文献类型：期刊文献

英文题名：The Spatial and Electronic Effects of Substituent Groups on the Thermal Curing of Bio-Based Benzoxazines

作者：Li, Rumeng[1];Zhan, Guozhu[2];Ma, Qi[1];Yang, Yunhe[1];Liu, Xiaoyun[1];Zhang, Yitong[1];Zhuang, Qixin[1]

机构：[1]East China Univ Sci & Technol, Minist Educ, Lab Specially Funct Polymer Mat & Related Technol, Shanghai 200237, Peoples R China;[2]Eighth Acad CASC, Inst 806, Huzhou 313000, Peoples R China

年份：2021

卷号：9

期号：12

起止页码：2093

外文期刊名：JOURNAL OF RENEWABLE MATERIALS

收录：;EI(收录号：20212810623716);WOS:【SCI-EXPANDED(收录号:WOS:000664384100004)】；

基金：This work was partially supported by the National Natural Science Foundation of China (51773060, and 52073091), Shanghai Natural Science Foundation (20ZR1414600), Shanghai Aerospace Science and Technology Innovation Fund (SAST2020-087), and the Fundamental Research Funds for the Central Universities (50321042017001).

语种：英文

外文关键词：Benzoxazine; spatial effects; electronic effects; bio-based

摘要：To explore the influence of substituent groups on thermally induced curing, eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were synthesized. The thermal curing of these bio-based benzoxazines was studied in detail. Combined with the curing reaction kinetics, simulation and calculation of Highest Occupied Molecular and Lowest Unoccupied Molecular values, the spatial and electronic effects of different substituent groups on the curing of benzoxazine was explored. It was found that when the substituent was located at the position directly connected to the N atom, the steric hindrance effect of the group was dominant. When the substituent group was located on the benzene ring connected to the O atom, both the electronic effect and the spatial effect influenced the curing of benzoxazine. When an electron-withdrawing group was connected ortho position to the O atom, the curing reaction was promoted due to the decreased electron cloud density of O- on the oxazine ring, making the C-O bond easier to break. When an electron-donating group was connected to the meta position of the O atom it also promoted the curing reaction, possibly because it increased the electron cloud density of the +CH2 reaction site and thereby facilitated electrophilic substitution via attack of +CH2 on the cross linking reaction centre. This work provides a deeper understanding of how spatial and electronic effects of substituents affect the curing of benzoxazine.