含硫有机硅磷阻燃成炭剂的合成与应用  

Synthesis and Application of Sulfur-containing Organic Silicon Phosphorus Flame Char-forming Agent

作　　者：贺婧[1] 杨海军[1] 王彦林[1] 

机构地区：[1]苏州科技大学化学生物与材料工程学院,江苏苏州215009

出　　处：《精细化工》2017年第6期633-636,644,共5页Fine Chemicals

摘　　要：以二苯基二甲氧基硅烷(DMDPS)和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,合成了一种Si、P、S三元素协同阻燃成炭剂二苯基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯(DPSSPE)。考察了溶剂、反应温度、反应时间及原料物质的量比等对DPSSPE产率的影响。结果表明,最佳反应条件为:n(DMDPS)∶n(SPEPA)=1.0∶2.2,无溶剂下,反应温度为140℃,分馏反应时间为7 h,此时DPSSPE产率为94.5%。通过FTIR、~1HNMR、TG及极限氧指数(LOI)对产物的结构及性能进行了表征与测试。测试结果表明:该化合物热稳定性良好,分解温度达350℃;当DPSSPE的加入量为20%时[以聚对苯二甲酸丁二醇酯(PBT)的质量为基准],PBT的LOI达到28%,且燃烧时成炭不滴落,表明DPSSPE应用于PBT中有良好的阻燃及成炭防滴落效果;当DPSSPE与三聚氰胺聚磷酸盐(MPP)的加入量分别为12%和8%时(以PBT的质量为基准),PBT的LOI达到34%,且能迅速成炭,表明DPSSPE与MPP复配用于PBT阻燃时表现出协同增效性。A synergistic flame retardant containing three flame-retardant elements, silicon, phosphorus and sulfur,diphenyl silieic acid bis-l-phosphorus heteroaryl thio-2,6,7-trioxabicyclo [2. 2.2] octyl-4- methyl ester （DPSSPE） ,was synthesized from dimethoxydiphenylsilane （DMDPS） and 1-thiophospha- 4-hydroxymethyl-2,6,7-trioxabieyelo [ 2.2. 2 ] octane （ SPEPA ）. The effects of solvent, reaction temperature, reaction time and the molar ratio of materials on the yield of DPSSPE were investigated. Under the optimal conditions of n （DMDPS） ： n （SPEPA） of 1.0：2.2, at 140 ℃, fractionating for 7 h, the yield of DPSSPE was up to 94. 5 %. The structure and properties of the product were characterized by means of FTIR, 1 HNMR,TG and and limiting oxygen index （LOI） test. The results showed that the product had good thermal stability with a decomposition temperature of 350 ℃. When the mass fraction of DPSSPE in polybutylece terephthalate （PBT） was 20%, the LOI of PBT reached 28%, and formed char after combustion did not drip, indicating that DPSSPE had high flame-retardant and anti-dripping efficiency for PBT. Besides, when PBT comprised 12% DPSSPE and 8% melamine polyphosphate （MPP）, the LOI of PBT reached 34%, and the char could form rapidly. The result showed that the mixture of DPSSPE and MPP had a high synergistic effect in anti-flaming when applied to PBT.

关 键 词：二苯基二甲氧基硅烷 成炭 协同 防滴落 功能材料 

分 类 号：TQ314.24[化学工程—高聚物工业]