Synthesis and Blending of Two Poly(ethylene-co-vinyl alcohol) Polymers with Mixed 1,2-Diol Stereochemistry

Jimenez Antenucci, Pedro M.; Radzanowski, Anne N.; Fastow, Eli J.; Votruba-Drzal, James; Redder, Madyson; Winey, Karen I.; Coughlin, E. Bryan; Kozlowski, Marisa C.

doi:10.1021/acsapm.5c00785

Synthesis and Blending of Two Poly(ethylene-co-vinyl alcohol) Polymers with Mixed 1,2-Diol Stereochemistry

Journal Article · Fri May 16 00:00:00 EDT 2025 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.5c00785· OSTI ID:2583359

^[1]; ^[2]; ^[1]; Votruba-Drzal, James ^[1]; Redder, Madyson ^[2]; ^[1]; ^[2]; ^[1]

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

Parallel pathways for the postpolymerization modification of double bonds in a polycyclooctene (PCOE) backbone generate vicinal 1,2-diol-containing polymers with mixed but opposite stereochemistry, depending on the trans:cis ratio of the C═C in PCOE. Beginning from the same batch of PCOE, epoxidation and subsequent ring-opening with sulfuric acid and water produce a polymer with the majority erythro diols, whereas an osmium-catalyzed dihydroxylation results in diols in the majority threo orientations. These postpolymerization modification approaches enable access to previously unexplored polymers with a mixture of erythro and threo diols, offering tunable diol stereochemistry to tailor material properties. The majority erythro diols lead to hexagonal crystallites with higher melting temperatures and overall crystallinity when compared to the majority threo diols that form monoclinic crystallites. When blended, the two diastereomers phase separate as evidenced by distinct melting endotherms and crystal structures corresponding to the two component polymers, suggesting a route to tune the barrier or mechanical properties. Furthermore, this investigation synthesized polymers with mixed stereochemical diols and elucidated the thermal and morphological properties of regioregular linear poly(ethylene-co-vinyl alcohols) and their blends.

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 Institutes of Health (NIH); National Science Foundation (NSF)

Grant/Contract Number:: SC0022238

OSTI ID:: 2583359

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 11 Vol. 7; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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Synthesis and Blending of Two Poly(ethylene-co-vinyl alcohol) Polymers with Mixed 1,2-Diol Stereochemistry

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