酯交换熔融缩聚法制备脂肪族聚碳酸酯  

Preparation of aliphatic polycarbonate by ester exchange melt condensation method

作　　者：李振环[1,2] 邹彦琪 刘成志 LIZhenhuan;ZOUYanqi;LIU Chengzhi(School of Material Science and Engineering,Tiangong University,Tianjin 300387,China;State Key Laboratory of Separation Membranes and Membrane Processes,Tiangong University,Tianjin 300387,China;School of Chemical Engineering and Technology,Tiangong University,Tianjin 300387,China)

机构地区：[1]天津工业大学材料科学与工程学院,天津300387 [2]天津工业大学省部共建分离膜与膜过程国家重点实验室,天津300387 [3]天津工业大学化学工程与技术学院,天津300387

出　　处：《天津工业大学学报》2024年第6期51-60,共10页Journal of Tiangong University

基　　金：国家自然科学基金资助项目(21878231);天津市自然科学基金重点项目(22JCZDJC00100)。

摘　　要：针对传统脂肪族聚碳酸酯(APC)的工业制备方法高污染和高能耗的问题,采用一锅法,以不同碳酸二烷基酯和直链二元醇作为缩聚单体,熔融缩聚制备APC类可降解工程塑料,研究不同碳酸二烷基酯、催化剂种类、催化剂用量、预聚时间、缩聚温度、直链二元醇碳原子数等因素对APC产物平均分子质量和产率的影响,优化缩聚工艺,并对产物的结构和热力学性能进行表征。结果表明:优化工艺条件为碳酸二甲酯(DMC)和1,4-丁二醇作为缩聚单体、乙酰丙酮锂作为催化剂且其用量为1,4-丁二醇物质的量的1.4%、预聚反应时间为4.5 h、缩聚温度达到245℃,此条件下所制备聚碳酸丁二醇酯(PBC)的重均分子质量达到最大值MW=4.04×10^(4)g/mol,产率达到82.0%;分别采用DMC/1,4-丁二醇、DMC/1,5-戊二醇、DMC/1,6-己二醇制备的3种APC的初始热分解温度达到250℃以上,可以满足相应的使用温度条件。In response to the high pollution and energy consumption issues of traditional industrial preparation methods for aliphatic polycarbonate(APC),using a one pot method with different alkyl carbonates and linear diols were used as condensation monomers,and APC type degradable engineering plastics were prepared by melt condensation.The influence of different types of dialkyl carbonate,catalyst types,catalyst dosages,prepolymerization times,temperature and the number of carbon atoms in diols on the MW and yield of APC products was studied.The condensation process was optimized and the structure and thermodynamic properties of the prepared product were characterized.The results indicate that the optimized process conditions are dimethyl carbonate(DMC)and 1,4-butanediol as condensation monomers,lithium acetylacetonate is used as a catalyst and its dosage is 1.4%of the amount of 1,4-butanediol substance,the pre-polymerization reaction time is 4.5 h and the condensation temperature reaches 245℃.The weight average molecular weight of the prepared polybutylene carbonate reaches MW=4.04×10^(4) g/mol,and the yield reaches 82.0%.Using DMC/1,4-butanediol,DMC/1,5-pentanediol,DMC/1,6-hexanediol,respectively,three types of APC are prepared and its initial thermal decomposition temperature reaches above 250℃,which can meet the corresponding temperature conditions for usage.

关 键 词：脂肪族聚碳酸酯 碳酸二烷基酯 直链二醇 酯交换 熔融缩聚法 

分 类 号：TQ316.4[化学工程—高聚物工业] TQ320.62