呋喃基磷杂菲阻燃剂的合成及在阻燃环氧树脂中的应用  

Synthesis of Furan-based Phosphaphenanthrene Flame Retardant and Its Application in Anti-flammable Epoxy Thermosets

作　　者：唐刚[1] 陶熠 邓丹[2] 张冬欣 张诗华[1] 刘秀玉[1] 伍强 沈海峰 孙俊杰 TANG Gang;TAO Yi;DENG Dan;ZHANG Dongxin;ZHANG Shihua;LIU Xiuyu;WU Qiang;SHEN Haifeng;SUN Junjie(School of Architecture and Civil Engineering,Anhui University of Technology,Ma’anshan 243032,China;Department of Polymer Science and Engineering,Jiaxing University,Jiaxing 314001,China;Institute of Molecular Engineering and Applied Chemistry,Anhui University of Technology,Ma’anshan 243002,China)

机构地区：[1]安徽工业大学建筑工程学院,马鞍山243032 [2]嘉兴学院高分子材料与工程系,嘉兴314001 [3]安徽工业大学分子工程与应用化学研究所,马鞍山243002

出　　处：《高等学校化学学报》2024年第4期142-150,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:51403004);安徽省自然科学基金(批准号:2108085ME178,2008085ME176);安徽省科技重大专项(批准号:202203a06020003)资助。

摘　　要：以5-羟甲基糠醛、糠胺、三氯氧磷和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料合成了一种呋喃基磷杂菲阻燃剂(Furan-2DOPO),并利用傅里叶变换红外光谱(FTIR)、核磁共振波谱(^(1)H NMR和^(31)P NMR)对其结构进行了表征.进一步利用Furan-2DOPO对环氧树脂进行阻燃改性,得到一系列阻燃环氧固化物.考察了Furan-2DOPO的用量对阻燃环氧固化物的力学性能、热稳定性以及阻燃性能的影响.研究结果表明,当Furan-2DOPO的添加量(质量分数)仅为5%时(磷质量分数为0.47%),环氧固化物的氧指数达到31.0%,且能够通过UL-94垂直燃烧V-0级测试.与未改性环氧树脂相比,添加2.5%和5%Furan-2DOPO的环氧固化物的最大热释放速率分别下降了31%和35%.此外,2种添加Furan-2DOPO的环氧固化物的拉伸强度均比未改性环氧树脂提升了约28%.炭层分析结果表明,Furan-2DOPO具有良好的催化成炭性能,有利于减少燃烧过程中可燃性气体的逸出,从而提升阻燃性能.A novel bio-based flame retardant(Furan-2DOPO)was synthesized from 5-hydroxymethylfurfural,furfuramine,phosphorus oxychloride and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO).Its struc⁃ture was characterized by Fourier transform infrared spectroscopy,proton-and phosphorus-nuclear magnetic resonance spectroscopy.A series of cured flame retarded epoxy products was obtained by modification of epoxy resin with Furan-2DOPO.The effects of the loading of Furan-2DOPO on the mechanical properties,thermal stability and flame retardant properties of the cured epoxy products were investigated.The results showed that when the addition amount of Furan-2DOPO was only 5%(mass fraction,phosphorus mass fraction was 0.47%),the oxygen index of the cured epoxy product reached 31.0%,and can pass the UL-94 V-0 test;compared with the unmodified epoxy resin,the peak heat release rate of the cured epoxy products containing 2.5%(mass fraction)and 5%(mass fraction)Furan-2DOPO was decreased by 31%and 35%,respectively.In addition,the tensile strength of the cured epoxy products containing 2.5%and 5%Furan-2DOPO was about 28%higher than that of the unmodified epoxy resin,respectively.The results of char analysis indicated that Furan-2DOPO possessed excellent catalytic charring performance,which was conducive to reducing the escape of combustible gases during combustion,so as to improve the flame retardant performance.

关 键 词：环氧树脂 呋喃基磷杂菲 阻燃剂 热降解 

分 类 号：O633[理学—高分子化学]