Synthesis andPostfunctionalization of Acrylate-AppendedPoly(cyclohexene carbonate)s: Modulation of Properties of CO₂-Based Polymers

Functional CO₂-based polycarbonates are expected to be sustainable materials. Herein, a bifunctional aluminum porphyrin catalyzed the terpolymerization of cyclohexene oxide (CHO), acrylate-appended CHO, and CO₂ to provide poly(cyclohexene carbonate)s (PCHCs) with acrylate groups. Postfunctionalization of PCHCs via Michael addition or Heck reaction enabled the incorporation of thiol, amine, and aromatics into PCHCs with high selectivity and efficiency. PCHCs with the flexible long alkyl chains showed a glass-transition temperature (<i>T</i>_g) of down to 52 °C, which was much lower than that of PCHC (127 °C). In sharp contrast, PCHCs with rigid pyrenyl groups showed <i>T</i>_g values of up to 152 °C and fluorescence emission. Thus, a wide range of polymers were obtained by robust and sustainable synthetic methods, and the functional groups modulated the properties of the CO₂-based polycarbonates.