Depolymerization of polycarbonate waste by glycolysis using ethylene glycol without catalyst was explored in order to get the monomer bisphenol A (BPA). The depolymerized products were identified by GC/MS and FTIR spectroscopy. The effects of operation variables such as reaction time, reaction temperature, ethylene glycol/polycarbonate (EG/PC) weight ratio, and the kinetics of glycolysis were studied. A maximum yield of BPA of 95.6% was achieved at a reaction temperature of 220 °C for 85 min with an EG/PC weight ratio 4. It was found that the depolymerization reaction has two different activation energies, indicating that the reaction occurs in series. A new model was proposed to explain the depolymerization reaction which consists of a series of reactions: random scission from high molecular weight PC to its solid oligomer, dissolution from the solid oligomer to liquid oligomer, and homogeneous degradation from the liquid oligomer to its monomer, BPA. The activation energies were found to be 98.9 kJ/mol for the random scission reaction, 32.7 kJ/mol for the dissolution, and 355.8 kJ/mol for the homogeneous reaction, respectively. The predicted values by the proposed model were shown in good agreement with the experimental ones.
Polyethylene terephthalate (PET) was depolymerized to monomer bis(2-hydroxyethyl) terephthalate (BHET) using excess ethylene glycol (EG) in the presence of metal oxides that were impregnated on different forms of silica support [silica nanoparticles (SNPs) or silica microparticles (SMPs)] as glycolysis catalysts. The reactions were carried out at 300 degrees C and 1.1 MPa at an EG-to-PET molar ratio of 11:1 and a catalyst-to-PET-weight ratio of 1.0% for 40-80 min. Among the four prepared catalysts (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nanocomposite had the highest monomer yield (> 90%). This high yield may be explained by the high surface area, amorphous and porous structure, and existence of numerous active sites on the nanocomposite catalyst. The BHET yield increased with time and reached the highest level where equilibrium was established between BHET and its dimer. The catalysts were characterized by their SEM, TEM, and BET surface areas, and via XRD, whereas the monomer BHET was characterized by HPLC and FT-IR. The glycolysis with the Mn3O4/SNPs nanocomposite as the glycolysis catalyst produced a maximum BHET in a short reaction time.
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