低聚羟丙基磷酸乙酯阻燃剂的合成及应用

Synthesis and Application of Oligohydroxypropyl ethyl phosphate Flame Retardant

摘要:

以五氧化二磷、环氧丙烷等为原料合成了低聚羟丙基磷酸乙酯阻燃剂。考察了环氧丙烷的滴加温度及用量、反应温度、反应时间、反应压力等因素对其酸值的影响。得到最优工艺条件为环氧丙烷与中间体Ⅱ的质量比为0.67:1，环氧丙烷滴加温度为15 ℃，反应压力为0.5 MPa，反应温度为70 ℃，反应时间为1.5 h，酸值可达0.6 mgKOH/g。利用FTIR、GPC、TGA、化学滴定法等对其结构及性能进行了表征。将合成的低聚羟丙基磷酸乙酯阻燃剂对聚氨酯硬泡（RPUF）进行了阻燃改性。TGA数据表明，当添加量为10%（质量分数，以聚醚多元醇质量计）时，900 ℃的残炭量就由7.9%提升到20.71%；其阻燃性能测试数据表明，当添加量为30%，极限氧指数值（LOI）可达27.1%，通过垂直燃烧（UL-94）V-0级，且保留了泡沫基本的机械性能。

Abstract:

Phosphorus pentoxide, propylene oxide, etc. were used as raw materials to synthesize oligomeric hydroxypropyl ethyl phosphate flame retardant. The effects of dropping temperature and dosage of propylene oxide, reaction temperature, reaction time, reaction pressure on the acid value of the target product were studied. The results showed that the optimum conditions were as follows: mass ratio of propylene oxide to intermediate Ⅱ was 0.67:1, propylene oxide dropping temperature 15 ℃, reaction pressure 0.5 MPa, reaction temperature 70 ℃, reaction time 1.5 h, the acid Value of target product reached 0.6 mgKOH/g . Its structure and performance were characterized by FTIR, GPC, TGA and chemical titration. Subsequently, the synthesized flame retardant was then used to modify polyurethane rigid foam. TGA data showed the composite containing 10% product Ⅲ, the residual mass at 900 ℃ increased from 7.9% to 20.71%; its flame-retardant performance test data showed the composite containing 30% product Ⅲ achieved UL-94 V-0 rating with a LOI value of 27.1% and retained the basic mechanical properties of RPUF