4,4′,4′′-三膦酸甲酯三苯胺的合成及应用  

Synthesis and application of hexamethyl[nitrilotris(benzene-4,1-diyl)]tris(phosphonate)

作　　者：杨旭锋 陈栋栋 职慧珍[2] 杨锦飞[2] YANG Xufeng;CHEN Dongdong;ZHI Huizhen;YANG Jinfei(Department of Chemistry&Chemical Engineering,Luliang University,Luliang 033001,Shanxi,China;School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,Jiangsu,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：《精细化工》2020年第10期2120-2124,共5页Fine Chemicals

基　　金：山西省高等学校科技创新项目(2019L0966、2019L0941);江苏省产业前瞻与共性关键技术竞争项目(BE2017165)。

摘　　要：以三苯胺为原料,通过亲电取代反应制备得到中间体4,4’,4"-三碘代三苯胺(TITPA),该中间体与亚磷酸三甲酯在Pd(PPh3)2Cl2催化下经Arbuzov重排得到目标产物4,4’,4"-三膦酸甲酯三苯胺(TPTPA)。通过1HNMR、13CNMR、31PNMR、高分辨质谱和元素分析对目标产物进行了结构表征,并考察了催化剂种类与用量、反应温度、反应时间对目标化合物产率的影响。结果表明,最佳合成条件为:n[Pd(PPh3)2Cl2):n(TITPA)=0.18:1.00,反应温度150℃,反应时间5 h。在该条件下,目标产物TPTPA的收率可达82.5%。进一步地,将TPTPA用于PVC的阻燃改性。结果表明,当TPTPA添加量为10%(以PVC树脂的质量为基准,下同),样品的极限氧指数可达29.6%、UL-94垂直燃烧达V-0级,且力学性能良好。4,4’,4"-Nitrilotris(1-iodobenzene)(TITPA)was synthesized using triphenylamine as raw material through electrophilic substitution reaction.Subsequently,a classic Arbuzov rearrangement reaction between intermediate TITPA and trimethyl phosphite was performed in a catalytic amount of Pd(PPh3)2Cl2 to obtain hexamethyl[nitrilotris(benzene-4,1-diyl)]tris(phosphonate)(TPTPA).The target product was characterized by 1 HNMR,13CNMR,31PNMR,HR-MS and elemental analysis.The effects of catalyst types,catalyst dosage,reaction temperature and reaction time on the yield of the target compound were investigated.The results showed that the optimum conditions were obtained as follows:n[Pd(PPh3)2Cl2]:n(TITPA)=0.18:1.00,reaction temperature of 150℃,reaction time of 5 h.Under these conditions,the yield of hexamethyl[nitrilotris(benzene-4,1-diyl)]tris(phosphonate)could reach 82.5%.Subsequently,TPTPA as a flame retardant was used for flame retardant modification of PVC.The results indicated that the prepared sample with an additive amount of TPTPA of 10%(based on the mass of PVC resin,the same below)had limited oxygen index of 29.6%and vertical combustion test of UL-94 up to V-0 level as well as maintained excellent mechanical properties.

关 键 词：膦酸酯 阻燃剂 4 4’ 4"-三碘代三苯胺 Arbuzov反应 橡塑助剂 

分 类 号：TQ314.24[化学工程—高聚物工业]