Crystalline CO₂‐Based Aliphatic Polycarbonates with Long Alkyl Chains

Abstract

Carbon dioxide (CO2) is an easily available, renewable carbon source and can be utilized as a comonomer in the catalytic ring‐opening polymerization of epoxides to generate aliphatic polycarbonates. Dodecyl glycidyl ether (DDGE) is copolymerized with CO2 and propylene oxide (PO) to obtain aliphatic poly(dodecyl glycidyl ether carbonate) and poly(propylene carbonate‐co‐dodecyl glycidyl ether carbonate) copolymers, respectively. The polymerization proceeds at 30 °C and high CO2 pressure utilizing the established binary catalytic system (R,R)‐Co(salen)Cl/[PPN]Cl. The copolymers with varying DDGE:PO ratios are characterized via NMR, FT‐IR spectroscopy, and SEC, exhibiting high molecular weights between 11 400 and 37 900 g mol−1 with dispersities (Ð = M w/M n) in the range of 1.37–1.61. Copolymers with T gs of −11 °C or T ms from 5 to 15 °C and thermal decomposition >200 °C depending on the comonomer ratio, are obtained as determined by differential scanning calorimetry/TGA.

Synthesis of PPC-graft-poly(PEOMA) Brush and PPC Gels via Post-polymerization Modification of Hydroxyl-Functionalized Poly(propylene carbonate)

“…However, the exible molecular chains imparted by the considerable amount of ether bonds within PPC lead to extremely low glass transition temperature (T g ), poor mechanical strength and inferior dimensional stability at temperatures above 40°C [9]. Besides, PPC tends to decompose into cyclic carbonate by the mechanism of "back biting" at a temperature of only about 180°C causing the narrow processing temperature [10,11].…”