膦腈碱催化己内酯开环聚合制备线型/支化聚己内酯  

Preparation of Linear/Branched Polycaprolactone by Phosphazene-Catalyzed Ring-Opening Polymerization of Caprolactone

作　　者：黄文艳 宋肄业 柴晨琼 韩彪 蒋其民 薛小强 杨宏军 蒋必彪 HUANG Wenyan;SONG Yiye;CHAI Chenqiong;HAN Biao;JIANG Qimin;XUE Xiaoqiang;YANG Hongjun;JIANG Bibiao(School of Materials Science and Engineering,Changzhou University,Changzhou 213164,China;Huaide College,Changzhou University,Jingjiang 214500,China)

机构地区：[1]常州大学材料科学与工程学院,江苏常州213164 [2]常州大学怀德学院,江苏靖江214500

出　　处：《常州大学学报（自然科学版）》2020年第1期36-43,共8页Journal of Changzhou University：Natural Science Edition

基　　金：国家自然科学青年基金资助项目(21304010);江苏省自然科学优秀青年基金资助项目(BK20170056);江苏高校优势学科建设工程资助项目(PAPD)

摘　　要：以膦腈碱t-BuP4为催化剂分别催化乙酸乙酯(EAc)和甲基丙烯酸乙酰氧基乙酯(AcEMA)引发己内酯(CL)的开环聚合反应,制备了线型和支化聚己内酯。利用核磁共振氢谱(1H NMR)、三检测体积排阻色谱仪(TD-SEC)和差示扫描量热仪(DSC)对共聚物进行了表征。结果表明,t-BuP4催化EAc引发CL的开环聚合反应时,随n(CL)∶n(EAc)的增加,聚合物的分子质量增加。t-BuP4催化AcEMA引发CL的开环聚合反应可成功制备支化PCL。当n(AcEMA)∶n(t-BuP4)为10∶2时,CL的转化率接近100%。所得聚合物的Mark-Houwink参数α值为0.36,结晶度仅有39.68%。Organic phosphazene superbase t-BuP4 was employed to catalyze ethyl acetate(EAc)and acetoxyethyl methacrylate(AcEMA)to initiate the ring opening polymerization ofε-caprolactone(CL).The structures of resulting polymers were characterized in detail by nuclear magnetic resonance spectroscopy(1H NMR),triple detection size exclusion chromatography(TD-SEC),and differential scanning calorimetry(DSC).The results showed that t-BuP4 could catalyze EAc to initiate the ring opening polymerization of CL resulting a linear poly(ε-caprolactone)(l-PCL).The molecular weight of the l-PCL increased with the increasing of n(CL)∶n(EAc)ratios.By using AcEMA as an initiator,branched poly(ε-caprolactone)(b-PCL)were obtained.When the molar ratio of n(AcEMA)∶n(t-BuP4)was 10∶2,the conversion of CL was close to 100%.The mark-houwink constant(α)and the degree of crystallinity of the corresponding b-PCL was 0.36 and 39.68%,respectively.

关 键 词：聚己内酯 膦腈碱 开环聚合 

分 类 号：TQ316.334[化学工程—高聚物工业]