Hydrocarboxylation of C=C Bonds in Polycyclooctene: Progress Toward Valorization of Waste Polyolefins

Ogbu, Ikechukwu Martin; Fastow, Eli J.; Zhu, Weihao; Wells, Lucille A.; Chethalen, Roshni J.; Nair, Vivek; Hinton, Zachary R.; Balzer, Alex H.; Hu, Weiguo; Coughlin, E. Bryan; Winey, Karen I.; Kozlowski, Marisa C.

doi:10.1021/acs.macromol.4c00771

Hydrocarboxylation of C=C Bonds in Polycyclooctene: Progress Toward Valorization of Waste Polyolefins

Journal Article · Tue Jun 04 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c00771· OSTI ID:2396677

^[1]; ^[2]; Zhu, Weihao ^[2]; Wells, Lucille A. ^[2]; Chethalen, Roshni J. ^[3]; Nair, Vivek ^[2]; Hinton, Zachary R. ^[4]; ^[4]; Hu, Weiguo ^[3]; Coughlin, E. Bryan ^[3]; ^[2]; ^[2]

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

Upcycling of waste polyolefins into higher-value functional polymers through chemical functionalization is a promising strategy to recover value and minimize their environmental impact. We report the hydrocarboxylation of polycyclooctene as a model for accessing ethylene acrylic acid copolymers (EAA) from waste polyethylene. The effects of various process parameters on the hydrocarboxylation were investigated. The relationship between carboxylic acid concentration and material properties, including crystallinity, melting temperature, glass transition temperature, adhesive properties, and wettability, was studied in comparison to an unfunctionalized polyethylene. Among the catalysts evaluated, Co₂(CO)₈ exhibited relatively slow kinetics toward the hydrocarboxylation and was not compatible with 2,6-di-tert-butyl hydroxytoluene, a common additive present in commercial polyolefins. PdCl₂(PPh₃)₂ exhibited a higher reactivity toward the hydrocarboxylation, though polymer gelation was observed with extended reaction times or high catalyst loadings. Carboxylic acid incorporation into the polymer was readily controlled by varying the reaction time. Altogether, the resultant COOH-functionalized polyolefins possessed properties analogous to commercial EAA.

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:: 2396677

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 12 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
42 ENGINEERING
Functionalization
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Hydrocarboxylation of C=C Bonds in Polycyclooctene: Progress Toward Valorization of Waste Polyolefins

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