膨胀型季戊四醇磷酸酯类阻燃剂合成研究

Study on Intumescent Flame Retardant of Pentaerythritol Phosphate

以季戊四醇和三氯氧磷为原料合成了两种膨胀型阻燃剂中间体,分别为双环笼状磷酸酯1-氧基磷杂-4-羟甲基-2,6,7-三氧杂双环[2,2,2]辛烷(化合物Ⅰ)和二(2,6,7-三氧杂-1-氧基磷杂双环[2,2,2]辛烷-4-亚甲基)磷酰氯(化合物Ⅱ)。研究了物料配比、反应温度和反应时间对化合物Ⅰ产率的影响,结论表明:化合物Ⅰ的反应溶剂二氧六环,反应的摩尔比n(POCI_3):n季戊四醇)为1:0.9,梯度升温7 h,乙醇提纯重结晶,产率86%。同时,还研究了分批加入化合物Ⅰ和原料配比对化合物Ⅱ的影响,结果表明:乙腈作溶剂,反应的摩尔比n化合物Ⅰ):n(POCI_3)为1.9:1,反应温度是75~80℃,产率78%。用红外光谱图的方法表征了产品的结构;热失重数据表明:化合物ⅠⅡ具有良好的热稳定性和成炭性,其初始热分解温度分别为270℃和340℃在600℃时残炭率分别为58.918%、56.751%。

Used pentaerythritol and phosphorus oxychloride as raw materials synthesed two intermediates of intumescent flame retardant,which are caged bicyclic phosphate. 1 -oxo-4 -hydroxymethyl -2,6,7 -tri- oxa - 1 - phospha-bicyc-lo [ 2,2,2] octane （ compound [ ）, and bis （2,6,7 - trioxa - 1 - phospha-bicyclo [ 2,2, 2 ] octane - 4 - methanol） chlorophosphate （ compound Ⅱ ）. The effects of molar ratio, reaction temperature, time and other factors on the product yields are discussed, the results shows that n（ POCI3）：n（pentaerythritol）is 1 ： 0. 9, temperature rise, react time is 7 hours, and alcohol as solvent for post treatment, the yield is attained up to 86%. In otherwise,the results shows that n（POCI3 ）：n（ compound I ）is 1：1.9 ,the reaction temperature is 75- 80℃, production rate is 78%. The products were characterized by ultrared analysis （FTIR）. The result of thermal analysis showed that they all have high thermal stability and execent char-forming ability. The decomposition temperatures of compound Ⅰ -Ⅱ were 300℃ and 340℃. and residual carbon under 500℃ were 58.918% and 56. 751%.