CN107474185B - 一种n-苯基马来酰亚胺衍生物的共聚体组合物 - Google Patents
一种n-苯基马来酰亚胺衍生物的共聚体组合物 Download PDFInfo
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Abstract
本发明公开了一种N‑苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:其方法为:加热油浴锅至50‑90℃,将N‑苯基马来酰亚胺衍生物、苯乙烯、马来酸酐和二甲苯在此温度下搅拌20‑60min;加入二甲苯,通入N2气,搅拌、加热至90‑120℃后回流;再加入引发剂并升温至125℃反应,得到初产物;趁热将初产物溶于丙酮,加入甲醇;将得到的产物真空干燥,得到粉状树脂。
Description
技术领域
本发明涉及一种N-苯基马来酰亚胺衍生物的共聚体组合物,具体属于树脂原料、医药农药中间体的合成领域。
背景技术
马来酰亚胺及其衍生物作为树脂原料、医药农药等原料,是一种有用的化合物,特别是,为了提高ABS树脂、AS树脂、AB树脂、ACS树脂、AES树脂、AAS树脂等的苯乙烯系树脂、以及聚氯乙烯树脂、聚甲基丙烯酸甲酯树脂、酚醛树脂等的耐热性,大多作为共聚成分之一而被使用。其中,由于N-苯基马来酰亚胺在反应性及耐热性方面优异,因此被特别地广泛使用。
有关N-苯基马来酰亚胺及其衍生物的制造方法,从现有技术中已知有许多方法。文献综述及相关专利多有报道:一步法、酸酐法、脱酸法、酯化法及共沸法等。
有关N-苯基马来酰亚胺及其衍生物的共聚物作为耐热剂的制备和使用也多有文献报道。但提高聚合物耐热温度有限,尤其是在尼龙6中的应用,如专利CN 104356297A的报道。
发明内容
本发明要解决的技术问题是:提供一种N-苯基马来酰亚胺衍生物的共聚体组合物,以解决现有技术中耐热剂提高聚合物耐热温度有限,尤其是在尼龙6中的应用中的局限性。
本发明的技术方案是:一种N-苯基马来酰亚胺衍生物的共聚体组合物,其方法为:加热油浴锅至50-90℃,将N-苯基马来酰亚胺衍生物、苯乙烯、马来酸酐和二甲苯在此温度下搅拌20-60min;加入二甲苯,通入N2气,搅拌、加热至90-120℃后回流;再加入引发剂并升温至125℃反应,得到初产物;趁热将初产物溶于丙酮,加入甲醇;将得到的产物真空干燥,得到粉状树脂。
所述的N-苯基马来酰亚胺衍生物为
所述的N-苯基马来酰亚胺衍生物的制备方法:(1)以马来酸酐和对氨基苯甲酸为原料,DMF为溶剂,在室温下反应,得到中间产物CPMA;(2)将CPMA溶于DMF,将脱水剂、催化剂、阻聚剂进行反应得到CPMI;(3)将CPMA与氯化亚砜酰氯化,得到CPMIC;(4)将CPMIC与KH550进行反应,最终得到最终产物CPMI-KH550;(5)将反应体系在真空下浓缩,而后柱层析提纯。
所述的步骤(1)马来酸酐和对氨基苯甲酸的投料比为1-1.3:1mol/mol,所用溶剂为DMF、二甲苯或DMF与二甲苯的混合溶剂。
所述的步骤(2)中的脱水剂为乙酸酐,催化剂为无水乙酸钠;阻聚剂为对苯二酚。
所述的步骤(3)中,反应温度为50-80℃。
所述的步骤(4)中,KH550的滴加温度在5℃以下,反应温度为室温;反应体系中的干燥剂为无机硫酸钠和硫酸镁;缚酸剂为无机的碳酸氢钠及有机的吡啶。
本发明的有益效果:本发明制备了含有特定官能团的N-苯基马来酰亚胺衍生物(CPMI-KH550),及CPMI-KH550的二元、三元及以上的共聚物等;该类聚合物具有良好的耐热性能,不仅可以作为PVC、ABS等普通塑料的耐热改性剂,也可以作为PA、PPO等工程塑料的耐热改性剂且效果良好。如专利CN 104356297A报道的N-苯基马来酰亚胺/马来酸酐二元共聚物虽然能够提高PA、PPO等的耐热温度,但是在使用同等质量份数时,本发明的耐热性能提高的较多。尼龙6的热变形温度由56℃升高到98℃,极大的增加了尼龙6的运用领域。
附图说明
图1为本发明制备的CPMI-KH550的氢核磁图谱。
具体实施方式
下面通过具体实例进一步说明本发明,但实例并不限制本发明的保护范围。
实施例1
CPMA的合成步骤:(1)将1.078g MAH溶于10mL的DMF中;(2)将1.51g对氨基苯甲酸溶于10mL的DMF,而后将溶液在15-30min内滴加到MAH的DMF溶液中;(3)在40度下反应6h;(4)反应结束后,将反应体系冷却到室温,而后用碎冰提取;将反应溶液倒入到碎冰上,放置3-5min,趁冷抽滤;(5)放在40℃烘箱内烘CPMA。
称取2.17g第一步合成的N-(4-羧基苯基)马来酰胺酸(CPMA),将其溶于DMF中。加入0.2g的催化剂无水乙酸钠、2mL脱水剂醋酸酐、0.2g阻聚剂对苯二酚,升温,将温度控制在50-55℃之间,反应2h,溶液变为淡黄色透明状,冷却至室温后,静置,将溶液倒入碎冰中沉淀出现大量黄色针状晶体,再进行抽滤、洗涤、干燥,得到纯净的淡黄色晶体—N-(4-羧基苯基)马来酰亚胺(CPMI)。
将1.085g CPMI与氯化亚砜溶液在三口烧瓶中80℃回流2h;而后将多余的氯化亚砜蒸馏出来,得CPMIC。
将0.235gCPMIC溶于氯仿中,同时,将0.23g的硫酸钠放在溶液中,而后将KH550逐滴加入到溶液中,其次,用碳酸氢钠进行提纯,最后,用氯仿:甲醇=10:1的淋洗剂层析提纯,真空下浓缩液体,最终得到油装粘稠液体。
