1,3,5-苯三甲基膦酸铝的合成及在硬质聚氨酯泡沫中应用  

Synthesis of Aluminum 1,3,5-Phenyltrimethylphosphonate and Its Application on Rigid PUR Foams

作　　者：杨旭锋 刘德标 陈龙 Yang Xufeng;Liu Debiao;Chen Long(Department of Chemistry&Chemical Engineering,Lyuliang University,Lyuliang 033001,China;Jiangsu Sanjili Chemical Co.,Ltd.,Lianyungang 222066,China)

机构地区：[1]吕梁学院,化学化工系,山西吕梁033001 [2]江苏三吉利化工股份有限公司,江苏连云港222066

出　　处：《工程塑料应用》2023年第3期136-141,共6页Engineering Plastics Application

基　　金：山西省高等学校科技创新项目(2021L568);校级教学改革创新项目(XJJGZ202204)。

摘　　要：为提高硬质聚氨酯泡沫(RPUF)的阻燃性能,避免火灾发生,制备了一种新型的膦酸铝阻燃剂1,3,5-苯三甲基膦酸铝(APMP)。首先以1,3,5-三甲苯和N-溴代丁二酰亚胺(NBS)为原料,通过自由基反应制备得到中间体1,3,5-三(溴甲基)苯(Ⅰ),随后该中间体I与亚磷酸三乙酯反应得到1,3,5-苯三甲基膦酸乙酯(Ⅱ),中间体Ⅱ依次通过水解反应和复分解反应得到1,3,5-苯三甲基膦酸(Ⅲ)和目标产物APMP。采用核磁氢谱、单晶衍射、电感耦合等离子体原子发射和粒度分析等手段对中间体和目标产物结构进行了表征,并得出了各反应的最佳条件,在该条件下APMP的总收率为61.6%。通过极限氧指数(LOI)测定仪和万能试验机等对RPUF的阻燃和力学性能进行测试。结果表明,APMP能够有效提高RPUF的阻燃性能,当APMP质量分数为20%(以聚醚多元醇的质量为基准),RPUF的LOI高达29.3%,UL-94垂直燃烧为V-0级,且材料的力学性能保持良好。Aluminum 1,3,5-phenyltrimethylphosphonate(APMP),a novel aluminum phosphonate flame retardant,was synthesized and used to improve the flame retardancy of rigid polyurethane foams(RPUF)and avoid fire.1,3,5-tris(bromomethyl)benzene(I)was firstly prepared using mesitylene and N-bromosuccinimide(NBS)as raw materials through radical reaction.Subsequently,the intermediate I and triethyl phosphite further reacted to obtain 1,3,5-phenyltrimethylphosphonate ethyl ester(II),which was then hydrolyzed to give the 1,3,5-phenyltrimethylphosphonic acid(III).The compound III was allowed to react with aluminium sulfate octadecanhydrous to provide the target product APMP.The intermediates and target product were characterized by nuclear magnetic resonance,single crystal X-ray diffraction,ICP and particle size analysis,and the optimal conditions for all reactions were obtained.Under these conditions,the total yield of the APMP is 61.6%.The flame retardancy and mechanical properties of RPUF were tested by limiting oxygen index(LOI)meter and universal testing machine.The experimental results show that the flame retardancy of RPUF can be effectively improved by APMP.When the amount of flame retardant in the prepared sample is 20%(based on the mass of polyether polyols),the sample passed the V-0 rating in UL 94 and the LOI is up to 29.3%.Whats more,the mechanical properties of material is well maintained.

关 键 词：1 3 5-三(溴甲基)苯 阻燃剂 膦酸铝 硬质聚氨酯泡沫 极限氧指数 

分 类 号：TQ265.1[化学工程—有机化工]