硫元素在磷杂菲基阻燃环氧树脂中的作用  

Effect of Sulfur Element on Flame-Retardant Epoxy Resin Based on Phosphaphenanthrene

作　　者：叶小林[1] 许志彦 许松江 侯泽明 祁钰昭 宝冬梅[1] 龙丽娟[2] 张道海 周国永 蔡晓东 文竹 吴中立 Xiaolin Ye;Zhiyan Xu;Songjiang Xu;Zeming Hou;Yuzhao Qi;Dongmei Bao;Lijuan Long;Daohai Zhang;Guoyong Zhou;Xiaodong Cai;ZhuWen;ZhongliWu(School of Chemical Engineering,Guizhou Minzu University,Guiyang 550025,China;National Engineering Research Center for Compounding and Modification of Polymer Materials,Guiyang 550014,China;Faculty of Mechanical Engineering and Automation,Liaoning University of Technology,Jinzhou 121001,China)

机构地区：[1]贵州民族大学化学工程学院,贵州贵阳550025 [2]国家复合改性聚合物材料工程技术研究中心,贵州贵阳550014 [3]辽宁工业大学机械工程与自动化学院,辽宁锦州121001

出　　处：《高分子材料科学与工程》2022年第11期58-65,共8页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(51863004,52163001);贵州省省级科技计划项目(黔科合基础[2020]1Y211,ZK[2021]一般248,ZK[2022]216,黔科合平台人才-CXTD[2021]005);贵州省2018年度高层次创新型人才培养-千层次人才项目;辽宁省博士启动基金(20180540110);贵州省高等学校“绿色化学与资源环境创新团队”(黔教技[2022]13号);贵州民族大学高分子复合材料工程研究中心(GZMUGCZX[2021]-01)。

摘　　要：为了探讨硫元素在磷杂菲基阻燃环氧树脂中的作用,将阻燃剂9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS)按照不同添加量分别添加至环氧树脂(EP)中,以4,4’-二氨基二苯砜(DDS)为固化剂制备了阻燃复合材料。采用热重(TG)、极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热(CONE)、热重-红外光谱分析(TG-IR)和扫描电镜(SEM)等手段,对比研究了阻燃复合材料EP/DOPO和EP/DOPS的热稳定性、阻燃性能和成炭性能,并深入分析了其阻燃机理。结果表明,当DOPO和DOPS的添加量为10%时,EP/DOPO和EP/DOPS均达到UL-94 V-0级,LOI值分别为31.0%和30.6%;两者的热释放速率(HRR)、总热释放量(THR)和平均质量损失速率(av-MLR)值均低于纯EP,有效改善了EP的阻燃性能。而且,EP/DOPS的残炭量和阻燃性能均优于EP/DOPO,归因于DOPS中P和S元素的协同阻燃,能更好地促进基材脱水成炭,增强其凝聚相阻燃作用。SEM和TG-IR分析结果表明,阻燃剂DOPO和DOPS在气相和凝聚相共同发挥阻燃作用,但以气相阻燃作用为主,DOPS在凝聚相发挥的阻燃作用优于DOPO。In order to investigate the effect of sulfur element on flame-retardant epoxy resin based on phosphaphenanthrene,flame-retardants 9,10-dihydro 9-oxa 10-phosphaphenanthrene 10-oxide(DOPO)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide(DOPS)were added to EP according to the mass fraction of 5%,7.5%and 10%respectively,and 4,4'-diaminodiphenylsulfone(DDS)was used as curing agent to prepare flame retardant composites.Thermogravimetric analysis(TG),limiting oxygen index(LOI),vertical flame test(UL 94),cone calorimeter test(CONE),thermogravimetric-infrared spectroscopy analysis(TG-IR)and scanning electron microscopy(SEM)were used to compare the thermal stability,flame retardancy and charring properties of EP/DOPO and EP/DOPS,and their flame retardancy mechanisms were analyzed.The results show that when the mass fraction of DOPO and DOPS is 10%,EP/DOPO and EP/DOPS reach UL 94 V 0,with LOI values of 31.0%and 30.6%respectively.The heat release rate(HRR),total heat release rate(THR)and average mass loss rate(av-MLR)of the two composites are lower than those of pure EP,which effectively improve the flame retardancy of EP.Moreover,the char residue and flame retardancy of EP/DOPS are better than those of EP/DOPO,which is attributed to the synergistic flame retardancy of P and S elements in DOPS,which could better promote the dehydration of substrate into carbon and enhance the flame retardancy of condensed phase.SEM and TG-IR results show that DOPO and DOPS have flame retardancy in both gas phase and condensed phase,but mainly in gas phase,and DOPS has better flame retardancy in condensed phase than DOPO.

关 键 词：硫元素 磷杂菲 阻燃剂 环氧树脂 阻燃机理 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]