可逆络合共聚制备支化聚苯乙烯  

Synthesis of Branched Polystyrene by Reversible Complexation-Mediated Copolymerization

作　　者：韩彪 杨宏军 王中睿 曹磊 黄文艳 薛小强 蒋其民 蒋必彪 HAN Biao;YANG Hong-jun;WANG Zhong-rui;CAO Lei;HUANG Wen-yan;XUE Xiao-qiang;JIANG Qi-min;JIANG Bi-biao(Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials,School of Materials Science and Engineering,Jiangsu Collaborative Innovation Center ofPhotovolatic Science and Engineering,Changzhou University,Changzhou 213164,China;Changzhou University Huaide College,Jingjiang 214500,China)

机构地区：[1]江苏省绿色环保重点实验室,常州大学材料科学与工程学院,江苏省光伏科学与工程协同创新中心,江苏常州213164 [2]常州大学怀德学院,江苏靖江214500

出　　处：《高校化学工程学报》2018年第3期562-567,共6页Journal of Chemical Engineering of Chinese Universities

基　　金：江苏省自然科学优秀青年基金(BK20170056)

摘　　要：偶氮二异丁腈(AIBN)和单质碘(I_2)原位生成碘化物,在催化剂碘化钠(NaI)的作用下,引发苯乙烯(St)和二甲基丙烯酸1,4-丁二醇酯(BDDMA)的可逆络合共聚反应,成功制备了支化聚苯乙烯。通过气相色谱仪(GC)、三检测体积排阻色谱仪(TD-SEC)、核磁共振氢谱(~1H-NMR)对聚合物和聚合反应过程进行表征和分析。结果表明,在配方[St]/[BDDMA]/[AIBN]/[I_2]/[NaI]=80/1.0/1.0/0.4/0.4时,80℃下反应24 h后St的转化率可达80%,所得聚合物的重均分子量高达13.8×10~4 g×mol^(-1),与同分子量的线型聚合物相比具有明显小的流体力学半径和特性黏度,BDDMA反应进入聚合物链后有69.9%的悬垂双键参与了支化反应。反应过程研究表明,聚合物的支化度随反应时间的延长而增加。Reversible complexation-mediated copolymerization（RCMcP） of styrene（St） and 1,4-butanediol dimethacrylate（BDDMA） was studied for the synthesis of branched polystyrene. Polymerization was first studied with [St]/[BDDMA]/[AIBN]/[I_2]/[NaI] molar ratio of 80/1.0/1.0/0.4/0.4. A soluable polymer in organic solvent with weight-averaged molecular weight（M_（w.MALLS）） of 1.38×105 g×mol^（-1） was obtained after 24 h, 80℃.The conversion of St determined by gas chromatography（GC） is over 80%.~1H-NMR results suggest that 69.9% of pendant vinyl bonds react to produce branched structures. Triple detection size exclusion chromatography（TD-SEC） results show that the hydrodynamic（R_h） and intrinsic viscosity（[η]） values of the resulting polymers are significantly lower than those corresponding linear polymers. These results further confirm the branched structure of the resulting polymer. Kinetic study suggests that the Zimm branching factor（g′） decreases with St conversion, which implies the formation and development of branching.

关 键 词：支化聚合物 可逆络合聚合 苯乙烯 二甲基丙烯酸1 4-丁二醇酯 

分 类 号：O316.32[理学—一般力学与力学基础]