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Developing effective recycling pathways for polyolefin waste, enabling a move to a circular economy, is an imperative that must be met. Post-use modification has shown promising results in upcycling polyolefins, removing the limitation of inertness, and improving the final physical properties of the recycled material while extending its useful lifetime. Grafting of maleic anhydride groups to polypropylene is an established industrial process that enhances its reactivity and provides a convenient route to further functionalization and upcycling. In this work, maleic anhydride grafted polypropylene (PPgMAH) was hydroxylated, and subsequently cured with a diisocyanate to form a thermoset polyurethane (PU). The crystal structure (unit cell and lamellar structure) of the polypropylene (PP) was preserved in the PU. At room temperature, the PU showed high modulus due to the crystallization behavior of the PP; upon increasing the temperature above the melting temperature, the modulus decreased to a rubbery plateau, consistent with formation of a network. The resulting PU showed higher glass transition temperature and lower degree of crystallinity than its PP predecessor due to the crosslinked nature of the polymer. The mechanical integrity of the PU was maintained through several reprocessing cycles due to the melt processability enabled by the presence of a urethane exchange catalyst. This functionalization and upcycling route thus offers a promising alternative to repurposing PP waste, in which the creation of melt-processable thermoset polymers expands applications for the materials. 

The physical properties of an ABA triblock copolymer-based thermoplastic elastomer, containing a poly(lauryl methacrylate-co-methacrylic acid) midblock and poly(methyl methacrylate) endblocks, were enhanced through neutralization of the methacrylic acid (MAA) repeat units with NaOH to form ionic interactions in the midblock. Rheological properties of the midblock and mechanical properties of the triblock copolymer were investigated as functions of acid (MAA) and ion content. Midblock relaxation times (τ) increased with increasing acid and ion content, however the activation energy extracted from an Arrhenius analysis appeared constant for all acid and ion contents. Meanwhile, the factors of enhancement of the strain at break and tensile strength (as compared to the baseline polymer without ionic interactions or hydrogen bonding) collapsed onto master curves when plotted as functions of log τ, indicating the mechanical behavior of the triblock copolymer could be tuned through varying the relaxation time of the midblock. The tensile strength increased by as much as a factor of 17 times greater than that of the baseline polymer. More moderate enhancements were observed in the strain at break, with the maximum strain at break occurring at intermediate relaxation times. This suggests that midblock chain dynamics are a governing factor for the mechanical property enhancements, due to the effects of the ionic aggregates and chain mobility on stress dissipation under tensile deformation. 

Covalently networked polymers offer desirable non-crystallinity and mechanical strength for solid polymer electrolytes (SPEs), but the chemically active cross-links involved in their construction could deteriorate the compatibility with high-energy cathode materials that are electrophilic and/or in the charged state. Herein we reveal a strong dependence of cyclability of such cathodes on the reactivity of covalently networked SPEs and demonstrate a polymer design that renders these SPEs chemically inert. We designed and synthesized two hybrid networks, both with polyethylene oxide as the cation conducting component and polyhedral oligomeric silsesquioxane as the branch point, but respectively use alkylamino and chemically inert triazole groups as cross-links. All-solid-state cells using the alkylamino-containing SPE underwent rapid degradation while cells using triazole SPEs showed stable cycling.