Increasing Branching and Functionalization Decreases Crystallinity and Crystallization Rate in Linear EVOH

Fastow, Eli J.; Radzanowski, Anne N.; Coughlin, E. Bryan; Winey, Karen I.

doi:10.1021/acsapm.4c03361

Title: Increasing Branching and Functionalization Decreases Crystallinity and Crystallization Rate in Linear EVOH

Journal Article · 20 January 2025 · ACS Applied Polymer Materials

DOI: https://doi.org/10.1021/acsapm.4c03361 · OSTI ID:2506968

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

Here, we report the crystallization behavior of a linear poly(ethylene-co-vinyl alcohol) (LEVOH) under isothermal crystallization as a function of both OH incorporation and undercooling, and compare the results to conventional branched EVOH. This LEVOH is synthesized by post-polymerization functionalization of polycyclooctene, and it exhibits a half-crystallization time and primary crystallization rate nearly an order of magnitude faster than branched EVOH at ~ 6 mol% OH incorporation. While the LEVOH obtains approximately twice the extent of crystallization compared to the branched equivalent, as OH incorporation increases, the crystallization kinetics and crystallinity of LEVOH decrease. The crystal structure of LEVOH is orthorhombic at low functionalization (≤ 11 mol% OH), a mixture of orthorhombic and hexagonal at moderate functionalization (17 - 21 mol%), and hexagonal at high functionalization (23 %). The LEVOH crystallizes into plates, with crystallite widths ~ 20 - 60 times the crystallite thickness. Ultimately, we show LEVOH crystallizes faster and to a greater extent than commercial branched EVOH, a potential advantage of post-polymerization functionalization as part of polymer-to-polymer upcycling.

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

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

Grant/Contract Number:: SC0022238

OSTI ID:: 2506968

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 3 Vol. 7; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright 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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Title: Increasing Branching and Functionalization Decreases Crystallinity and Crystallization Rate in Linear EVOH

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