丁香酚基双酚及聚硫醚碳酸酯的制备及性质研究  

Synthesis and Property of Eugenol-based Bisphenols and Poly(thioether carbonate)s

作　　者：黄彩娟 黄梦倩 陈沁 罗筑 谢海波 Cai-juan Huang;Meng-qian Huang;Qin Chen;Zhu Luo;Hai-bo Xie(Department of Polymeric Materials and Engineering,College of Materials&Metallurgy,Guizhou University,Guiyang 550025)

机构地区：[1]贵州大学材料与冶金学院高分子材料与工程系,贵阳550025

出　　处：《高分子学报》2022年第9期1095-1103,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号22065006,21704019);贵州省科技计划项目(项目号黔科合基础[2020]1Z004)资助。

摘　　要：以丁香酚和不同碳链长度的二硫醇为原料,通过紫外光引发的硫醇-烯点击反应,合成了丁香酚基含硫醚结构的双酚单体;之后与三光气反应制备了丁香酚基聚硫醚碳酸酯,并通过硫醚的氧化实现后氧化改性获得聚砜碳酸酯.采用核磁氢谱、核磁碳谱、红外研究丁香酚基双酚单体及其聚碳酸酯的结构,采用凝胶渗透色谱测定其分子量及分布,通过热重分析仪及示差扫描量热仪对丁香酚基聚碳酸酯的热性能进行研究,结果表明丁香酚基聚碳酸酯分子量在3.27×10^(4)~6.05×10^(4)g/mol之间,热失重5%的温度大于340℃,玻璃化转变温度在12.2~24.4℃之间,表现出良好的热稳定性,后氧化改性后热稳定性和玻璃化转变温度有所下降.Polycarbonate is one of the most important polymeric materials in human society,which has found wide application in various areas owning to its excellent properties.However,traditional polycarbonates are derived from non-renewable petroleum-based chemicals,some of which are highly toxic.Therefore,the search for renewable resources,such as biomass and carbon dioxide,to replace petroleum-based chemicals for polymer synthesis has received great attention in recent years.In this work,thioether-containing bisphenols were synthesized from bio based eugenol and dithiols with different lengths of carbon chain via thiol-ene click reaction initiated by UV light.The structures of eugenol-based bisphenols were confirmed by^(1)H-nuclear magnetic resonance(1H-NMR),13C nuclear magnetic resonance(13C-NMR)and Fourier-transform infrared spectroscopy(FTIR),and the yield reached 76.2%.The obtained bisphenols were polymerized with triphosgene under mild conditions to prepare eugenol based poly(thioether carbonate)s with satisfying yields.The structures of eugenol-based poly(thioether carbonate)s were illustrated by 1H-NMR,13C-NMR and FTIR,which demonstrated the successful preparation of poly(thioether carbonate)s.Gel permeation chromatography(GPC)analysis revealed that the molecular weight of those eugenol based poly(thioether carbonate)s was in the range from 3.27×10^(4 )g/mol to 5.72×10^(4 ) g/mol with polydispersity index between 1.1 and 1.9.The results of the thermal gravimetric analysis revealed that all the eugenol-based poly(thioether carbonate)s exhibited a one-step degradation pattern with a weight loss of 5%in the range of 343-359℃,and maximum degradation rates were found between 379 and 395℃,indicating the good thermostability of the as-prepared eugenol-based poly(thioether carbonate)s.The glass transition temperature of eugenol-based poly(thioether carbonate)s decreased from 24.4℃to 12.2℃as the lengths of the carbon chain of dithiols increased.Finally,one eugenol-based poly(thioether carbonate)was post-oxidized

关 键 词：丁香酚 聚碳酸酯 硫醇-烯点击反应 后氧化改性 

分 类 号：TQ317[化学工程—高聚物工业]