High-Pressure Depolymerization of Poly(lactic acid) (PLA) and Poly(3-hydroxybutyrate) (PHB) Using Bio-Based Solvents: A Way to Produce Alkyl Esters Which Can Be Modified to Polymerizable Monomers
The polyesters poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) used in various applications such as food packaging or 3D printing were depolymerized by biobased aliphatic alcohols&mdash;methanol and ethanol with the presence of para-toluenesulphonic acid (p-TSA) as a catalyst at a temperature of 151 &deg;C. It was found that the fastest depolymerization is reached using methanol as anucleophile for the reaction with PLA, resulting in the value of reaction rate constant (k) of 0.0425 min&minus;1 and the yield of methyl lactate of 93.8% after 120 min. On the other hand, the value of constant k for the depolymerization of PHB in the presence of ethanol reached 0.0064 min&minus;1 and the yield of ethyl 3-hydroxybutyrate was of 76.0% after 240 min. A kinetics study of depolymerization was performed via LC&ndash;MS analysis of alkyl esters of lactic acid and 3-hydroxybutanoic acid. The structure confirmation of the products was performed via FT-IR, MS, 1H NMR, and 13C NMR. Synthesized alkyl lactates and 3-hydroxybutyrates were modified into polymerizable molecules using methacrylic anhydride as a reactant and potassium 2-ethylhexanoate as a catalyst at a temperature of 80 &deg;C. All alkyl esters were methacrylated for 24 h, guaranteeing the quantitative yield (which in all cases reached values equal to or of more than 98%). The methacrylation rate constants (k&prime;) were calculated to compare the reaction kinetics of each alkyl ester. It was found that lactates reach afaster rate of reaction than 3-hydroxybutyrates. The value of k&prime; for themethacrylated methyl lactate reached 0.0885 dm3/(mol&middot;min). Opposite to this result, methacrylated ethyl 3-hydroxybutyrate&rsquo;s constant k&prime; was 0.0075 dm3/(mol&middot;min). The reaction rate study was conducted by the GC-FID method and the structures were confirmed via FT-IR, MS, 1H NMR, and 13C NMR.