Ring opening metathesis polymerization of the natural sesquiterpenes caryophyllene and humulene, optionally complemented by exhaustive post-polymerization hydrogenation, yields non-crosslinked linear polymers with unprecedented microstructures reflecting the specific scaffolds of the feedstocks and with low glass transition temperatures in the range from −15 to −50°C. Scheme 1 Synthesis of poly(caryophyllene) and poly(hydrocaryophyllene), left, and poly(humulene) and poly(hydrohumulene), right.

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... a: ROMP of the sesquiterpene; b: post-polymerization hydrogenation. † Electronic supplementary information (ESI) available: Text giving experimental details, NMR spectra of polymers and monomers, DSC thermograms of polymers, 3D and HOMO views of caryophyllene and humulene. See