将所得的N-苯基马来酰亚胺衍生物(CPMI-KH550)、苯乙烯、马来酸酐共聚,得到三元共聚产物。
加热油浴锅至76℃,将0.623gNPMI、1.437g St和4.2g MAH和25ml的二甲苯加入烧杯,并在此温度下搅拌40min;把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的250ml四颈瓶中,加入70ml二甲苯,通入N2气,搅拌、加热至90℃后恒温5min;再加入引发剂DCP并升温至125℃反应,反应4h,得到初产物。趁热将初产物溶于丙酮,用甲醇作沉淀剂重沉淀去除残留的单体和小分子,将得到的产物与60℃真空干燥24h,以去除小分子。得到粉状三元共聚物树脂样品。
实施例2
CPMA的合成步骤:(1)将10.78g MAH溶于10mL的DMF中;(2)将15.1g对氨基苯甲酸溶于100mL的DMF,而后将溶液在15-30min内滴加到MAH的DMF溶液中;(3)在40度下反应6h;(4)反应结束后,将反应体系冷却到室温,而后用碎冰提取;将反应溶液倒入到碎冰上,放置3-5min,趁冷抽滤;(5)放在40℃烘箱内烘CPMA。
称取21.7g第一步合成的N-(4-羧基苯基)马来酰胺酸(CPMA),将其溶于DMF中。加入2g的催化剂无水乙酸钠、20mL脱水剂醋酸酐、2g阻聚剂对苯二酚,升温,将温度控制在50-55℃之间,反应2h,溶液变为淡黄色透明状,冷却至室温后,静置,将溶液倒入碎冰中沉淀出现大量黄色针状晶体,再进行抽滤、洗涤、干燥,得到纯净的淡黄色晶体—N-(4-羧基苯基)马来酰亚胺(CPMI)。
将10.85g CPMI与氯化亚砜溶液在三口烧瓶中80℃回流2h;而后将多余的氯化亚砜蒸馏出来,得CPMIC。
将10.85gCPMIC溶于氯仿中,同时,将2.3g的硫酸钠放在溶液中,而后将KH550逐滴加入到溶液中,最后,用碳酸氢钠进行提纯,最后用氯仿:甲醇=10:1的淋洗剂层析提纯,真空下浓缩液体,最终得到油装粘稠液体,其氢核磁如图所示。
将所得的N-苯基马来酰亚胺衍生物、苯乙烯、马来酸酐共聚,得到三元共聚产物。
加热油浴锅至86℃,将6.23gCPMI-KH550、14.37g St和42g MAH和25ml的二甲苯加入烧杯,并在此温度下搅拌40min;把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的250ml四颈瓶中,加入70ml二甲苯,通入N2气,搅拌、加热至90℃后恒温5min;再加入引发剂DCP并升温至125℃反应,反应4h,得到初产物。趁热将初产物溶于丙酮,用甲醇作沉淀剂重沉淀去除残留的单体和小分子,将得到的产物与60℃真空干燥24h,以去除小分子。得到粉状三元共聚物树脂样品。将实例2中得到的产物加入到PA6进行提高尼龙6的耐热性能,结果如下表所示:
注:表中1号为未添加三元共聚,2号添加了5份三元共聚,3号添加了10份,4号添加了15份。
专业人员能够通过常识联想到的N-苯基马来酰亚胺取代位置在邻位、间位的化合物同样受到保护;只要含有N-苯基马来酰亚胺衍生物的二元、三元及以上的共聚物也在保护的范围之内。
Claims (6)
1.一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:其方法为:加热油浴锅至50-90℃,将N-苯基马来酰亚胺衍生物、苯乙烯、马来酸酐和二甲苯在此温度下搅拌20-60min;加入二甲苯,通入N2气,搅拌、加热至90-120℃后回流;再加入引发剂并升温至125℃反应,得到初产物;趁热将初产物溶于丙酮,加入甲醇;将得到的产物真空干燥,得到粉状树脂;所述的N-苯基马来酰亚胺衍生物为
2.根据权利要求1所述的一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:所述的N-苯基马来酰亚胺衍生物的制备方法:(1)以马来酸酐和对氨基苯甲酸为原料,DMF为溶剂,在室温下反应,得到中间产物CPMA;(2)将CPMA溶于DMF,加入脱水剂、催化剂、阻聚剂进行反应得到CPMI;(3)将CPMI与氯化亚砜酰氯化,得到CPMIC;(4)将CPMIC与KH550进行反应,最终得到最终产物CPMI-KH550;(5)将反应体系在真空下浓缩,而后柱层析提纯。
3.根据权利要求2所述的一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:步骤(1)马来酸酐和对氨基苯甲酸的投料比为1-1.3:1mol/mol,所用溶剂为DMF、二甲苯或DMF与二甲苯的混合溶剂。
4.根据权利要求2所述的一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:步骤(2)中的脱水剂为乙酸酐,催化剂为无水乙酸钠;阻聚剂为对苯二酚。
5.根据权利要求2所述的一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:步骤(3)中,反应温度为50-80℃。
6.根据权利要求2所述的一种N-苯基马来酰亚胺衍生物的共聚体组合物,其特征在于:步骤(4)中,KH550的滴加温度在5℃以下,反应温度为室温。
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