2024/11/15 by Ikechukwu Martin Ogbu, Eli J. Fastow, Karen I. Winey +1 · 2 voices
Engineering · Materials Science · #Fiber-reinforced polymer composites #Polymer crystallization and properties #biodegradable polymer synthesis and properties
paper · doi:10.1021/acs.macromol.4c02074
openalex publication_date 2024/11/15 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/15
To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene- co -ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C═C bonds were subsequently hydrogenated. The bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.