文献类型：期刊文献

英文题名：Thermal self-initiated polymerization of divinylbenzene under refining conditions

作者：Zhu, Jiang-Yi[1];Yuan, Pei-Qing[1];Cao, Gui-Ping[1];Gong, Gao-Xu[1];Zhu, Xue-Dong[1];Li, Rui-Jiang[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2024

卷号：1238

外文期刊名：COMPUTATIONAL AND THEORETICAL CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001262035700001)】；

语种：英文

外文关键词：Divinylbenzene; Thermal polymerization; Refining process; Reaction kinetics; Density functional theory

摘要：To understand the thermal self-initiated polymerization of vinyl monomers during the divinylbenzene refining process, the differences in reaction behavior among these monomers were studied by density functional theory calculations. The calculations reveal that para-divinylbenzene (para-DVB) exhibits higher reactivity than other monomers in polymerization. Specifically, among the first step of initiation which is a Diels-Alder reaction, the reaction between para-DVB molecules shows the lowest activation energy (Ea) of 134.6 kJ/mol. Subsequently, para-DVB preferentially undergoes molecule-assisted homolysis with the products of the aforementioned DielsAlder reaction and formatting free radicals with an Ea of 74.8 kJ/mol and a reaction rate constant (kTST) of 3.48 x 10-3 L/mol center dot s. In the propagation stage, para-DVB also exhibits the highest monomer reactivity, with a kTST approximately 1.4-2.25 times greater than other monomers. The polymerization preformed under refining conditions confirms that the consumption of para-DVB is faster than that of other monomers, consistent with the DFT calculations.