以地沟油制废弃油脂脂肪酸甲酯(WOFAME)与马来酸二丁酯(DBM)为原料,在自制ZnCl2/凹凸棒石催化剂作用下合成结构不同的生物增塑剂C22-三酸酯.采用IR、MS、1H-NMR和HPLC等手段对合成产物进行定性、定量分析,根据产物的组成结构对可能的合成路径进行探讨;试验优化了产物合成工艺条件,研究了产物的耐热及增塑性能.结果表明,在ZnCl2/凹凸棒石作用下WOFAME中亚油酸甲酯与DBM可分别经Diels-Alder环加成及双烯加成反应合成“环己烯式”与“悬挂式”的C22-三酸酯;合成产物的适宜工艺条件为:反应温度240℃,反应时间4h,n(DBM)∶n(亚油酸甲酯)=1.1∶1,催化剂用量为WOFAME用量的10％;此条件下,亚油酸甲酯转化率及产物选择性分别可达97％、94％以上.与碘催化反应相比,三分子加成副产物显著减少.此外,合成的C22-三酸酯的耐热性能及增塑性能均优于碘催化合成的产物,且明显优于邻苯类增塑剂DOP.%This study was to investigate the synthesis of C22-tricarboxylic acid triesters with different structures through reaction between waste oils fatty acid methyl esters (WOFAME) and dibutyl maleate (DBM) with selfmade ZnCl2/attapulgite catalyst.The qualitative and quantitative analyses of synthetic product were conducted by IR,MS,1H-NMR,and HPLC technologies.A probable synthetic route was developed according to the structure of product.What's more,the synthesis conditions were optimised,and heating resistance and plasticized performance of the product were also investigated.Results showed that C22-tricarboxylic acid triesters with'cyclohexene structure'were'suspension structure'were synthesized by the Diels-Alder and Ene reaction of WOFAME with DBM using ZnCl2/attapulgite catalyst.It was found that the suitable conditions for the synthesis of product were as follows:reaction temperature of 240 ℃,reaction time of 4 h,molar ratio of DBM and methyl linoleate of 1.1 ∶ 1,and the catalyst amount of 10％ (wt ％,based on the amount of WOFAME).Under the optimal conditions,the methyl linoleate conversion and product selectivity were above 97％ and 94％,respectively.Compared to the reaction catalyzed by iodine,the side product of three molecular adduct was decreased remarkably.In addition,the heat-resistant performance and mechanical properties of C22-tricarboxylic acid triesters catalyzed by ZnCl2/attapulgite were better than the synthetic product catalyzed by iodine,and significantly better than phthalates plasticizer DOP.
展开▼
