生物基异山梨醇聚碳酸酯的合成和性能  

Preparation and Performances of Isosorbide-Based Polycarbonate

作　　者：冯俊 李进 冯健 魏忠[1,2] 王自庆 宋晓玲 Feng Jun;Li Jin;Feng Jian;Wei Zhong;Wang Ziqing;Song Xiaoling(Xinjiang Tianye(Group)Co.,Ltd.,Shihezi 832000,China;School of Chemistry and Chemical Engineering,Shihezi University/Key Laboratory of Green Chemical Processes,Shihezi 832001,China)

机构地区：[1]石河子大学化学化工学院/兵团绿色化工过程重点实验室,新疆石河子832000 [2]新疆天业(集团)有限公司,新疆石河子832001

出　　处：《工程塑料应用》2022年第10期16-20,共5页Engineering Plastics Application

基　　金：新疆生产建设兵团“揭榜挂帅”重大科技计划项目(2022AA002);石河子市“揭榜挂帅”重大科技计划项目(2022JB02)。

摘　　要：研究了以1,8-二氮杂双环[5.4.0]十一碳-7-烯、157-三叠氮双环(4.4.0)癸-5-烯(TBD)、4-二甲氨基吡啶、7-甲基六元二环胍和四丁基氢氧化铵为有机碱催化剂催化碳酸二苯酯和异山梨醇酯交换缩聚合成生物基异山梨醇聚碳酸酯(PIC)反应,解决含金属催化剂残留影响聚合物应用性能问题。研究发现,TBD在该反应中表现出最优活性。而后系统考察了催化剂浓度、聚合反应温度和时间对PIC的重均分子量(M_(w))和分子量分布系数(PDI)的影响,常压酯交换后获得的单体在250℃条件下缩聚90 min后,合成PIC的M_(w)为48760,对应的PDI值为1.64。差示扫描量热和热重分析测试结果显示,合成PIC聚合物的玻璃化转变温度(T_(g))和最大分解温度(T_(max))分别为164℃和378.8℃,1,4-丁二醇、1,5-戊二醇和1,6-己二醇链锻的引入会显著降低PIC的T_(g)和T_(max)值。1,8-Diazabicyclo[5.4.0]undec-7-ene,2,3,4,6,7,8-Hexahydro-1H-pyrimido[1,2-a]pyrimidine (TBD),4-Dimethyl‐aminopyridine,7-methylhexamembered bicyclic guanidine and tetrabutylammonium hydroxide were adopted as organic base cata‐lysts to catalyze the transesterification polycondensation of diphenyl carbonate and isosorbide to bio-based isosorbide polycarbonate(PIC),which can solve the problem of metal-containing catalyst residues.It was found that TBD exhibited the best catalytic activity among all the tested catalysts in this reaction.The effects of catalyst concentration,polymerization reaction temperature and time on weight average molecular weight (M_(w)) and distribution index of molecular weight (PDI) of the obtained PIC polymer were then sys‐tematically investigated.The M_(w)of the synthesized PIC is 48 760 at 250℃for 90 min,the corresponding PDI value of 1.64.Based on the results of differential scanning calorimetry and thermogravimetric analysis tests,the glass transition temperature (T_(g)) and max‐imum decomposition temperature (T_(max)) of the obtained PIC polymer are found to be 164^(o)C and 378.8℃,respectively,and the intro‐duction of 1,4-butanediol,1,5-pentanediol and 1,6-hexanediol into the molecular chain of PIC would significantly reduce the T_(g )and T_(max)values of PIC.

关 键 词：有机碱 酯交换缩聚 碳酸二苯酯 异山梨醇 生物基聚碳酸酯 

分 类 号：TQ323.43[化学工程—合成树脂塑料工业]