有机硅双环笼状膦酸酯阻燃剂合成与应用  

Synthesis and Application of Organosilicon Bicyclic Caged-phosphonate Flame Retardant

作　　者：马肃 蒋子程 戴毅 张笑研 张苗苗 张刚 Ma Su;Jiang Zicheng;Dai Yi;Zhang Xiaoyan;Zhang Miaomiao;Zhang Gang(School of Chemistry and Life Science,Suzhou University of Science and Technology,Suzhou 215009,China;Tianping College of Suzhou University of Science and Technology,Suzhou 215009,China)

机构地区：[1]苏州科技大学化学与生命科学学院,江苏苏州215009 [2]苏州科技大学天平学院,江苏苏州215009

出　　处：《工程塑料应用》2021年第11期132-138,共7页Engineering Plastics Application

基　　金：江苏省自然科学基金项目(BK20190943)。

摘　　要：以三(羟甲基)氨基甲烷盐酸盐、三氯氧磷和甲基乙烯基二氯硅烷为主要原料,两步合成了一种有机硅双环笼状膦酸酯阻燃剂,即甲基乙烯基二(1–氧代–1–膦杂–2,6,7–三氧杂双环[2.2.2]辛烷基–4–亚氨基)硅烷(MVDIS),并通过傅里叶变换红外光谱、核磁共振氢谱表征产物的化学结构。确定最佳的反应条件为:在氮气保护下,溶剂为二乙二醇二甲醚,反应温度为90℃,笼状膦酸酯胺与甲基乙烯基二氯硅烷物质的量比2.1∶1的条件下反应10 h,产物MVDIS的产率可达91.4%。通过热重–差热、极限氧指数、垂直燃烧和扫描电镜对阻燃性能与机理及烧蚀产物的微观形貌进行分析。结果表明,MVDIS具有良好的热稳定性与气相阻燃机理,且作为阻燃单体引入不饱和聚酯树脂后获得了良好的阻燃与自熄性能。An organosilicon bicyclic caged phosphonate flame retardant,methylvinyldi(1-oxo-1-phosphine-2,6,7-trioxyheterobicyclo[2.2.2]octanyl-4-imino)silane was synthesized in two steps from tris-hydroxymethyl aminomethane hydrochloride,phosphorus oxychloride and methylvinyldichlorosilane,while the chemical structure of the product was characterized by FTIR and 1H-NMR.The optimum synthesis route of MVDIS were investigated as follows,under nitrogen atmosphere,n(cagedphosphonate amine)∶n(methylvinyl dichlorosilane)=2.1∶1,diethylene glycol dimethyl ether as solvent and keeping the reaction at 90℃for 10 h,while the yield of product was 91.4%.The flame retardancy,mechanism and microstructure of ablation products were investigated by TG–DTA,LOI,UL–94 and SEM.The results showed that MVDIS had good thermal stability and a gas-phase flame retardant mechanism worked.An outstanding flame retardant and self-extinguishing properties were obtained when MVDIS was introduced into UPR matrix.

关 键 词：有机硅阻燃剂 三(羟甲基)氨基甲烷盐酸盐 协同效应 不饱和聚酯树脂 笼状结构 

分 类 号：TQ32[化学工程—合成树脂塑料工业]