Synthesis Of ε-caprolactone Over Oxidation Of Cyclohexanone With Solid Peracid

ε-Caprolactone(ε-CL), as an important intermediate of organic synthesis, is mainly used to produce poly(ε-caprolactone)(PCL) and polyesters, which have good thermoplasticity and formation workability. It is widely used in degradable material, environmental protection and medical fields due to its biocompatibility, nontoxicity, medicine permeability and biological degradability, which results in research on the synthesis of the ε-caprolactone monomer to be more and more important.In this paper, solid monopersuccinic acid (PSA) is applied to synthesis of ε-CL by oxidation of cyclohexanone, which overcomes the unsafe shortcomings of peracid oxidation, and long reaction time, low yield shortcomings of H2O2indirect oxidation methods.The research primary coverage includes:(1) In the absence of catalyst,70%hydrogen peroxide is used to oxidize succinic anhydride to PSA with high activities, and the purity of PSA is measured by iodometry;(2) PSA is applied to synthesis of ε-CL by oxidation of cyclohexanone, and single factor experiment is adopted to optimize synthetic conditions for improving cyclohexanone conversion, ε-CL yield and selectivity;(3) Solid precipitated in the process of synthesizing ε-CL is dehydrated via reactive distillation for preparing crude succinic anhydride, and single factor experiment is adopted to optimize synthetic conditions for improving crude succinic anhydride yield;(4) Crude succinic anhydride is carried out recrystallization for improving succinic anhydride purity, which is characterized by melting point, IR and’HNMR, and achieves material recycle;(5) Selecting a suitable Aspen model for crude product distillation seperation simulation.The result indicated:(1) Solid peracid with high activities can be successfully synthetized from oxidation of succinic anhydride using70%hydrogen peroxide as oxidant, and the purity of PSA is78.82%;(2) Conversion of cyclohexanone, yield and selectivity of ε-CL are upto98.08%,97.45%and99.36%respectively under optimal synthetic conditions:molar ratio of PSA to cyclohexanon,2:1(cyclohexanon9.8g, PSA26.8g); acetic acid dosage,70mL/0.2mol PSA; reaction temperature,40℃; reaction time,3h;(3) Yield of succinic anhydride reaches78.67%under optimal synthetic conditions:solvent dosage,70mL(solid30g); water-carrying agent dosage15mL; reaction time,1h;(4) Recrystallization product turns out to be succinic anhydride by melting point, IR and1HNMR tests. Recovery rate of succinic anhydride reaches85.71%under optimal preparing conditions:solvent dosage,40mL(crude succinic anhydride,14g): recrystallization temperature,90℃recrystallization time,1h;(5) Industrialization simulation of ε-CL separation process was carried out via Aspen software, and the material balance and the energy balance results of the separation process, the operation parameter of the rectifying tower, the column internals parameter, the column tray parameter distribution map, the hydraulic parameter list and so on are botained, wich are the industrialization data with extremely value.