(1)端羟基聚丙烯酸甲酯的制备(设计分子量1000)
在装有温度计、搅拌桨的四口烧瓶中加入丙烯酸甲酯20.00g(0.2323mol)、引发剂α-溴代异丁酸羟丁酯4.7884g(20.026mmol)、CuBr2 0.02082g(0.09293mmol)和五甲基二乙烯基三胺PMDETA 0.3221g(1.8585mmol)、还原剂辛酸亚锡Sn(EH)2 0.7529g(1.8585mmol)以及溶剂甲苯10.00g,混合均匀后,通氮气鼓泡,在70℃油浴下反应210min,转化率达81%后停止反应,产物过中性氧化铝柱后,沉淀烘干备用。
(2)含羟基聚甲基丙烯酸甲酯的制备
在装有甲苯的500ml反应瓶中缓慢滴加甲基丙烯酸甲酯80g(0.7990mol)、丙烯酸羟乙酯20g(0.1722mol)和过氧化二苯甲酰0.5g的混合单体溶液,85℃下反应6小时结束,降温出料,产物用甲醇沉淀后烘干。
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸甲酯的制备
取端羟基聚丙烯酸甲酯10g(0.0100mol)、甲苯15g、异氟尔酮二异氰酸酯2.6675g(0.01200mol)、二月桂酸二丁基锡,60℃下反应2小时后,加入含羟基聚甲基丙烯酸甲酯10g,升温至80℃,反应4小时后停止,产物用甲醇沉淀,烘干至恒重。
实施例2
(1)端羟基聚丙烯酸乙酯的制备(设计分子量3000)
在装有温度计、搅拌桨的四口烧瓶中加入丙烯酸乙酯20.00g(0.1998mol)、引发剂α-溴代异丁酸羟丁酯1.5941g(6.6667mmol)、CuBr2 0.01790g(0.0799mmol)和PMDETA0.2759g(1.5981mmol)、还原剂Sn(EH)2 0.6474g(1.5981mmol)以及甲苯10g,混合均匀后通氮气鼓泡,在75℃油浴下反应255min,转化率达到86%后停止,产物过中性氧化铝柱后,用甲醇沉淀,烘干。
(2)含羟基聚甲基丙烯酸甲酯的制备
在装有甲苯的500ml反应瓶中缓慢滴加甲基丙烯酸甲酯80g(0.7990mol)、丙烯酸羟乙酯5g(0.04306mol)和过氧化二苯甲酰0.255g的混合单体溶液,85℃下反应6小时结束,降温出料,产物用甲醇沉淀后烘干。
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸乙酯的制备
取端羟基聚丙烯酸乙酯10g(0.0033mol)、甲苯15g、异氟尔酮二异氰酸酯2.6675g(0.01200mol)、二月桂酸二丁基锡,60℃下反应2.5小时后,加入含羟基聚甲基丙烯酸甲酯15g,升温至80℃,反应6小时后停止,产物用甲醇沉淀,烘干至恒重。
实施例3
(1)端羟基聚丙烯酸丁酯的制备(设计分子量5000)
在装有温度计、搅拌桨的四口烧瓶中加入丙烯酸丁酯20.00g(0.1560mol)、引发剂α-溴代异丁酸羟丁酯0.9564g(4.000mmol)、CuBr2 0.01398g(0.06242mmol)和PMDETA0.2163g(1.2483mmol)、还原剂Sn(EH)2 0.5057g(1.2483mmol)以及甲苯15g,混合均匀后通氮气鼓泡,在80℃油浴下反应215min,转化率达到85%后停止,产物过中性氧化铝柱后用甲醇沉淀烘干。
(2)含羟基聚甲基丙烯酸甲酯的制备
在装有甲苯的500ml反应瓶中缓慢滴加甲基丙烯酸甲酯80g(0.7990mol)、丙烯酸羟乙酯15g(0.1292mol)和过氧化二苯甲酰0.285g的混合单体溶液,85℃下反应7小时结束,降温出料,产物用甲醇沉淀后烘干。
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸丁酯的制备
取端羟基聚丙烯酸丁酯10g(0.0020mol)、甲苯15g、异氟尔酮二异氰酸酯0.5334g(0.0024mol)、二月桂酸二丁基锡,60℃下反应3.5小时后,加入含羟基聚甲基丙烯酸甲酯15g,升温至80℃,反应8小时后停止,产物用甲醇沉淀,烘干至恒重。
实施例4
(1)端羟基聚丙烯酸-2-乙基己酯的制备(设计分子量8000)
在装有温度计、搅拌桨的四口烧瓶中加入丙烯酸-2-乙基己酯20.00g(0.1085mol)、引发剂α-溴代异丁酸羟丁酯0.5978g(2.500mmol)、CuBr20.009724g(0.04341mmol)和PMDETA 0.1505g(0.8682mmol)、还原剂Sn(EH)20.3517g(0.8682mmol)以及甲苯15g,混合均匀后,通氮气鼓泡,在75℃油浴下反应300min,转化率达80%后停止反应,产物过中性氧化铝柱后,沉淀烘干备用。
(2)含羟基聚甲基丙烯酸甲酯的制备
