新型磷-氮有机金属阻燃剂的合成及其热稳定性

以γ-氨丙基三乙氧基硅烷(1)和二苯基氯化膦(2)为原料，经取代反应制得N-(二苯基膦基)-1,1-二苯基-N-［3-(三乙氧基甲硅烷)丙基］膦氮配体(3)； 3与六水合氯化镍(4)反应合成了一种新型的磷-氮有机金属阻燃剂(5)，其结构经¹H NMR, ³¹P NMR和FT-IR表征。研究了物料比［r=n(2) : n(1)］、溶剂、反应时间和反应温度对3收率的影响。结果表明：在最佳反应条件［二氯甲烷为溶剂，1 19 mmol, r=2.3，于25 ℃反应14 h］下，3收率89.5%。 TGA测试结果表明：5的初始分解温度为252 ℃， 700 ℃残炭为31.9%。

Synthesis and Thermal Stability of A Novel P-N Organometallic Flame Retardant

N-(diphenylphosphino)-1,1-diphenyl-N-(3-(triethoxysilyl)propyl)phosphinamine(3) was prepared by substitution reaction of γ-aminopropyl triethoxysilane(1) with chlorodiphenyl phosphine(2). A novel P－N organometallic flame retardant(5) was synthesized by the reaction of 3 with nickel chloride hexahydrate(4). The structures were characterized by ¹H NMR, ³¹P NMR and FT-IR. Effects of molar ratio［r=n(2) : n(1)］, solvent, reaction time and reaction temperature on the yield of 3 were investigated. The optimum reaction conditions were as followed: dichloromethane was solvent, 1 was 19 mmol, r was 2.3, reacted at 25 ℃ for 14 h. The yield of 3 was 89.5% under the optimum conditions. TGA results showed that the initial decomposition temperature of 5 was 252 ℃ and the char yield was about 31.9% at 700 ℃.