双噁唑啉对聚碳酸1,2-环己二酯的扩链研究  

CHAIN EXTENSION OF MALEIC ANHYDRIDE END-CAPPED POLY(1,2-CYCLOHEXYLENE CARBONATE) BY BISOXAZOLINES

作　　者：高凤翔[1,2] 周庆海[1] 秦玉升[1] 王献红[1] 赵晓江[1] 王佛松[1] 

机构地区：[1]中国科学院生态环境材料高分子重点实验室长春应用化学研究所,长春130022 [2]中国科学院研究生院,北京100039

出　　处：《高分子学报》2011年第7期772-777,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20634040)资助项目

摘　　要：采用马来酸酐封端聚碳酸1,2-环己二酯(PCHC),使其末端羟基转变为端羧基(MA-PCHC),并以2,2'-双-(2-噁唑啉)(BOZ)为扩链剂进行扩链反应.研究发现,BOZ与MA-PCHC中的羧基等摩尔情况下,扩链效果最佳.扩链后的PCHC的数均分子量从扩链前的5.6×104增长到12.4×104.扩链后的PCHC热稳定性能得到了明显的提高,起始热分解温度(Td-5%)由260℃提高到317℃,玻璃化转变温度(Tg)由114℃提高到133℃,而且在凝胶含量没有明显变化的情况下熔体黏度提高了30倍.封端扩链后的PCHC的拉伸强度从普通PCHC的35.81 MPa增加至40.22 MPa,断裂伸长率从4.59%增加至6.22%,而且封端扩链后的PCHC甚至出现了一定的应力屈服的现象.Poly（1,2-cyclohexylene carbonate）（PCHC） was prepared by copolymerization of carbon dioxide and cyclohexene oxide with Y（CCl3COO）3-ZnEt2-glycerin rare earth metal coordination ternary catalyst.The result polymer showed number average molecular weight（Mn） of 56.3×103 with polydispersity index of 4.9.Though PCHC showed high glass transition temperature（Tg）,PCHC was easy to degrade during melt processing,accompanied by severe deterioration of its mechanical performance,which constituted one of the main obstacles for commercialization of PCHC.In order to impove the thermal stability and mechanical properties of PCHC,the thermal decomposition reaction was compensated by the chemical chain extension reaction.At first,maleic anhydride was used as end-capper of PCHC to prevent its chain unzipping reaction,the MA and PCHC in weight ratio of 1∶100 were added into dichloromethane to make a 20 wt% solution,and refluxed at 41~43℃ for 48 h,then the polymer was precipitated by ethanol to obtain maleic anhydride end-capped PCHC（MA-PCHC）.MA-PCHC was then subjected to chain extension reaction at 180℃ and 60 r/min in the a Haake mixer for 5 min using 2,2′-bis（2-oxazoline）（BOZ） as chain extender.The optimal chain extension condition was found when equimolar BOZ and carboxyl group in MA-PCHC were used,the Mn of MA-PCHC increased from 5.6×104 to 12.4×104.The thermal stability of PCHC after chain extension was greatly improved,compared with the as-polymerized PCHC,the thermal decomposition temperature at 5 wt% loss（Td-5%） for chain extended PCHC increased from 260℃ to 317℃,the Tg increased from 114℃ to 133℃,and most importantly,the melt viscosity increased by 30 times.It should be noted that no significant change in gelatin content was observed during chain extension reaction.Moreover,the chain extended PCHC showed tensile strength increase from 35.8 MPa（as polymerized PCHC） to 40.2 MPa,and the elongation at break increased from 4.59% to 6.22%,yielding phenomenon was observed in

关 键 词：二氧化碳-氧化环己烯共聚物 2 2'-双-(2-噁唑啉) 马来酸酐 封端 扩链 

分 类 号：O631.3[理学—高分子化学]