新型二烷基二硫代氨基甲酸盐的制备及性能研究
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摘要
二烷基二硫代氨基甲酸(盐)酯类化合物是一类重要的有机化合物，广泛应用于橡胶、石油、农业、矿业、医药、环境保护、分析化学等领域。本文对这类化合物的应用研究进展进行了系统的阐述，对二烷基二硫代氨基甲酸盐(酯)类化合物及中间体N—氰乙基N—烷基仲胺的合成工艺路线进行了评述，通过综合对比分析，选择仲胺—二硫化碳路线合成二烷基二硫代氨基甲酸盐。通过实验制备了五种具有N—氰乙基N—烷基二硫代氨基甲酸钠结构的新型化合物，并对其反应机理及制备工艺进行了系统的研究。同时对N，N—二烷基二硫代氨基甲酸钠、N—苯基N—烷基二硫代氨基甲酸钠的制备工艺进行了优化研究。
采用不同的伯胺与丙烯腈反应，通过亲核加成反应，制备了五种具有N—氰乙基结构的仲胺。研究了溶剂种类、溶剂用量、原料配比、反应温度及反应时间对五种仲胺制备的影响．确定了其最佳制备工艺条件。五种仲胺的收率(以伯胺计)均大于82.0％，其产品主含量均大于97.5％。
采用不同的仲胺与二硫化碳及氢氧化钠反应，采用不同溶剂结晶法制备了N—氰乙基N—烷基二硫代氨基甲酸钠、N，N—二烷基二硫代氨基甲酸钠、N—苯基N—烷基二硫代氨基甲酸钠三个系列十三种不同取代基的二硫代氨基甲酸钠盐，并采用红外光谱对产品结构进行了表征。研究了溶剂种类、溶剂用量、原料配比、反应温度、反应时间、结晶温度及母液循环套用对各种产品制备的影响，确定了其最佳制备工艺条件。除N，N—二甲基二硫代氨基甲酸钠的收率为72.5％外，其余十二种产品的收率(以仲胺计)均大于93.0％：其产品主含量均大于95.2％。
采用所制得的产品作为矿物浮选捕收剂，浮选德兴铜矿样，研究其浮选性能。研究表明，N—氰乙基N—正丙基二硫代氨基甲酸钠的浮选性能最好，其浮选指标高于丁基黄药及乙硫氮，是一种性能优异的新型高效硫化铜矿捕收剂，具有很好的工业应用前景。
The salts and esters of N,N-dialkyldithiocarbamate are a kind of very important organic compounds, and were applied to many fields. The research progresses on application of these compounds were reviewed systematically in this paper. The preparing technologies of the salts and esters of N,N-dialkyldithiocarbamate and the intermediates N-cyanoethyl, N-alkylamine were described and evaluated systematically. Five new compounds with the structure of N-cyanoethyl,N-alkyldithiocarbamate have been synthesized, their structures were confirmed by IR, and their reaction mechanism and preparing technologies were studied systematically. Moreover, the preparing technologies of the sodium salts of N,N-dialkyldithiocarbamate and N-phenyl,N-alkyldithiocarbamate were optimized.
In this paper, five secondary amines with the structure of N-cyanoethyl have been synthesized by cyanoethylation using aliphatic primary amine and acrylonitrile as raw materials. The influences of types and amounts of solvents, the molar ratio of reactants and the time and temperature of reaction on the reaction results were studied. The optimum reaction conditions for the preparation of different products were obtained. The average yield (calculated by primary amines) of every secondary amines is more than 82.0%, and the purity of every secondary amines is higer than 97.5%.
Five sodium salts with the structure of N-cyanoethyl,N-alkyldithio-carbamate, four sodium salts with the sructure of N,N-dialkyldithiocarba-mate and four sodium salts with the structure of N-phenyl,N-alkyldithio-carbamate have been prepared by crystallizing from different solvents using different secondary amines, carbon disulfide and sodium hydroxide as raw materials. The influences of types and amounts of solvents, the molar ratio of reactants, the time and temperature of reaction, the crystal temperature and the recycling of solvents on the preparation of these compounds were studied, and the optimum operation conditions for the preparation of these products were obtained. The average yield (calculated by secondary amine) of the sodium salt of N,N-dimethyldi-
thiocarbamate is 72.5%, and the average yields of the other twelve products are all more than 93.0%. the purities of all these products are higer than 95.2%.
