Study On The Novel Environment Benign Process Of Dicycolpentadiene Diepoxide From Dicycolpentadiene With Heteropolyacids As Catalysts

The epoxidation of olefin is one of the important reactions in organic synthesis. The epoxide is a broad variety of organic materials and intermediates, and is used in many domains, such as petrochemical, fine chemical, organic synthesis and so on. C₅ is a kind of byproduct in splitting petroalkyl materials to make ethane. Dicyclopentadiene is a sort of main composing in C₅, accounting of 14-19% approximately. The epoxide of dicyclopentadiene, dicyclopentadiene diepoxide, is a kind of predominant capability epoxide. Owing to much excellent properties, such as heat-resistant, climate-resistant, upper rigidity, well electrical insulation, it can apply in high-temperature-resistant run material, glass steel, bond, laminated material, dope and so on. So dicyclopentadiene diepoxide is a great developing foreground product.Be established in practicality, we associate with China Petroleum Natural Gas Group JiLin Filiale to study and empolder the C₅ fraction lower fine chemical product, namely the epoxidation of dicyclopentadiene in C₅ fraction. Based on the viewpiont of protecting environmental, this paper studied the epoxidation of dicyclopentadiene with hydrogen peroxide as oxidant and heteropolyacids as catalyst. The new green catalytic technics way for preparation of dicyclopentadiene diepoxide was studied in three reaction systems.1) Epoxidation of dicyclopentadiene catalyzed by H3PW12O40 supported on SiO2/H₂O₂ system: We used normal temperature dipping method and sol-gel method to make two catalysts. The best epoxidation conditions by catalysts prepared normal temperature dipping method were 0.75g 30% H₃PW₁₂O₄0)/SiO₂, 65℃, 16h, CHCl3 as solvent, and 30%H₂O₂ as oxidant. The best epoxidation conditions by catalysts prepared sol-gel method were 0.5g H₃PW₁₂O₄0)/SiO₂, 65℃, 12h, and CHCl3 as solvent. We compared catalysis effect by the two catalysts.2) Epoxidation of dicyclopentadiene catalyzed by phase transfer/H₂O₂ system: The epoxidation was carried out by phase transfer catalytic theory with quaternary ammonium salts of heteropolyacids as catalysts, so the reaction was put along in organic phase. The key factors influencing the epoxidation were also studied, such as the amount of catalysts, reaction temperature, reaction time and solvent. And the optimal synthesis conditions were detailed as: 0.026mmol CWP, 6.5mmol C₁₀H₁₆, 13mmol 30%H₂O₂, 15ml CHCl₃, 65℃, and 6h. Under these conditions, the conversion rate of dicyclopentadiene was 83.75% and the selectivity of dicyclopentadiene diepoxide was 98.47%.3) Epoxidation of dicyclopentadiene catalyzed by HPA-ionic liquid-H₂O₂ system: The epoxidation was tried to use green solvent--ionic liquid instead of poisonous organic solvent. The key factors influencing the epoxidation were studied, such as the amount of catalysts, mole ratio between dicyclopentadiene and H₂O₂, reaction temperature, and reaction time. The best synthesis conditions were 0.01g H₃PW₁₂O₄₀, C10H16:H₂O₂ =1:2, 65℃, and 6h. The conversion rate of dicyclopentadiene was 43.63% and the selectivity of dicyclopentadiene diepoxide was 98.33%.