Synthesis Of Organic Peroxides Catalyzed By Solid Superacids

Organic peroxide can be thought of as the product that one or two hydrogen atoms of H2O2 is replaced. Its general formula is R1-O-O-R2. According to the different substituent functional groups, it can be classified as alkyl peroxide, peroxyacid, acyl peroxide, peroxyester, ketone peroxide, and so on. Traditionally,sulfuric acid is used as catalyst in the production of organic peroxides, which causes the corrosion of equipment and expensive handling of the waste acid. Therefore, it is necessary to develop new synthetic methods to prepare organic peroxides. On the basis of the review, we had mainly done the following studies.1. Tert-butyl hydroperoxide(TBHP) and di-tert-butyl peroxide(DTBP) were synthesized by oxidation of tert-butyl alcohol(TBA) with hydrogen peroxide using 12-phosphotungstic acid as catalyst. The effects of temperature, reaction time, mass of catalyst, dosage ratio of raw materials on the reaction were investigated in the ways of single factor and orthogonal design. The optimum condition is that the reaction temperature is 83?, the reaction time is 3 h, the molar ratio of tert-butyl alcohol to phosphotungstic acid is 298.8 : 1 and the molar ratio of tert-butyl alcohol to hydrogen peroxide is 0.7 : 1. The sequence of the impact of various factors on the yield is time > temperature > material ratio > dosage of catalyst. Under the best condition, the conversion of tert-butyl alcohol could reach to more than 95.0%, the yield of TBHP and DTBP are 75.9% and 19.4%, respectively.2. Methyl ethyl ketone peroxide(MEKP) was synthesized by oxidation of methyl ethyl ketone(MEK) with hydrogen peroxide using 12-phosphotungstic acid as catalyst. The effects of temperature, reaction time, mass of catalyst, dosage ratio of raw materials on the reaction were investigated in the ways of single factor and orthogonal design. The optimum condition is that the molar ratio of hydrogen peroxide to MEK is 2 : 1, the molar ratio of MEK to 12-phosphotungstic acid is 143.9 : 1, the reaction temperature is 20? and the reaction time is 40 min. The sequence of the impact of various factors on the yield is temperature > time > materials ratio > dosage of catalyst. Under the best condition, the content of active oxygen could reach to 13.2%.3. Tert-butyl hydroperoxide(TBHP) and di-tert-butyl peroxide(DTBP) were synthesized by oxidation of tert-butyl alcohol with hydrogen peroxide using Amberlyst-15 as catalyst. The effects of temperature, reaction time, mass of catalyst, dosage ratio of raw materials on the reaction were investigated in the ways of single factor and orthogonal design. The optimum condition is that the molar ratio of tert-butyl alcohol to hydrogen peroxide is 0.6 : 1, the mass ratio of TBA to Amberlyst-15 is 21.1 : 1, the reaction temperature is 83? and the reaction time is 5h. The sequence of the impact of various factors on the yield is temperature > time > dosage of catalyst > material ratio. Under the best condition, the conversion of tert-butyl alcohol could reach to more than 92.7%, the yield of TBHP and DTBP are 79.5% and 13.2%, respectively. After Amberlyst-15 is repeatedly used 8 times, the conversion of tert-butyl alcohol, the yield of TBHP and DTBP basically stay the same.