The prepared sodium salts of N, N-dialkyldithiocarbamate were used as collectors for the froth flotation of chalcopyrite of Dexing. The experimental results showed that the sodium salts of N-cyanoethyl, N-(n-propyI)dithiocarbamate is the most excellent collector of sulfide minerals in these products, and its flotation properties are better than the common butyl xanthate and SN-9.
采用不同的伯胺与丙烯腈反应，通过亲核加成反应，制备了五种具有N—氰乙基结构的仲胺。研究了溶剂种类、溶剂用量、原料配比、反应温度及反应时间对五种仲胺制备的影响．确定了其最佳制备工艺条件。五种仲胺的收率(以伯胺计)均大于82.0％，其产品主含量均大于97.5％。
采用不同的仲胺与二硫化碳及氢氧化钠反应，采用不同溶剂结晶法制备了N—氰乙基N—烷基二硫代氨基甲酸钠、N，N—二烷基二硫代氨基甲酸钠、N—苯基N—烷基二硫代氨基甲酸钠三个系列十三种不同取代基的二硫代氨基甲酸钠盐，并采用红外光谱对产品结构进行了表征。研究了溶剂种类、溶剂用量、原料配比、反应温度、反应时间、结晶温度及母液循环套用对各种产品制备的影响，确定了其最佳制备工艺条件。除N，N—二甲基二硫代氨基甲酸钠的收率为72.5％外，其余十二种产品的收率(以仲胺计)均大于93.0％：其产品主含量均大于95.2％。
采用所制得的产品作为矿物浮选捕收剂，浮选德兴铜矿样，研究其浮选性能。研究表明，N—氰乙基N—正丙基二硫代氨基甲酸钠的浮选性能最好，其浮选指标高于丁基黄药及乙硫氮，是一种性能优异的新型高效硫化铜矿捕收剂，具有很好的工业应用前景。
The salts and esters of N,N-dialkyldithiocarbamate are a kind of very important organic compounds, and were applied to many fields. The research progresses on application of these compounds were reviewed systematically in this paper. The preparing technologies of the salts and esters of N,N-dialkyldithiocarbamate and the intermediates N-cyanoethyl, N-alkylamine were described and evaluated systematically. Five new compounds with the structure of N-cyanoethyl,N-alkyldithiocarbamate have been synthesized, their structures were confirmed by IR, and their reaction mechanism and preparing technologies were studied systematically. Moreover, the preparing technologies of the sodium salts of N,N-dialkyldithiocarbamate and N-phenyl,N-alkyldithiocarbamate were optimized.
In this paper, five secondary amines with the structure of N-cyanoethyl have been synthesized by cyanoethylation using aliphatic primary amine and acrylonitrile as raw materials. The influences of types and amounts of solvents, the molar ratio of reactants and the time and temperature of reaction on the reaction results were studied. The optimum reaction conditions for the preparation of different products were obtained. The average yield (calculated by primary amines) of every secondary amines is more than 82.0%, and the purity of every secondary amines is higer than 97.5%.
Five sodium salts with the structure of N-cyanoethyl,N-alkyldithio-carbamate, four sodium salts with the sructure of N,N-dialkyldithiocarba-mate and four sodium salts with the structure of N-phenyl,N-alkyldithio-carbamate have been prepared by crystallizing from different solvents using different secondary amines, carbon disulfide and sodium hydroxide as raw materials. The influences of types and amounts of solvents, the molar ratio of reactants, the time and temperature of reaction, the crystal temperature and the recycling of solvents on the preparation of these compounds were studied, and the optimum operation conditions for the preparation of these products were obtained. The average yield (calculated by secondary amine) of the sodium salt of N,N-dimethyldi-
thiocarbamate is 72.5%, and the average yields of the other twelve products are all more than 93.0%. the purities of all these products are higer than 95.2%.
The prepared sodium salts of N, N-dialkyldithiocarbamate were used as collectors for the froth flotation of chalcopyrite of Dexing. The experimental results showed that the sodium salts of N-cyanoethyl, N-(n-propyI)dithiocarbamate is the most excellent collector of sulfide minerals in these products, and its flotation properties are better than the common butyl xanthate and SN-9.
引文
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