植物油基环氧化聚甘油多酯增塑剂的合成及应用

Synthesis and Application of A Plant Oil-Base Epoxy Polyglycerol Esters Plasticizer

以生物柴油的副产物粗甘油为原料,通过聚合反应得到聚合甘油;再与油酸通过酯化反应得到中间产物聚甘油不饱和脂肪酸多酯。然后在无溶剂条件下,以硫酸为催化剂进行环氧化反应得到增塑剂环氧化聚甘油多酯。考察了反应温度、反应时间、甲酸用量以及H2O2用量对产物的环氧值的影响。同时采用了傅立叶变换红外光谱和热重分析对产物的结构和热稳定性进行表征。结果表明,最佳环氧化条件为:反应温度65℃,反应时间6 h,聚甘油不饱和脂肪酸多酯、甲酸、30%H2O2质量比为1∶0.5∶1.2。产品的酸值为1.24 mg KOH/g,环氧值为6.4%,残留碘值为6.8 mg/100 g,具有较好的热稳定性,应用到PVC树脂中可有效地提高PVC的增塑性。

With the by-product of biological diesel oil crude glycerine as raw material,polyglycerol was got by polymerization. Then polyglycerol unsaturated fatty acid ester was prepared by esterification reaction. Using sulfuric acid as catalyst without solvent, plasticizer of epoxy polyglycerol ester was prepared via epoxidation reaction. The influences of epoxidation reaction conditions such as reaction temperature,reaction time,the amounts of H2O2 and formic acid on the epoxy value of products were investigated. The structure and thermostability of the products were characterized by Fourier transform infrared spectrum and thermogravimetric analysis respectively. The results show that the optimized reaction conditions of epoxidation are as follows ：the mass ratio of polyglycerol unsaturated fatty acid ester,formic acid and 30% H2O2 is 1∶0.5∶1.2,reaction temperature is 65℃ and reaction time is 6 h. The acid value is 1.24 mg KOH/g,epoxy value of product is 6.4%,residual iodine value is 6.8 mg/100 g. The plasticizer own preferably heat stability,when used in PVC resin can effectively increase the increasing of PVC plastic.