Synthesis And Application Of Organic Phosphate Series Flame Retardants

With the standards of fire safety increasingly stringent,the demand of the global flame retardants market have been showing a tendence of increaseing in recent years,the many countries researchers are developing and applying the flame retardants in constantly.For the reasons of rich resources,varieties kinds,low prices and wide range uses,phosphate flame-retardants are one of the main series in the flame retardants.The studies have shown that halogen phosphate flame retardants for the phosphorus-halide synergying,so flame retardant effect is better.This article synthesized three kinds of flame retardants with[Et3NHCl]-xAlCl3 instead of the traditional catalysts:They are tri(β-chlorocthyl)phosphate ester(TCEP),tri(2,3-dichloropropyl)phosphate ester(TDCP),tris(iso-clorpropyl)Phosphate ester(TCPP).Also synthesized four(2-propyl chloride)-1-methyl-1,2-ethyl double phosphate ester flame retardant.The effect of the catalysts,the reaction time,the reaction temperature and the reaction molecular ratio on the reaction yield were investigated by orthogonal experiment and single factor.The optimal reaction conditions of tri(β-chlorocthyl)phosphate ester was obtained:the reaction temperature was 50～55℃,n(POCl3):n(ethylene oxide)mole ratio was 1:3.2,the epoxy ethane dropping time was 5 h,catalyst dosage was 0.06 g,the yield of the product can be up to 98.5%;The optimal reaction conditions of tri(2,3-dichloropropyl)phosphate ester was obtained:the reaction temperature was 60～65℃,n(POCl3):n(propylene oxide)mole ratio was 1:3.3,the epoxy propane dropping time was 3 h,catalyst dosage was 0.05 g,the yield of the product can be up to 98.0%;The optimal reaction conditions of tris(iso-clorpropyl)phosphate ester was obtained:the reaction temperature was 70～75℃,n(POCl3):n(epichlorohydrin)mole ratio was 1:3.3,the epoxy chloropropane dropping time was 7 h,catalyst dosage was 0.12 g,the yield of the product can be up to 88.5%;The optimal reaction conditions of four(2-propyl chloride)-1-methyl-1,2-ethylidene double phosphate:reaction temperature was 180℃,reaction time was 9 h,catalyst KOH dosage was 2.0 g,the yield of the product can be up to 89.5%.IR and 1HNMR were used to characterize their chemical structures,matching with their target molecules.The results showed the four oligomeric phosphonate flame retardants have better tests the acid value,viscosity and thermal stability.On the base of literatures at home and abroad,the tris(iso-clorpropyl)Phosphate ester(TCPP)was respectively tested polyurethane foam.The flame retardant properties and mechanical properties of the materials were studied.The results showed that TCPP is a kind of high performance flame retardant.