一种反应性含磷乳化剂的合成研究

Synthesis of a reactive phosphate emulsifier

采用甲基丙烯酸缩水甘油酯(GMA),十二酸(LA)为原料,合成了一种仲醇结构的中间体,得到优化的工艺条件为:用等摩尔的GMA和LA,采用N,N-二甲基苄胺为催化剂,用量为反应物总量的0.6%,于105℃下反应8 h,转化率可达99%以上。以POCl3作为磷化剂,与仲醇中间体反应,再水解制得含甲基丙烯酰基团的反应性含磷乳化剂。研究了反应介质和反应温度对产物结构的影响。较佳的磷化工艺条件为:POCl3和仲醇中间体的摩尔比为1.2∶1.0,反应介质为甲苯,于-30℃反应2 h可得到单酯质量分数62.5%的磷酸酯,将得到的产物提纯后制得单酯质量分数较高的磷酸酯。用红外光谱分析了原料、仲醇中间体和提纯后的磷酸酯的结构,并用核磁共振波谱(13C3、1P)对提纯后的磷酸酯的结构进行了表征。结果表明,最终得到的磷酸酯乳化剂的结构与设计的基本相符。

Through the reaction of glycidyl methacrylate （GMA） and lauric acid （LA）, an intermediate with a secondary alcohol structure （GMA - LA） was prepared under conditions as molar ratio of GMA to LA is 1 ： 1 ; using N, N - dimethylbenzylamine as catalyst with dosage of 0.6% of the total mass of the reactants; reaction at 105 ℃ for 8 h. The yield can achieve 99%. The intermediate GMA - LA further reacted with POCl3 and after hydrolysis of the reaction product, a reactive phosphate emulsifier product was obtained. The molar ratio of POCl3 to intermediate GMA - LA is 1.2： 1. The reaction is carried in a solvent medium of toluene and at a temperature of - 30 ℃ for 2 h and the mass fraction of mono- phosphate in the product can achieve 63.5 %. The product is further purified in order to get a sample of higher content of mono - phosphate and the sample is to be used for characterization. The starting materials, the intermediate and the purified product sample were characterized by IR spectra and the purified product sample was further characterized by 13CNMR spectrum and 31PNMR spectrum. The results showed that the product meets the targeted requirement.