含磷三嗪环低聚物的合成及表征  

Synthesis and Characterization of Phosphorus-Containing Triazine Oligomer

作　　者：生启[1] 刘刚[1] 程晓乐[1] 刘述梅[1] 叶华[1] 赵建青[1] 

机构地区：[1]华南理工大学材料科学与工程学院,广东广州510640

出　　处：《石油化工》2007年第12期1244-1249,共6页Petrochemical Technology

基　　金：国家自然科学基金项目(20574020);广东省经贸委粤港招标项目(20060106-2);广州市科技攻关项目(2006Z2-D2031)

摘　　要：以亚磷酸三乙酯、三聚氰氯、季戊四醇和吗啉为原料,经3步反应合成了含磷三嗪环低聚物,考察了反应条件对中间体及产物收率的影响,对中间体及产物的结构和热性能进行了表征。实验结果表明,合成含磷三嗪环低聚物的适宜条件为:第一步,n(亚磷酸三乙酯):n(三聚氰氯)=3.1,室温下滴加亚磷酸三乙酯,70℃下反应6h,中间体2,4,6-三磷酸二乙酯基-1,3,5-三嗪(化合物Ⅰ)的收率为86.1%;第二步,n(化合物Ⅰ):n(吗啉)=1,室温下反应3h,中间体2-吗啉-4,6-二磷酸二乙酯基-1,3,5-三嗪(化合物Ⅱ)的收率为92.5%;第三步,n(化合物Ⅱ):n(季戊四醇)=1,130℃,二丁基氧化锡催化下反应24h,含磷三嗪环低聚物的收率为93.6%。3步实验合成含磷三嗪环低聚物的总收率为74.6%。该低聚物可用作聚烯烃的单组分膨胀型阻燃剂。A phosphorus -containing triazine oligomer was synthesized from triethyl phosphite, cyanuric chloride, pentaerythritol and morpholine through three steps. The chemical structures of the intermediates and the product was characterized by means of GPC, FTIR, ^1H NMR and ^31P NMR, and thermal stability of the product was evaluated by TG. Effects of reaction temperature, reaction time and feed ratio on synthesis of end product were investigated. Optimal conditions for preparation of first - step intermediate 2,4,6 - tri （ diethyl phosphate ） - 1,3,5 - triazine （ compound Ⅰ） ： dropping addition of triethyl phosphite at room temperature, n （ triethyl phosphite ） ： n （ cyanuric chloride） = 3.1, reaction time 6 h at 70 ℃ and compound Ⅰ yield 86. 1% ; for second -step intermediate 2 - morpholine -4,6 - di（diethyl phosphate） -1,3,5-triazine （compound Ⅱ）： reaction time 3 h at room temperature, n（compound Ⅰ） ： n（morpholine） = 1 and compound Ⅱ yield 92.5%; as for end product： dibutyltin oxide as catalyst, n（compound Ⅱ） ： n （pentaerythritol） = 1, reaction time 24 h at 130 ℃ and end product -phosphorus containing triazine oligomer yield 93. 6%. Total yield of three steps is 74. 6%. The product with highly thermal stability at 180 ℃ can be used as flame retardant with swelling property in polyolefin.

关 键 词：单组分膨胀型阻燃剂 三嗪环低聚物 亚磷酸三乙酯 三聚氰氯 季戊四醇 吗啉 

分 类 号：TQ314.248[化学工程—高聚物工业]