Functional Polymer Synthesis From CO, CO 2 , and Butadiene

ABSTRACT Carbon dioxide (CO 2 ) and carbon monoxide (CO) are among the most abundant, renewable C1 building blocks that have been widely used to synthesize sustainable polymers. However, their markedly different thermodynamic profiles have precluded their simultaneous incorporation into a single polymer. Here we report a novel reaction strategy for the selective construction of formal CO/CO 2 /butadiene terpolymers in a 1:1:2 molar ratio. This protocol involves the Pd‐catalyzed telomerization of CO 2 with butadiene to form a lactone‐based intermediate (EVP), followed by its catalytic alternating copolymerization with CO, affording functional polyketones bearing pendent unsaturated lactone side groups in high yields. Notably, both the ketone and lactone functionalities within the functional polymers can be quantitatively reduced to hydroxyl groups using sodium borohydride (NaBH 4 ) at room temperature. The obtained multi‐hydroxy functionalized polymer exhibits strong adhesion to common substrates (adhesion strength up to 10.13 MPa on wood) together with desirable oxidative degradability.