文献类型：期刊文献

英文题名：Construction and Regulation on Thiol-Acrylate Networks through Binary Polymerization of Thiol-Ene Polymerization and Free Radical Polymerization

作者：Li, Xiaoyu[1];Ren, Ning[2];Xiao, Yan[1];Li, Xinxin[3];Lang, Meidong[1];Zhu, Xinyuan[2]

机构：[1]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Key Lab Ultrafine Mat,Minist Educ, Shanghai 200237, Peoples R China;[2]Shanghai Jiao Tong Univ, Frontiers Sci Ctr Transformat Mol, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China;[3]East China Univ Sci & Technol, Sch Mat Sci & Engn, Key Lab Specially Funct Polymer Mat & Related Tech, Minist Educ, Shanghai 200237, Peoples R China

年份：2024

卷号：57

期号：20

起止页码：9867

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20244217206022);WOS:【SCI-EXPANDED(收录号:WOS:001330107400001)】；

基金：The authors are grateful for the financial support provided by the National Natural Science Foundation of China (No. 52273009), Yangtze River Scholar Program (No. WF221411002) and the Innovative Research Group Project of National Natural Science Foundation of China (No. 52421006).

语种：英文

外文关键词：Alkylation - Atom transfer radical polymerization - Crosslinking - Elastomers - Free radicals - Orthogonal functions - Reaction kinetics

摘要：Thiol-acrylate photopolymerization has emerged as a prevalent approach for network formation due to its reaction efficiency, monomer versatility, and simple process. However, the reaction mechanism of network formation and eventual regulation of the network properties remain unclear and challenging. Different from the conventional unimechanism of thiol-acrylate photopolymerization, herein, thiol-acrylate photopolymerization was considered as a binary polymerization between thiol-ene polymerization of thiol and acrylate (TEP) and free radical polymerization of acrylates (FRP). The kinetic behavior of diacrylate and multithiols (dithiol, trithiol, and tetrathiol) was monitored by real-time in situ FTIR and treated with a binary polymerization model. By simulation of the hybrid function and calculation of the hybrid parameters, the binary polymerization revealed that there existed a mutual interaction instead of orthogonal behavior between TEP and FRP. Notably, a significant transition from inhibition to a promotion effect was observed with increasing thiol composition and thiol functionality. Moreover, the physical/mechanical properties of the photo-cross-linked networks could be easily regulated through adjusting the mutual interaction of TEP and FRP. By increasing thiol functionality, the gel content of the formed networks increased, and the uniformity of networks was improved. Consequently, the reaction mechanism of thiol-acrylate polymerization can be perfectly interpreted by binary polymerization, which provides guidance for variable multithiol-diacrylate networks with tunable properties.