DFT-supported Mechanistic Understanding of the Ring-opening Polymerization of Cyclic Trithiocarbonates Mediated by Organic Base

聚合 单体 聚合物 亲核细胞 化学 硫黄 密度泛函理论 戒指(化学) 高分子化学 计算化学 有机化学 催化作用
作者
Xinjie Wang,Bai‐Hao Ren,Jin-Zhuo Zhao,Tianjun Yue,Xiaohui Kang,Wei‐Min Ren
出处
期刊:Chemical Research in Chinese Universities [Springer International Publishing]
卷期号:39 (5): 772-776 被引量:1
标识
DOI:10.1007/s40242-023-3034-0
摘要

Sulfur-rich polymers are endowed with several enhanced features, such as high refractive index and excellent thermal and mechanical properties, owing to the incorporation of sulfur atoms into the polymer main chain. As an important category of sulfur-rich polymers, polytrithiocarbonates can be efficiently synthesized through ring-opening polymerization(ROP) of cyclic trithiocarbonates(CTCs) mediated by 1,5,7-triazabicyclo[4.4.0] dec-5-ene(TBD) and benzyl mercaptan(BnSH). However, the mechanistic investigations of this reaction are limited. In this study, we attempted to understand this reaction by simulating chain initiation, propagation, and termination in the ROP of CTCs using density functional theory(DFT) calculations. As demonstrated, the acceleration of the ROP of δ-CTC by BnSH can be attributed to the smaller size of BnS− compared to TBD when nucleophilic attacking, and [TBDH]+ enhancing the interaction with the monomer and stabilizing the generated active species in the initiating process. In addition, the ability of BnSH to tune the topological structures of the final polymers is ascribed to the suppressed transesterification between the thiolate species and the first trithiocarbonate unit initiated by BnS−. Furthermore, the limitations that hinder the ROP of five- and six-membered CTCs under general conditions are the unfavored thermodynamic factors, wherein the ROP of six-membered CTC is possible below −75 °C.
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