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

Abstract

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 (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 °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

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

“…12 Importantly, it is also possible to regulate T g of the CO 2 /epoxide copolymer via Zn−Co(III) DMCC catalysis by tuning the reaction temperature and CO 2 pressure. 29,52 For copolymers with side branched alkyl and aryl groups, the T g s increased from 35 to 84°C with increasing steric hindrance (i.e., carbon numbers C2, C4, and C6 to C7) of the substituent groups. This could effectively inhibit the free rotation of the backbone.…”

“…14,16,28,29 Recently, a nanolamellar Zn−Co(III) DMCC was observed to effectively catalyze the alternating copolymerization of CO 2 with epoxides with long side alkyl groups. 30 These results led us to systematically study the substituent effects of the epoxides on the alternating copolymerization of CO 2 /epoxide using this catalyst.…”

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

“…Moreover, the copolymer with 70.7% carbonate content presents high thermal decomposition temperature of 250 o C and relatively high T g of 31.2 o C. Although we observed that Zn-Co(III) DMCC was a regioselective catalyst for ROP of epichlorohydrin on the site of methine group [142], we had no direct evidence for supporting the regioselective CO 2 /epichlorohydrin copolymerization. Terpolymerization of two epoxides with CO 2 could also performed well by Zn-Co(III) DMCC catalyst, affording terpolymers with tunable T g s [143]. The terpolymerization of CO 2 , styrene oxide and 1, 2-epoxydodecane with electron-donating dodecane group was successfully performed by using Zn-Co(III) DMCC catalyst, resulting in a new random terpolymer with single T g s in a wide range of 3 to 56 o C.…”

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

“…However, Zhang and co‐workers showed that also aliphatic polycarbonates with a flexible backbone may exhibit T g s up to 84 °C depending on their side chains. While the T g decreases with increasing alkyl length to −38 °C, the glass transition may increase up to 84 °C by steric influences . Also long alkyl side chains with up to 20 carbon atoms were already incorporated in aliphatic polycarbonates to tune the thermal properties .…”

“…Using a binary or bifunctional Co(III)‐based catalyst system, the incorporation of PO resulted in a random terpolymerization and the incorporation of CHO in an alternating terpolymerization with more than 99% carbonate linkages . In addition, Fan and co‐workers introduced random terpolymers obtained from styrene oxide, 1,2‐epoxydodecane, and CO 2 with T g s in a range of 3–56 °C depending on the comonomer ratio …”