三羟甲基硝基甲烷酯类化合物合成及应用研究

Research on the synthesis and application of trihydroxymethylnitromethane esters

以三羟甲基硝基甲烷(THNM)为原料、对甲苯磺酸为催化剂,分别与棕榈酸、12-羟基硬脂酸以及肉豆蔻酸进行酯化反应,合成相应的THNM酯类化合物。以产物酯化率为指标,研究了反应温度、反应时间、催化剂用量和反应投料比对反应酯化率的影响,确定的最佳反应条件为:对甲苯磺酸用量为总投料质量的1%、反应物料比为n(THNM)/n(酸)=1/3.0、三羟甲基硝基甲烷三(棕榈酸)酯和三羟甲基硝基甲烷三(肉豆蔻酸)酯的反应温度为150℃,反应时间5h;三羟甲基硝基甲烷三(12-羟基硬脂酸)酯的反应温度为130℃,反应时间6h。测定和计算了产物的羟值和皂化值,采用热重分析了其热稳定性,并通过DSC证实了3种产物对于硝酸铵Ⅲ~Ⅱ相转变过程均有明显的抑制作用。

Trihydroxymethylnitromethane(THNM)was synthesized by esterification with palmitic acid,12-hydroxystearic acid and myristate acid using THNM as raw material and p-toluenesulfonic acid as catalyst.The effects of reaction temperature,reaction time,amount of catalyst and reaction feed ratio on the esterification rate of products were studied,and the optimal reaction conditions were determined as follows:the dosage of p-toluenesulfonic acid was 1%of the total feed mass,the reaction material was n(THNM)/n(acid)=1/3.0,the reaction temperature was 150°C and the reaction time was 5h in synthesis of trihydroxymethylnitromethane tri(palmitic acid)ester and trihydroxymethylnitromethane tri(myristate acid)ester,the reaction temperature was 130C and the reaction time was 6h in synthesis of trihydroxymethylnitromethane tri(12-hydroxystearic acid)ester.The hydroxyl value and saponification value of the product were determined and calculated.Thermal stability was analyzed by thermogravimetric analysis.DSC showed that the three products had obvious inhibition on the phase transition of ammonium nitrate II~Il.