窄分布三元醇聚酯的酶催化合成和链增长机理研究  

Synthesis of Narrow Distributed Triol-polyesters and An Insight into Chain Growth Behaviors

作　　者：石阿鹏 饶子昆 郝建原 SHI A-peng;RAO Zi-kun;HAO Jian-yuan(School of Materials and Energy,University of Electronic Science and Technology of China,Chengdu 610054,China)

机构地区：[1]电子科技大学材料与能源学院,四川成都610054

出　　处：《合成化学》2020年第11期949-954,共6页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(31670979,51273034);四川省科技项目(2018GZ0460,2019YFS0132)。

摘　　要：分别以三羟甲基乙烷和辛二酸二乙酯为反应单体,通过酶催化的方式,得到了窄分的树枝状3元醇聚酯。通过1H NMR,13C NMR以及GPC测试表征,对比了三羟甲基乙烷聚酯与丙三醇聚酯的链增长行为。结果显示:拥有3个等活性伯羟基的三羟甲基乙烷在与辛二酸聚合过程中,先后经历短时间的接枝链增长和长时间的树枝状链增长,最终形成了结构规则,分子量分布窄的树枝状结构。丙三醇同时含有伯羟基和仲羟基,脂肪酶对伯羟基的选择性催化导致其与辛二酸聚合过程中先后经历线型增长、接枝增长和“接枝+树枝状”增长,最终形成高分子量分布的无规树枝状结构。Herein,a narrow distributed dendritic trimethylolethane(TME)polyester was robustly obtained through polymerizing with suberic acid by lipase catalysis.A comparison had been made between chain growth behaviors of TME and glycerol polyesters by 1H NMR,13C NMR and GPC analysis.It was revealed that TME with three equal hydroxyls underwent a short term of grafted growth and longtime of dendritic growth,giving regular dendritic scaffolds with narrow molecular weight distribution.The glycerol with both primary and secondary hydroxyls would undergo linear growth,grafted growth and“grafted+dendritic”growth successively due to selective catalysis of lipase to primary hydroxyls.Thereby,only irregular dendritic scaffolds could be obtained.

关 键 词：酶催化 链增长机理 树枝状聚酯 三元醇聚酯 合成 

分 类 号：O621.3[理学—有机化学]