Organocatalytic depolymerization of poly(trimethylene carbonate)

Abstract

Aliphatic polycarbonates have attracted attention as degradable and sustainable materials contributing to the circular plastic economy. Their chemical recycling has not been sufficiently studied. In this study, the efficacy of organocatalysts for depolymerization of poly(trimethylene carbonate) (PTMC), a representative aliphatic polycarbonate, is investigated using several organic acids and bases. The hydrolysis of PTMC produces the water-soluble degradates propane-1,3-diol (PD) and CO2. A phosphazene base P2-t-Bu shows high activity for the hydrolysis, yielding up to 31% and 89% of PD in the homogeneous reaction at around 27°C and the inhomogeneous reaction under the reflux condition, respectively. By contrast, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) exhibits exceptionally high catalytic activity for the methanolysis of PTMC, producing PD and dimethyl carbonate. This is because of dual hydrogen-bonding activation, which completes the inhomogeneous reaction in a few hours at around 27°C while yielding more than 90% of PD. The reaction rate of the TBD-catalyzed methanolysis depends on the concentration of the nucleophile and catalyst, and the ratio of the nucleophile to the substrate affects the PD yield. These results provide a highly promising standard for chemical recycling of functionalized aliphatic polycarbonates that could potentially be applied to sustainable materials in the future.