Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization

Ogbu, Ikechukwu Martin; Fastow, Eli J.; Winey, Karen I.; Kozlowski, Marisa C.

doi:10.1021/acs.macromol.4c02074

Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization

Journal Article · Thu Nov 14 23:00:00 EST 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c02074· OSTI ID:2478231

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University of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania
University of Pennsylvania, Philadelphia, PA (United States)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: University of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0022238

OSTI ID:: 2478231

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 22 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ethyl groups
Functionalization
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Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization

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