A dual seven-membered cyclic carbonate/olefin monomer was synthesized from CO2 and cis-1,4-butenediol and polymerized. The properties of the polymer were controlled using divergent catalytic strategies toward the stereochemistry of the olefin. Ring-opening polymerization of the cyclic carbonate using an organocatalytic approach retained the cis-stereoconfiguration of the olefin and yielded a hard semicrystalline polymer (Tm 115 °C). Ring-opening metathesis polymerization using Grubbs’ catalyst proceeded with high trans-stereoregularity (95%) and produced a soft amorphous polymer (Tg −22 °C). Cis to trans isomerization of the polymer was possible using Cu(I) salts under UV light. In all polymers, the C═C double bond remained available for postpolymerization modification and thermoset resins were formed by cross-linking. From this single monomer, cis-trans-cis triblock copolymers, with potential applications as thermoplastic elastomers, were synthesized by combining both strategies using cis-1,4-butenediol as a chain transfer agent.
ASJC Scopus subject areas
- Colloid and Surface Chemistry
McGuire, T. M., Pérale, C., Castaing, R., Kociok-Köhn, G., & Buchard, A. (2019). Divergent Catalytic Strategies for the Cis/Trans Stereoselective Ring-Opening Polymerization of a Dual Cyclic Carbonate/Olefin Monomer. Journal of the American Chemical Society, 141(34), 13301-13305. https://doi.org/10.1021/jacs.9b06259