Synthesis, Properties, and Metathesis Activity of Polyurethane Thermoplastics and Thermosets from a Renewable Polysesquiterpene Diol

Kovel, Carli B.; Perine, Hannah; Chirik, Paul J.; Mohadjer Beromi, Megan

doi:10.1021/acs.macromol.4c02436

Title: Synthesis, Properties, and Metathesis Activity of Polyurethane Thermoplastics and Thermosets from a Renewable Polysesquiterpene Diol

Journal Article · Fri Aug 01 00:00:00 UTC 2025 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.4c02436 · OSTI ID:2583417

^[1]; Perine, Hannah ^[2];

^[1];

^[2]

Princeton Univ., NJ (United States)
US Naval Academy, Annapolis, MD (United States)

Polyurethanes (PUs) are the sixth most commonly utilized plastic class, yet ∼80% of commodity material is landfilled or incinerated at the end of life. Disposal of thermosets is particularly problematic as cross-linking prevents the repurposing of disposed material. Thus, there is considerable interest in the development of PUs derived from inexpensive feedstocks that can be inherently chemically deconstructed. Ring opening metathesis polymerization (ROMP) of the naturally occurring sesquiterpene β-caryophyllene in the presence of dihydroxy chain terminators afforded the polyol hydroxy-terminated polycaryophyllene (HTPCR). Incorporation of HTPCR into PUs through reaction with polyisocyanates produced polymers with thermal and rheological properties comparable to commodity materials. The feasibility of chemical degradation of both thermoplastic and thermoset materials was also demonstrated through ruthenium-mediated metathesis, utilizing the metathesis-active olefins within the repeat caryophyllene monomer unit. Overall, this work highlights the value of biorenewable, chemically reprocessable polysesquiterpenes in the PU space.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: Defense Threat Reduction Agency; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022303

OSTI ID:: 2583417

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 15 Vol. 58; ISSN 1520-5835; ISSN 0024-9297

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Synthesis, Properties, and Metathesis Activity of Polyurethane Thermoplastics and Thermosets from a Renewable Polysesquiterpene Diol

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