Efficient solvent‐free alternating copolymerization of CO2 with 1, 2‐epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis

The alternating copolymerization of CO₂ with the terminated epoxides anchoring long alkyl groups is rarely reported because of their low reactivity and polycarbonate selectivity. This work describes a well‐controlled solvent‐free copolymerization of CO₂ with 1, 2‐epoxydodecane (EDD) with a long electron‐donating alkyl group via the catalysis of Zn‐Co(III) double metal cyanide complex catalyst. The productivity of the catalyst was up to 2406 g polymer/g Zn, that is, EDD conversion was 99.2%. The alternating degree of CO₂‐EDD copolymers were more than 99% and had high number‐average molecular weights (M_ns) of >100 kg mol^?1, while only 1.0 wt % 4‐decyl‐1,3‐dioxolan‐2‐one (DC) were detected. Moreover, by introducing styrene oxide (SO) with electron‐withdrawing phenyl group into EDD‐CO₂ copolymerization system, a new random terpolymer with either electron‐withdrawing or electron‐donating side groups was produced with single glass transition temperatures (T_gs) in a wide range from 3 to 56 °C, which might be potentially used as biodegradable elastomers or plastics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 737–744