离子交换树脂Amberlyst-35催化合成过氧化乙酰丙酮及其热稳定性

Synthesis of Acetylacetone via Catalytic Peroxidation Using Amberlyst-35 and Its Thermal Stability

采用单因素法和正交实验设计法,以离子交换树脂Amberlyst-35为催化剂,由质量分数为50%的双氧水氧化乙酰丙酮合成过氧化乙酰丙酮。当双氧水与乙酰丙酮的物质的量的比为1.1,Amberlyst-35与乙酰丙酮的质量比为0.05,在20℃下反应4.5 h时,过氧化乙酰丙酮的活性氧质量分数为12.4%,主要产物为3,5-二羟基-3,5-二甲基-1,2-二氧戊环和5-氢过氧基-3-羟基-3,5-二甲基-1,2-二氧戊环,其分解热为1.64 kJ/g,分解活化能为70 kJ/mol。该法与传统的均相催化合成相比,制备条件温和,催化剂可循环使用,产品活性氧含量高。

Acetylacetone peroxides were synthesized by oxidation of acetylacetone with 50%hydrogen peroxide over Amberlyst-35 as catalyst,which was optimized by single factor and orthogonal design experimental method.Under the condition that the ratio of hydrogen peroxide to acetylacetone is 1.1,mass ratio of Amberlyst-35 to acetylacetone is 0.05,the reaction temperature is 20℃and time is 4.5 h,the activated oxygen content is 12.4%.The main products are 3,5-dihydroxy-3,5-dimethyl-1,2-dioxolane and 5-hydroperoxy-3-hydroxy-3,5-dimethy-1,2-dioxolane.The heat decomposition is 1.64 kJ/g and decomposition activation energy is 70 kJ/mol.In comparison with traditional homogeneous catalytic synthesis,the current preparation conditions are mild,the catalyst can be recycled and the active oxygen content of product is higher.