文献类型：期刊文献

英文题名：Kinetic and mechanistic elucidation of thermotropic liquid crystalline polyester (TLCP) pyrolysis for closed-loop recycling

作者：Li, Chenyang[1];Lin, Hongxing[1];Yan, Qing[2];Chen, Xinwei[1];Guo, Wenze[1,3];Lin, Shaoliang[4];Zhao, Ling[1];Xi, Zhenhao[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn & Low Carbon Technol, Shanghai Key Lab Multiphase Mat Chem Engn, Shanghai 200237, Peoples R China;[2]PetroChina Shanghai Adv Mat Res Inst Co Ltd, Shanghai 201306, Peoples R China;[3]East China Univ Sci & Technol, Key Lab Smart Mfg Energy Chem Proc, Minist Educ, Shanghai 200237, Peoples R China;[4]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

年份：2027

卷号：338

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001839980000001)】；

基金：This work is financially supported by the National Natural Science Foundation of China (Grant No. 22508116 and 22278129) and Funda-mental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM407) . The authors thank Xinyue Wang from Shiyanjia Lab ( www.shiyanjia.com ) for the help on TG-IR characterization.

语种：英文

外文关键词：Thermotropic liquid crystalline polyester; Pyrolysis; Kinetic; Reaction pathway

摘要：The multi-aromatic-ring structure of thermotropic liquid crystalline polyester (TLCP) leads to complex pyrolysis chemistry, producing both gaseous fragments and crosslinked aromatic char. Elucidating its kinetics and mechanisms is essential for directing TLCP waste toward high-value resource conversion. This study applied a multi-step kinetic deconvolution approach, followed by modeling with a discretized distributed activation energy model (DAEM). A seven-reaction DAEM was found to describe the pyrolysis of TLCP with higher precision, yielding average activation energies ranging from 329 to 766 kJ/mol. Among these, the reaction at a conversion of 0.47 contributed over 70% to the total mass loss. The main pyrolysis products, including CO, CO2, and phenolic compounds, were identified by pyrolysis experiments. Molecular simulations further revealed the relationship between chain-segment structure and cleavage sequence, as well as the reaction pathways of different products and their secondary transformations. Compared with the p-hydroxybenzoic acid homopolymer structure, the naphthalene-based segments showed higher susceptibility to bond cleavage. The scission of acyloxy bonds led to the formation of CO and phenols, while cleavage and dehydrogenation of alkoxy bonds resulted in the generation of CO2 and ketones.