DOPO基阻燃腈纶聚合物的制备与燃烧性能  

Preparation and Combustion Behavior of Copolymerized Polyacrylonitrile Using DOPO-Based Flame Retardant

作　　者：魏子行 秦统 奚桢浩[1,2] 赵玲[1,3] Zihang Wei;Tong Qin;Zhenhao Xi;Ling Zhao(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;Engineering lesearch Center of Process System Engineering,East China University of Science and Technology,Ministry of Education,Shanghai 200237,China;Key Laboratory of Oil and Gas Fine Chemicals,Ministry of Education,Xinjiang University,Xinjiang 830046,China)

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237 [2]华东理工大学过程系统工程教育部工程研究中心,上海200237 [3]新疆大学石油天然气精细化工教育部重点实验室,新疆乌鲁木齐830046

出　　处：《高分子材料科学与工程》2021年第4期40-48,共9页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(21878256,21978089);十三五国家重点研发计划(2016YFB0302701);中央高校基本科研业务费专项资金(22221817014,22221818014)。

摘　　要：文中合成了反应型有机磷酸酯功能阻燃剂9,10-二氢-9-氧杂-10-磷杂菲-10-氧甲基丙烯酸酯(DOPOAA),并通过水相沉淀聚合制备了原位共聚改性的阻燃聚丙烯腈,利用红外光谱分析了阻燃聚丙烯腈链段组成,并通过与二乙基膦酸甲基丙烯酸酯(DEAMP)进行对比,详细研究了改性聚丙烯腈的热稳定性和燃烧行为。结果表明,芳环结构有机磷酸酯DOPOAA与单体丙烯腈的竞聚率较为接近;原位共聚改性的聚丙烯腈热稳定性与阻燃性能显著提升;较脂肪结构磷酸酯阻燃剂DEAMP,DOPOAA在气相中也起到了关键的阻燃作用,且在较低的磷含量时即可表现出优异的阻燃性能。当DOPOAA质量分数为15%时,改性聚丙烯腈第1阶段失重温度提高约30℃,热分解残炭量提高约30%,极限氧指数值可达25.1%,热释放速率峰值(pkHRR)降低至598.16 kW/m^(2),总释放热(THR)下降为28.91 MJ/m^(2),燃烧后的炭层表面致密、平滑,结构完整,阻燃性能优异。Reactive organic phosphate functional flame retardant,(6-oxido-6 H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl acrylate(DOPOAA)was synthesized and copolymerized with acrylonitrile through an aqueous slurry route.The structure of flame retardant polyacrylonitrile(PAN)chains were confirmed by infrared spectrum,while the thermal stability as well as the combustion behavior were studied in detail by comparing with diethyl(acryloyloxymethyl)phosphonate(DEAMP).The results show that the incorporation of DOPOAA in polymeric chains can obviously improve the thermal stability and flame retardancy of copolymerized PAN.When the mass fraction of DOPOAA is 15%,the mass loss temperature at the first stage of thermal degradation of copolymerized PAN is increased by 30℃higher than that of unmodified PAN,and the corresponding carbon residue is increased about 30%at 700℃.Furthermore,the limit oxygen index(LOI)value of flame retardant PAN with DOPOAA increases to 25.1%,which is better than DEAMP.The peak heat release rate(pkHRR)is reduced to 598.16 kW/m^(2),and the total heat release(THR)is reduced to 28.91 MJ/m^(2).And the surface morphology of char residue shows dense and smooth with complete structure,but some macroporous bubbles exit inside.Besides the condensed phase flame retardant mechanism of aliphatic DEAMP,DOPOAA also has the mechanism of gas phase flame retardance,that contributes to better flame retardant performance of PAN/DOPOAA at relative lower phosphorus contents.

关 键 词：聚丙烯腈 9 10-二氢-9-氧杂-10-磷杂菲-10-氧化物 阻燃 燃烧性能 极限氧指数 

分 类 号：TQ342.31[化学工程—化纤工业]