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 (Р= M w /M n ) in the range of 1.37-1.61. Copolymers with T g s of -11 °C or T m s from 5 to 15 °C and thermal decomposition >200 °C depending on the comonomer ratio, are obtained as determined by differential scanning calorimetry/TGA.