Incorporation of Thioacetate Pendants on a Polyalkenamer Enables High Extensibility

Chethalen, Roshni John; Kim, Myounguk; Ruiz, Juan Correa; Tu, Chien-Hua; Gray, Jordan; Winey, Karen I.; Lesser, Alan J.; Crosby, Alfred J.; Coughlin, E. Bryan

doi:10.1021/acs.macromol.4c02110

Incorporation of Thioacetate Pendants on a Polyalkenamer Enables High Extensibility

Journal Article · Thu Oct 24 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c02110· OSTI ID:2478472

Chethalen, Roshni John ^[1]; ^[2]; Ruiz, Juan Correa ^[2]; ^[3]; Gray, Jordan ^[2]; ^[3]; Lesser, Alan J. ^[2]; ^[2]; ^[2]

University of Massachusetts, Amherst, MA (United States); University of Massachusetts Amherst
University of Massachusetts, Amherst, MA (United States)
University of Pennsylvania, Philadelphia, PA (United States)

This study focuses on functionalizing polycyclooctene (PCOE) with thioacetate groups using thiol–ene click chemistry. The ethylene thioacetate (EVSA) copolymers produced vary in thioacetate incorporation (4–25 mol %) via a controlled semibatch addition technique with AIBN dosing. Copolymers with 4–14 mol % thioacetate are semicrystalline, while those with 20–25 mol % are amorphous. Increased functionalization correlates with decreased crystallinity and increased stretchability, with the highest functionalization (25 mol %) showing a modulus of 0.045 MPa and 2000% elongation at break. Here, this behavior is due to the pseudoprecise functionalization of the thioacetate pendants and intrinsic cross-linking that occurs during melt processing. Broadband dielectric spectroscopy (BDS) indicates a low activation energy barrier (16 kJ/mol for the β process), suggesting potential self-healing applications.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0022238

OSTI ID:: 2478472

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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