Crystalline CO2‐Based Aliphatic Polycarbonates with Long Alkyl Chains

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. This work shows that aliphatic long alkyl chain polycarbonates with high molecular weights and tailorable degrees of crystallization are accessible via catalytic ring‐opening polymerization on the basis of C12 alkyl glycidyl ethers, propylene oxide, and carbon dioxide. The copolymers are comprehensively characterized by NMR‐, IR‐spectroscopy, SEC, differential scanning calorimetry, and TGA measurements.