在装有甲苯的500ml反应瓶中缓慢滴加甲基丙烯酸甲酯80g(0.7990mol)、丙烯酸羟乙酯10g(0.0861mol)和过氧化二苯甲酰0.18g的混合单体溶液,90℃下反应六小时结束,降温出料,产物用甲醇沉淀后烘干。
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸-2-乙基己酯的制备
取端羟基聚丙烯酸-2-乙基己酯10g(0.00125mol)、甲苯15g、异氟尔酮二异氰酸酯0.3334g(0.0015mol)、二月桂酸二丁基锡,60℃下反应5.5小时后,加入含羟基聚甲基丙烯酸甲酯10g,升温至80℃,反应9h后停止,产物用甲醇沉淀,烘干至恒重。
相容剂效果测试
分别以实施例1、2、3、4制备的接枝聚合物作为相容剂,与PMMA/ACM以35/15质量比例密炼共混,按照ASTM-D256标准制备冲击样条,测试混合树脂的冲击性能,冲击测试结果见表1。
表1
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (6)
1.一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:包括以下步骤:
(1)端羟基聚丙烯酸酯的制备:将引发剂Ⅰ、单体Ⅰ、络合液、还原剂和溶剂Ⅰ加入到反应容器中,将反应体系抽真空充氮气,50~100℃反应2~10小时,制得端羟基聚丙烯酸酯;
(2)含羟基聚甲基丙烯酸甲酯的制备:将引发剂Ⅱ、单体Ⅱ、甲基丙烯酸甲酯缓慢滴加到装有溶剂Ⅱ的反应容器中,60~100℃反应3~10小时,制得含羟基聚甲基丙烯酸甲酯;
(3)聚甲基丙烯酸甲酯-g-聚丙烯酸酯相容剂的制备:将步骤(1)制得的端羟基聚丙烯酸酯与二异氰酸酯在催化剂作用下,40~80℃反应0.5~6小时,再加入步骤(2)制得的聚甲基丙烯酸甲酯,80~100℃反应1~10小时,得到相容剂聚甲基丙烯酸甲酯-g-聚丙烯酸酯;
步骤(1)中引发剂Ⅰ为一个端基为羟基的有机卤代化合物,具体为α-溴代异丁酸羟乙酯、α-氯代异丁酸羟乙酯、α-溴代异丁酸羟丁酯、α-氯代异丁酸羟丁酯或2-溴-N-(2-羟乙基)-2-甲基丙酰胺中的一种;单体Ⅰ为丙烯酸酯类,具体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯或丙烯酸-2-乙基己酯中的一种或几种;络合液为氧化态的过渡金属卤化物、配体和乙醇在常温下搅拌均匀而得,氧化态的过渡金属卤化物为CuCl2、CuBr2、FeCl3或FeBr3中的一种或几种,配体为五甲基二乙烯基三胺、三-(N,N-二甲氨基乙基)胺或1,1,4,7,10,10-六甲基三亚乙基四胺中的一种或几种;
步骤(2)中引发剂Ⅱ为自由基引发剂,具体为偶氮二异丁腈或过氧化二苯甲酰中的一种或两种;单体Ⅱ为(甲基)丙烯酸羟乙酯或(甲基)丙烯酸羟丙酯类。
2.根据权利要求1所述的一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:所述的步骤(1)中还原剂为辛酸亚锡、抗坏血酸或葡萄糖中的一种或几种。
3.根据权利要求1所述的一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:所述的步骤(1)中单体Ⅰ:引发剂的摩尔比为10:1~100:1,氧化态的过渡金属卤化物:单体Ⅰ的摩尔比为0.00005:1~0.0005:1,氧化态的过渡金属卤化物:还原剂Ⅰ的摩尔比为1:10~1:25,氧化态的过渡金属卤化物:配体的摩尔比为1:10~1:30,溶剂Ⅰ用量为单体Ⅰ质量的10~100%。
4.根据权利要求1所述的一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:所述的步骤(2)中单体Ⅱ的质量为单体Ⅱ与甲基丙烯酸甲酯总质量的5~25%,引发剂Ⅱ的质量为单体Ⅱ与甲基丙烯酸甲酯总质量的1~5‰。
5.根据权利要求1所述的一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:所述的步骤(3)中二异氰酸酯具体为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1,5-二异氰酸酯、2,6-二异氰酸酯己酸甲酯或六甲基二异氰酸酯中的一种,催化剂为二月桂酸二丁基锡、三乙醇胺或辛酸亚锡中的一种或几种。
6.根据权利要求1所述的一种基于聚甲基丙烯酸甲酯相容剂的制备方法,其特征是:所述的步骤(3)中二异氰酸酯与端羟基聚丙烯酸酯的NCO/OH为2.0/1~3.0/1,端羟基聚丙烯酸酯与聚甲基丙烯酸甲酯的质量比为1:0.5~1:10。
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