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, i.e., EDD conversion was 99.2%. The alternating degree of CO2-EDD copolymers were more than 99% and had high number-average molecular weights (Mns) 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 (Tgs) in a wide range from 3 to 56 oC, which might be potentially used as biodegradable elastomers or plastics.
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