Premium
Depolymerization of Free‐Radical Polymers with Spin Migrations
Author(s) -
Yu Tianrong,
Gao Yang,
Wang Bo,
Dai Xing,
Jiang Wanrun,
Song Ruixia,
Zhang Zhanwen,
Jin Mingxing,
Tang Yongjian,
Wang Zhigang
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500645
Subject(s) - depolymerization , chemistry , polymer , monomer , density functional theory , molecular orbital , computational chemistry , population , chemical physics , polymer chemistry , organic chemistry , molecule , demography , sociology
The mechanism of depolymerization is one of the most essential issues in chemical engineering and materials science. In this work, we investigate the depolymerization reactions of three typical free‐radical poly(alpha‐methylstyrene) tetramers by using first‐principles density functional theory. The calculated results show that these reactions all need to overcome the energy barriers in the range of 0.58 to 0.77 eV, and that breaking the C−C bond at the chain end leads to the dissociation of alpha‐methylstyrene monomers from the polymers. Electronic‐structure analysis indicates that the reactions occur easily at the CR 3 unsaturated end, and that the frontier molecular orbitals that participate in the reactions are mainly localized at the unsaturated ends. Meanwhile, spin population analysis presents the unique net spin‐transfer process in free‐radical depolymerization reactions. We hope the current findings can contribute to understanding the free‐radical depolymerization mechanism and help guide future experiments.