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  1. Abstract

    The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene‐co‐vinyl alcohol) (EVOH) and related polymer blends – into alkane products. We report that Ru/ZrO2is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1−C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in‐situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C−C scission reveal that the hydrogenolysis of EVOH is slower than low‐density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.

     
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  2. ABSTRACT

    We demonstrate the directional alignment of perpendicular‐lamellae domains in fluorinated three‐armed star block polymer (BP) thin films using solvent vapor annealing with shear stress. The control of orientation and alignment was accomplished without any substrate surface modification. Additionally, three‐armed star poly(methyl methacrylate‐block‐styrene) [PMMA‐PS] and poly(octafluoropentyl methacrylate‐block‐styrene) were compared to their linear analogues to examine the impact of fluorine content and star architecture on self‐assembled BP feature sizes and interdomain density profiles. X‐ray reflectometry results indicated that the star BP molecular architecture increased the effective polymer segregation strength and could possibly facilitate reduced polymer domain spacings, which are useful in next‐generation nanolithographic applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2019, 57, 1663–1672

     
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  3. ABSTRACT

    Dual‐functional monomers consist of two distinctly different functional groups that enable chemical versatility. The most readily available epoxy‐methacrylate dual‐functional monomer is glycidyl methacrylate (GMA). In an effort to produce bio‐based, aromatic complements to GMA, asymmetric phenolic diols (vanillyl alcohol, syringyl alcohol, gastrodigenin, and tyrosol) were identified and selectively epoxidized at the aromatic hydroxyl followed by subsequent esterification at the aliphatic hydroxyl to prepare dual functional monomers, vanillyl alcohol epoxy‐methacrylate (VAEM), syringyl alcohol epoxy‐methacrylate (SAEM), gastrodigenin epoxy‐methacrylate (GDEM), and tyrosol epoxy‐methacrylate (TEM). These monomers are viable platforms for a multitude of applications due to their unique chemical functionalities. VAEM, SAEM, GDEM, and TEM were homopolymerized individually to produce aromatic, bio‐based epoxy‐functional thermoplastics analogous to poly(GMA). The molecular weight distributions and thermal properties of each polymer were evaluated, as were the surface characteristics of flow‐coated thin films from these polymers. Most of the newly prepared epoxy‐functional thermoplastics exhibited increased thermal stability (initial decomposition temperatures >260 °C in air) relative to poly(GMA), while retaining similar glass transition temperatures (~ 65 °C) and surface energies (~ 53 mJ m−2); thus, these materials could be substituted for poly(GMA) and enable use in higher‐temperature applications. © 2020 Wiley Periodicals, Inc. J. Polym. Sci.2020,58, 673–682

     
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