Synthesis Of Methyl Ethyl Ketone Peroxide And Acetylacetone Peroxide Catalyzed By Ion Exchange Resin

Organic peroxide can be thought of the product that one or two hydrogen atoms of hydrogen peroxide is replaced by organic group.Its chemical formula is R₁-O-O-R₂.In the traditional production process,inorganic acid is used as catalyst in the synthesis of organic peroxides,which causes the corrosion of equipment and expensive handling of the waste acid.Therefore,it is necessary to find a green catalyst to prepare organic peroxides.In addition,organic peroxides have potentially dangerous during production,use and storage because of the easy decomposition and liberate a lot of heat,so it has great practical significance to study the thermal stability.Based on the above issues,the following studies were done.1.Methyl ethyl ketone peroxide were synthesized by oxidation of methyl ethyl ketone using 30%hydrogen peroxide as oxidant and Amberlyst-15 as catalyst.The effects of reaction temperature,reaction time,dosage ratio of hydrogen peroxide and methyl ethyl ketone on the reaction,mass of Amberlyst-15 were investigated in the ways of single factor and orthogonal design.Under the condition of reaction temperature at 27?,reaction time for 55min,the molar ratio of hydrogen peroxide to methyl ethyl ketone is of 1.0 and the mass ratio of Amberlyst-15 to methyl ethyl ketone is of 0.06,the yield of methyl ethyl ketone peroxide can be reached about 86%and the activated oxygen content is 12.9%.Amberlyst-15 still keep good catalytic activity after recycling 8 times.The main products of methyl ethyl ketone peroxide were confirmed by using HLPC-MS for 2,2-Dihydroperoxybutane?A₂?and the polymer of2,2-Dihydroperoxybutane.The characterize of unused and used catalyst were conducted by FT-IR,SEM and TG.Study shows Amberlyst-15 has the advantages of high catalytic activity,good repeated utilization,cleaning and low corrosivity,which can be an new way for the production of organic peroxide.2.By use of TG-DSC simultaneous thermal analyzer,the thermal decomposition tests of methyl ethyl ketone peroxides were conducted and the heat decomposition was calculated for 749 J/g.The activation energy and pre-exponential factor changed with the conversion rate were analyzed by isoconversional method of Friedman.The self-accelerating decomposition temperature of methyl ethyl ketone peroxides under 50kg,100kg,200kg packing is 28?,26?and 24?calculated by AKTS combined with the DSC data.3.Acetylacetone peroxide were synthesized by oxidation of acetylacetone using50%hydrogen peroxide as oxidant and Amberlyst-35 as catalyst.The effects of reaction temperature,reaction time,mass of Amberlyst-35,dosage ratio of hydrogen peroxide and acetylacetone on the reaction were investigated in the ways of single factor and orthogonal design.Under the condition of reaction temperature at 20?,reaction time for 4.5 h,the molar ratio of hydrogen peroxide to acetylacetone is of 1.1and the mass ratio of Amberlyst-35 to acetylacetone is of 0.05,the activated oxygen content is 12.8%.Amberlyst-35 still keep good catalytic activity after recycling 8times.The main products of acetylacetone peroxide were confirmed by using HLPC-MS for?and?.By use of TG-DSC simultaneous thermal analyzer,the thermal decomposition tests of acetylacetone peroxide were conducted and the heat decomposition was calculated for 1636 J/g.The activation energy of acetylacetone peroxide is 70 kJ/mol analyzed by Ozawa equations combined with the DSC data.