三(4-膦酸二乙酯苯)胺阻燃剂的合成及应用  

Synthesis and Application of Tris(4-diethylphosphonatephenyl)amine Flame Retardant

作　　者：闫玉兵 杨旭锋 职慧珍[2] YAN Yubing;YANG Xufeng;ZHI Huizhen(Department of Chemistry&Chemical Engineering,Lyuliang University,Lyuliang,Shanxi 033001,China;College of Chemistry and Materials Science,Nanjing Normal University,Nanjing,Jiangsu 210023,China)

机构地区：[1]吕梁学院化学化工系,山西吕梁033011 [2]南京师范大学化学与材料科学学院,江苏南京210023

出　　处：《塑料》2022年第1期67-71,120,共6页Plastics

基　　金：江苏省产业前瞻与共性关键技术竞争项目(BE2017165);山西省高等学校科技创新项目(2019L0966);吕梁市引进高层次科技人才重点研发项目(2019105)。

摘　　要：采用N-溴代丁二酰亚胺(NBS)和三苯胺作为原料,通过自由基反应制备得到中间体三(4-溴苯)胺(TBTPA),然后,亚磷酸三乙酯与该中间体在无水NiCl_(2)催化下,经Michaelis-Arbuzov重排得到目标产物三(4-膦酸乙酯苯)胺(TDPPA)。通过核磁共振、高分辨质谱、元素分析等方法对化合物结构进行了表征,并研究了催化剂添加量、反应温度、反应时间对目标化合物产率的影响,确定了最佳的合成条件为n(NiCl_(2)):n(TBTPA)=0.20∶1.00,反应温度为150℃、反应时间为6 h,在该条件下,目标化合物的产率为76.5%。热重分析研究得知,TDPPA具有较高的热稳定性,将其用于硬质聚氨酯泡沫材料的阻燃改性,实验结果表明,当TDPPA添加量为25份时,样品的极限氧指数达到29.8%、UL 94垂直燃烧为V-0级。The intermediate tris(4-bromophenyl)amine(TBTPA)was synthesized using triphenylamine and N-bromosuccinimide as the raw materials through free radical reaction,then the TBTPA and triethyl phosphite were catalyzed by NiCl_(2) to synthesis the target product of tris(4-diethylphosphonatephenyl)amine(TDPPA)through the Michaelis-Arbuzov rearrangement reaction.The structure of the TDPPA was characterized by NMR,elemental analysis,high-resolution mass spectrometry.In addition,the effects of the dosage of catalyst,reaction temperature and reaction time on the yield of the desired compound were investigated.The results showed that the optimum conditions were as follows:n(NiCl_(2))∶n(TBTPA)=0.20∶1.00,reaction temperature is 150℃,reaction time is 6 hours.Under these conditions,the yield of TDPPA could be reached 76.5%.The high thermal stability of TDPPA has been confirmed by thermogravimetric analysis(TGA).The flame-retardant modification of rigid polyurethane foam(RPUF)materials by TDPPA has been studied.The experimental results showed that with the addition of 25%TDPPA,the value of limiting oxygen index and UL-94 vertical combustion of the composite material were 29.8%and V-0,respectively.

关 键 词：三(4-溴苯)胺 自由基反应 阻燃剂 膦酸酯 聚氨酯 极限氧指数 

分 类 号：TQ265.1[化学工程—有机化工] TQ314.248