Thiol–ene Click Chemistry Incorporates Hydroxyl Functionality on Polycyclooctene to Tune Properties

Chethalen, Roshni John; Fastow, Eli J.; Coughlin, E. Bryan; Winey, Karen I.

doi:10.1021/acsmacrolett.2c00670

Thiol–ene Click Chemistry Incorporates Hydroxyl Functionality on Polycyclooctene to Tune Properties

Journal Article · Thu Jan 05 00:00:00 EST 2023 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.2c00670· OSTI ID:1924538

Chethalen, Roshni John ^[1]; ^[2]; ^[3]; ^[2]

Univ. of Massachusetts, Amherst, MA (United States); Department of Materials Science and Engineering and Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of Massachusetts, Amherst, MA (United States)

Polyolefins compose the majority of plastic waste, but conventional mechanical recycling degrades their properties, thereby reducing their value. We report the functionalization of a model for dehydrogenated polyethylene, polycyclooctene (PCOE), with thiol–ene click chemistry to install pendant hydroxyl ethyl thioethers. Functionalization of PCOE using mercaptoethanol via thiol–ene click chemistry yielded functionalization between 1.4 and 22.9% based on ethylene monomeric units. Reactions were well-controlled by varying the reagent stoichiometry and reaction time. Crystallinity and melting temperature decreased, and glass transition temperature increased with greater functionalization. Contact angle measurements reveal an increase in surface polarity with functionalization. Here, comparisons with poly(ethylene-co-vinyl alcohol) (EVOH) show comparable surface polarity at similar levels of alcohol functionalization. At 12% functionalization, the ultimate shear stress (USS) of functionalized PCOE in an adhesive configuration is 4.10 ± 0.48 MPa, comparable to EVOH. At >12% functionalization, the failure mode changed from adhesive to mixed adhesive–cohesive, and the USS decreased.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022238

OSTI ID:: 1924538

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 1 Vol. 12; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Thiol–ene Click Chemistry Incorporates Hydroxyl Functionality on Polycyclooctene to Tune Properties

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