Random Terpolymer of Carbon Dioxide, Butadiene and Epoxides: Synthesis, Functionalization and Degradability

Comprehensive Summary The utilization of carbon dioxide (CO 2 ) as a C1 feedstock is consistently attractive, especially in the preparation of sustainable polymeric materials. In this contribution, a terpolymer of CO 2 , 1,3‐butadiene (BD) and epoxide is synthesized by scandium triflate catalyzed cationic ring‐opening copolymerization of α ‐ethylidene‐ δ ‐vinyl‐ δ ‐valerolactone (EVL), an intermediate derived from CO 2 and BD, with epoxides. The obtained terpolymer with a CO 2 content of 22 mol% has a number‐average molecular weight ( M n ) up to 7.8 kg/mol and a dispersity ( Đ ) of 2.4. The reactivity ratios of EVL and cyclohexene oxide (CHO) are determined as 0.01 and 1.07, respectively, suggesting random characteristic of the terpolymer. The preserved C=C double bonds from BD allow for the further modification of the terpolymer by photoinitiated crosslinking. The yielded networks are fluorescent and degradable. This method offers enhanced versatility to the synthesis and additional functionalization of CO 2 ‐based polymers.