微反应技术合成不敏感硝酸酯增塑剂TMETN和PGDN

Synthesis of Insensitive Nitrate Plasticizers TMETN and PGDN by Micro Reaction Technology

利用微反应技术,分别以1,2-丙二醇、三羟甲基乙烷为原料,硝硫混酸为硝化剂,合成了1,2-丙二醇二硝酸酯(PGDN)和三羟甲基乙烷三硝酸酯(TMETN);采用红外光谱、核磁共振等对其结构进行了表征,同时优化了微反应器硝化反应条件。结果表明,TMETN和PGDN结构与间歇式合成产物一致,合成TMETN的较佳硝化温度为17~20℃,硝酸与三羟甲基乙烷的最佳摩尔比为5.6∶1.0,收率达90.0%以上,纯度达98.5%;合成PGDN的较佳反应温度为20~22℃,硝酸与1,2-丙二醇的摩尔比为2.7∶1.0。该工艺具有反应温度范围宽、硝酸用量少和收率高等优点。

Trimethylethane trinitrate （TMETN） and 1, 2 propylene glycol dinitrate （PGDN） were synthesized by micro reaction technology, using 1, 2 propylene glycol and trimethylethane as raw materials and nitric acid/sulphu tic acid as nitrating agent respectively. Their structures were characterized by FTIR and NMR etc. and nitration re action conditions of micro reactor were optimized through the micro reactor method developed in this study. The re sults show that their structures were consistent with those from intermittent synthesis product. The better nitration temperature of TMETN is 17 20℃, and the optimum molar ratio of HNO3 and trimethylethane is 5.6 ： 1.0. The yield is over 90.0%. The purity is 98.5 %. The better reaction temperature of synthesizing PGDN is 20 22℃, and the molar ratio of HNO3 to 1, 2 propylene glycol is 2.7 ： 1.0. The process has the advantages of wide reaction tern perature range, low nitric acid dosage and high yield,etc.