Sulfur-substitution-enhanced crystallization and crystal structure of poly(trimethylene monothiocarbonate)  

作　　者：Xiaohan Cao Hongliang Wang Jialiang Yang Ruiyang Wang Xin Hong Xinghong Zhang Junting Xu Hai Wang 

机构地区：[1]MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027,China [2]Center of Chemistry for Frontier Technologies,Zhejiang University,Hangzhou 310027,China [3]Department of Chemistry,Zhejiang University,Hangzhou 310027,China [4]Department of Polymer Science and Engineering,College of Chemical Engineering,Dalian University of Technology,Dalian 116024,China

出　　处：《Chinese Chemical Letters》2022年第2期1021-1024,共4页中国化学快报（英文版）

基　　金：financial support of the National Natural Science Foundation of China (Nos.21774108 and 21574116);the Distinguished Young Investigator Fund of Zhejiang Province (No.LR16B040001);the China Postdoctoral Science Foundation (No.2020M681818);the Center of Chemistry for Frontier Technologies of Zhejiang University。

摘　　要：In this paper,the crystallization behavior of a novel poly(monothiocarbonate),poly(trimethylene monothiocarbonate)(PTMMTC),was investigated and compared with its polycarbonate analogue,poly(trimethylene carbonate)(PTMC).It is found that PTMMTC exhibits strong crystallizability,while un-stretched PTMC is amorphous.DSC and DMA results reveal that PTMMTC possesses higher glass transition temperature(T_(g))andβ-transition temperature(T_(β))than PTMC.Simulation based on density functional theory(DFT)shows that,the bond angle of C-S-C is evidently smaller than that of C-O-C,and thus a larger dipole moment.This leads to the stronger intermolecular interaction and more rigid chain confor-mation in PTMMTC,which is the origin of sulfur-substitution enhanced crystallization.The crystal struc-ture of PTMMTC was preliminarily determined for the first time.PTMMTC has an orthorhombic crystal structure with a planar zig-zag chain conformation.The parameters of unit cell are a=10.74 A,b=4.79 A,and c(fiber axis)=7.74 A.

关 键 词：Poly(monothiocarbonate) Polycarbonate Crystallization behavior Crystal structure Sulfur substitution enhanced crystallization 

分 类 号：TQ317[化学工程—高聚物工业]