氯化亚铜乙二胺苄氯体系引发甲基丙烯酸甲酯溶液聚合和共聚合研究-有机化学专业毕业论文.docxVIP

摘要研究了氯化亚铜／乙二胺／苄氯催化体系在溶剂乙腈中催化甲基 摘要 研究了氯化亚铜／乙二胺／苄氯催化体系在溶剂乙腈中催化甲基 丙烯酸甲酯聚合以及甲基丙烯酸甲酯和苯乙烯共聚合，考察了聚合反 应时间、聚合温度、催化剂浓度、单体浓度对聚合的影响；并对以乙 腈为溶剂，氯化亚铜／乙二胺／氯甲基化镍酞菁催化甲基丙烯酸甲酯聚 合作了一定的探讨。 研究了催化剂的最佳配比关系，结果为：氯化亚铜、乙二胺、苄 氯的物质的量之比1：1．5：l；该催化体系催化甲基丙烯酸甲酯80 ℃聚合反应5小时，聚合转化率达56％，得到分子量较高(Mv为3．1 ×105)、分子量分布较窄(MWD为1．2)的聚甲基丙烯酸甲酯；采用 红外光谱(IR)、1H-NMR和I)SC技术对PMMA的微结构进行了表征，结 果表明PMIdA的间同含量高达57％，其玻璃化温度高达128．4。C，说 明该催化体系具有较高的间同立构定向性；采用重量法研究了甲基丙 烯酸甲酯聚合反应动力学，聚合速率方程为：Rp=Kp·[M】·P／]o一，聚 合反应表观活化能Ea为32．5kJ·tool一。 用乙腈作溶剂，氯化亚铜／乙二胺／苄氯催化不同配比的苯乙烯与 甲基丙烯酸甲酯共聚；St／MMA为85／15(物质的量之比1，90℃聚合反 应14小时，聚合转化率可达7l％，共聚物数均分子量为4．5×104， 分子量分布为1．12．用1H．NMR测定共聚物组成，得到共聚反应的竞 聚率为：rl(St)=0．73+0．01，r2(MMA)=0．45_+0．04。 研究了乙腈为溶剂，氯化亚铜／乙二胺／氯甲基化镍酞菁催化甲基 丙烯酸甲酯聚合，制得分子量分布较窄(为1．35)的蓝色透明的聚 甲基丙烯酸甲酯。 关键词：氯化亚铜、乙二胺、苄氯、甲基丙烯酸甲酯、苯乙烯、溶液 聚合 The The polymerization of methyl methacrylate and copolymerization of styrene(St)～methyl methacrylate(MMA)by cuprous chloride／ethylene* diamine／benzyt o魏loride with acetonitrile鼯solvent have been studied。 the effect of components of catalyst，polymerization time，polymerization temperature，catalyst concentration，and monemer concentration on polymerization have been systematically investigated， 确嚣 polymerization of MMA by cuprous chloride／ethylenediamine／ chloromethyl nickel pathalocyanine with acetonitrile as solvent have also been studied。 The optimum ratio of catalyst are as follows：molar ratio of cuprous chloride／ethylenediamine／benzyl chloride is 1：1．5：l；The high molecular weight(Mv,3．1×105)and narrow polydispersity(1．签PMMA carl be obtained with yield(56％)when the polymerization is carried out at 80℃ for 5 hours．The microstructure of PMMA were characterized by 擞，1鞭《醚袋and DSC，the results show that syndiotactic PMMA is aS high as 57％and glass transition temperature of PMMA is 128．4C．These results disclose that the catalytic system has high syndiotactic stereospecificity覃醅kinetic of MMA polymerization has been studied with weight measuring method，the polymerization rate equation is Rr=Kp·[MI·Ⅳr and the appar