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

The alternating copolymerization of CO 2 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 CO 2 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 CO 2 -EDD copolymers were more than 99% and had high number-average molecular weights ( M n s) 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-CO 2 copolymerization system, a new random terpolymer with either electron-withdrawing or electron-donating side groups was produced with single glass transition temperatures ( T g s) 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