聚己内酯和聚碳酸酯型聚氨酯的合成及性能研究  

Synthesis and Properties of Polycaprolactone and Polycarbonate-based Polyurethanes

作　　者：程博翔 王明倩 丁志强 马哲 王彬[1] 李悦生[1] Bo-xiang Cheng;Ming-qian Wang;Zhi-qiang Ding;Zhe Ma;Bin Wang;Yue-sheng Li(School of Materials Science and Engineering,Tianjin University,Tianjin 300350)

机构地区：[1]天津大学材料科学与工程学院,天津300350

出　　处：《高分子学报》2024年第10期1346-1355,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52222302)资助项目

摘　　要：国内聚己内酯二元醇的产能无法满足聚酯型聚氨酯工业的生产需求,寻找与聚己内酯型聚氨酯(PCL-PU)性能相当的替代物具有重要研究意义.本工作利用Lewis pair催化的可控开环聚合分别制备了不同相对分子质量的聚己内酯(PCL-diol)和聚碳酸(1,4-丁二醇)酯多元醇(PC-diol),并通过核磁共振波谱和基质辅助激光解吸电离飞行时间质谱分析表征了2种聚酯二元醇的结构.将2种二元醇分别与2,4-甲苯二异氰酸酯(TDI)、扩链剂1,4-丁二醇(BDO)反应合成了PCL-PU及聚碳酸酯型聚氨酯(PC-PU).结合多种分析表征方法进一步对比研究了2种聚氨酯的热性质、结晶行为和力学性能.结果表明,PC-PU具有和PCL-PU相近的热稳定性和热分解过程,2种聚氨酯的初始分解温度均>260℃,且均具有2个热分解阶段.PCL-PU具有较快的结晶速率,而PC-PU的结晶速率较慢.相比于PCL-PU,PC-PU具有更高的断裂伸长率(>1200%)和断裂强度(>45 MPa).本工作为创制具有PCL-PU相当性能的PC-PU提供了科学基础与依据,有望促进聚氨酯工业的进一步发展.Polycaprolactone polyurethane(PCL-PU)has excellent mechanical properties,good biocompatibility and biodegradability,which is widely used in biomedical materials and other fields.However,the domestic production capacity of polycaprolactone diols is unable to meet the production demand of the polyester-based polyurethane industry.The search for alternatives with comparable properties to polycaprolactone-based polyurethanes is of great research importance.Therefore,in this study,three polycaprolactone(PCL-diol)and polycarbonate(1,4-butanediol)ester polyols(PC-diol)with different relative molecular masses were prepared using Lewis paircatalyzed controlled ring-opening polymerization,respectively.The structures of the two polyester diols were characterized by nuclear magnetic resonance hydrogen spectrometry(1H-NMR)and matrix-assisted laser desorption ionization time-of-flight mass spectrometry analysis(MALDI-TOF MS).PCL-PU and polycarbonate polyurethane(PC-PU)were synthesized by the reaction of two polyester diols with 2,4-toluene diisocyanate(TDI)and chain extender 1,4-butanediol(BDO),respectively.The thermal properties,crystalline behaviors,and mechanical properties of the two polyurethanes were further investigated in a comparative manner by thermogravimetric analysis,differential scanning calorimetry analysis,and stress/strain test.The results show that PC-PU has similar thermal stability and thermal decomposition process as PCL-PU,and the initial decomposition temperature of both polyurethanes is higher than 260℃,and both of them have two thermal decomposition stages.PCL-PU has a faster crystallization rate,while PC-PU has a slower crystallization rate.Compared to PCL-PU,PC-PU has higher elongation at break(>1200%)and breaking strength(>45 MPa).This paper provides a scientific basis and rationale for the creation of PC-PU with comparable properties of PCL-PU,and provides impetus for the development of the polyurethane industry.

关 键 词：聚己内酯 聚碳酸酯 聚酯二元醇 开环聚合 聚氨酯 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]