Polyolefin blends with co-continuous architectures enabled by dynamic covalent crosslinking

Neidhart, Eliza K. [Univ. of North Carolina, Chapel Hill, NC (United States)]; Ribet, Stephanie M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:000000027117066X); Lee, Taehyun A. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0009000109678286); Kearney, Logan [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000308113483); Bustillo, Karen C. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000220966078); Dailing, Eric A. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000222997783); Hua, Mutian [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of Washington, Seattle, WA (United States)] (ORCID:000000024079316X); Ophus, Colin [Stanford Univ., CA (United States)] (ORCID:0000000323488558); Fricke, Sophia N. [University of California, Berkeley, CA (United States)] (ORCID:000000020183466X); Song, Ah-Young [University of California, Berkeley, CA (United States)] (ORCID:0000000179310148); Reimer, Jeffrey A. [University of California, Berkeley, CA (United States)] (ORCID:0000000241913725); Alexanian, Erik J. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000202562133); Atkin, Joanna M. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000212115193); Helms, Brett A. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division] (ORCID:0000000339254174); Leibfarth, Frank A. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000177370331)

doi:10.1126/sciadv.aee2328

DOE OSTI · 3367511

Polyolefin blends with co-continuous architectures enabled by dynamic covalent crosslinking

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Abstract

Blending polymers produces brittle materials due to macrophase separation and poor interfacial adhesion, which is exemplified by mixtures of polyolefins. This presents a formidable challenge for the mechanical recycling of mixed plastic waste. Here, we demonstrate that dynamic covalent crosslinking of immiscible polyolefin blends creates macrophase separated co-continuous architectures, yet they display excellent mechanical properties, which challenges the conventional wisdom regarding morphology-property relationships in polymer blend compatibilization. We find that the position and orientation of dynamic crosslinks and their influence on crystallinity are key to understanding the structure-morphology-property relationships. In particular, high-resolution microscopy imaging reveals alignment of crystallite planes with strong orientational preference, particularly at polymer-polymer interfaces, which contribute to material performance. We further demonstrate that changes in crosslinker density and valency allow the properties of binary and ternary polyolefin blends to be tuned in a modular fashion.

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Neidhart, Eliza K. [Univ. of North Carolina, Chapel Hill, NC (United States)], Ribet, Stephanie M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:000000027117066X), Lee, Taehyun A. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0009000109678286), Kearney, Logan [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000308113483), Bustillo, Karen C. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000220966078), Dailing, Eric A. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry] (ORCID:0000000222997783), Hua, Mutian [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of Washington, Seattle, WA (United States)] (ORCID:000000024079316X), Ophus, Colin [Stanford Univ., CA (United States)] (ORCID:0000000323488558), Fricke, Sophia N. [University of California, Berkeley, CA (United States)] (ORCID:000000020183466X), Song, Ah-Young [University of California, Berkeley, CA (United States)] (ORCID:0000000179310148), Reimer, Jeffrey A. [University of California, Berkeley, CA (United States)] (ORCID:0000000241913725), Alexanian, Erik J. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000202562133), Atkin, Joanna M. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000212115193), Helms, Brett A. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division] (ORCID:0000000339254174), Leibfarth, Frank A. [Univ. of North Carolina, Chapel Hill, NC (United States)] (ORCID:0000000177370331). 2026-05-15. Polyolefin blends with co-continuous architectures enabled by dynamic covalent crosslinking. https://doi.org/10.1126/sciadv.aee2328

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