单一分子量γ-丁内酯齐聚物的合成及其结晶行为研究  

Crystallization Kinetics of Precisely Synthesized Discrete Oligo(γ-butyrolactone)s

作　　者：冯澳 段素华 曹晓环 谭睿 黄智豪 张晓华[2,3] 张正彪 Ao Feng;Su-hua Duan;Xiao-huan Cao;Rui Tan;Zhi-hao Huang;Xiao-hua Zhang;Zheng-biao Zhang(College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123;Center for Soft Condensed Matter Physics and Interdisciplinary Research,Soochow University,Suzhou 215006;School of Physical Science and Technology,Soochow University,Suzhou 215006)

机构地区：[1]苏州大学材料与化学化工学部,苏州215123 [2]苏州大学软凝聚态物理及交叉研究中心,苏州215006 [3]苏州大学物理科学与技术学院,苏州215006

出　　处：《高分子学报》2022年第9期1131-1141,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21925107,22171204)资助项目。

摘　　要：聚γ-丁内酯作为一种真正意义上可以实现“单体—聚合物—单体”的可循环聚酯种类,其结构性能的精准研究引起了广泛的兴趣.本文从生物基原料丁内酯和丁二酸酐出发,通过迭代指数级增长策略结合高效的酯化条件,合成了一系列单一分子量γ-丁内酯齐聚物,其结构经过了核磁共振氢谱,凝胶渗透色谱和大分子质谱的严格表征,并研究了这些单一分子量γ-丁内酯齐聚物的结晶行为.结果表明,单一分子量γ-丁内酯齐聚物的熔融温度随分子量的增加而升高,而多分散样品的熔融温度与分子量近似的单一分子量γ-丁内酯齐聚物相似.在相同结晶温度下,分子量越高,成核速率和球晶生长速率越大,结晶越快.多分散样品的结晶行为主要受高分子量组分的影响.As one of the chemical recycling to monomer polymer,poly(γ-butyrolactone)(PBL),polymerized from intrinsically recyclable five-memberedγ-butyrolactone ring,exhibits unique properties and complete recyclability.Therefore,it receives more and more attention in polymer science.In order to accurately understand the effect of structures of PBL on crystalline behaviors,a series of discrete oligo(γ-butyrolactone)s(o BLs)with different chain lengths were synthesized via iterative exponential growth strategy combined with efficient esterification conditions usingγ-butyrolactone and succinic anhydride as starting materials.The molecular structures of these discrete o BLs are validated by size-exclusion chromatography,matrix-assisted laser desorption ionization time-of-flight mass spectrometry and1H-NMR spectroscopy.We systematically investigate the crystalline behaviors of o BLs using differential scanning calorimetry and polarized optical microscopy.Specifically,we focus our attention on the effect of molecular weight(MW)and molecular weight distribution on nucleation,crystallization temperature,melting temperature,crystal growth rate and crystallization rate of o BLs.The nucleation rate,crystallization temperature,melting temperature,crystal growth rate and crystallization rate increase with an increase of molecular weight of discrete o BLs.For dispersed PBL,the high-MW components dominate the crystallization behaviors.Dispersed PBL exhibits relatively high nucleation rate,crystal growth rate and crystallization rate compared to discrete o BL with similar molecular weight.

关 键 词：单一分子量高分子 γ-丁内酯齐聚物 迭代指数及增长 结晶行为 

分 类 号：TQ317[化学工程—高聚物工业]