阻燃剂二羟基硅酸双硫代PEPA酯的 合成及应用

Synthesis and Application of Flame Retardant Dihydroxy Silicate Disulfide PEPA Ester

摘要:

以四氯化硅（STC）与1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷（SPEPA）为原料，合成二羟基硅酸双硫代PEPA酯阻燃剂，即二羟基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯(SDSPE)。探讨了溶剂、反应温度、反应时间及物料比等对产率的影响，最优化工艺条件：二氧六环作溶剂，四氯化硅与SPEPA物质的量比为1:2.1，在30℃下反应6h，再与二倍物质的量的水在60℃下反应4h，得二羟基硅酸双硫代PEPA酯，产率为93.9%。通过FTIR、1H-NMR、热重分析及极限氧指数测试等对产物的结构及性能进行了表征。测试结果表明，产物有很好的热稳定性，且应用于191不饱和树脂时，表现出了较好的阻燃效果。

Abstract:

A dihydroxysilicate disulfide PEPA ester flame retardant, dihydroxy silicate bis-1-thiophospha -2,6,7- trioxabicyclo [2.2.2] octyl-4-methyl ester(SDSPE), was synthesized by silicon tetrachloride(STC) and 1-thiophospha-4-hydroxymethyl-2,6,7-trioxabicyclo [2.2.2] octane (SPEPA). The effects of solvent, reaction temperature, reaction time and mass ratio on the yield were investigated. The optimal conditions were selected as follows: dioxane as solvent, the first step kept the reaction going at 30℃for 6h when the molar ratio of STC and SPEPA was 1:2.1, and then reacted with two times amount of water at 60癈 for 4h to obtain a dihydroxysilicate disulfide PEPA ester. The yield could reach to 93.9%. The structure and flame retardance of the product were characterized by means of FTIR, 1H -NMR, TG-DTA analysis and LOI technique. Results showed that the product had a good thermal stability and high flame-retardant efficiency when applied to 191 unsaturated polyester.