摘要
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ZnCl_2/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ZnCl_2/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4 h,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 self- made ZnC1E/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 prod- uct. 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 ： reac- tion 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 con- version and product selectivity were above 97% and 94%, respectively. Compared to the reaction catalyzed by io- dine, the side product of three molecular adduct was decreased remarkably. In addition, the heat - resistant perform- ance 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.
出处
《中国粮油学报》
EI
CAS
CSCD
北大核心
2017年第1期91-98,共8页
Journal of the Chinese Cereals and Oils Association
基金
江苏省科技厅前瞻性联合研究(BY2012091)
常州市科技支撑计划(CE20115002)
