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  1. Tailored glycolysis of Nylon 6 to enable upcycling into high-strength adhesives

    Nylon is a high-strength polyamide widely used in automotive, textiles, packaging, etc. However, its durability makes nylon waste difficult to manage, with recycling limited to mechanical grinding to make fillers. Here, we report a catalytic glycolysis approach to deconstruct Nylon 6 into controlled-length oligomers, enabling upcycling into value-added materials. A low-molecular-weight oligomer (Mn = 1.8 kg/mol) was repolymerized with diepoxy-terminated poly(bisphenol A-co-epichlorohydrin) via mechanochemistry to create a high-performance adhesive. This copolymer achieves lap shear strengths over 22 MPa on steel and bonds steel to carbon fiber composites, nearly tripling the performance of commercial adhesives even at 90°C. Thermomechanical analyses showmore » that the adhesive retains thermal stability similar to nylon 6 but melts at lower temperatures, allowing easier processing. The material can be reprocessed and reused without significant performance loss. This study demonstrates a strategy to convert nylon 6 waste into valuable materials, offering a sustainable path for difficult-to-recycle plastics.« less
  2. Simultaneous Degradation‐Depolymerization of Bioderived Comb Copolymers

    Poly(lactic acid) (PLA) is the most widely explored biodegradable alternative for polystyrene; however, its low toughness and glass transition temperature may limit its wider adoption as a sustainable replacement. To improve its material and thermal properties, PLA can be chemically or physically combined with other polymers, like poly(methyl methacrylate) (PMMA), though the incorporation of vinyl‐based polymer components complicates chemical recycling and reduces the sustainability of the material. Here, in this study, we synthesized polymethacrylate‐PLA comb copolymers designed to be thermally deconstructed. Our design strategically extends current polymer deconstruction methodologies to more complex macromolecular systems. Thermally labile units within the polymethacrylatemore » backbone permitted depolymerization that was concurrent with PLA side chain degradation during heating. This dual degradation‐depolymerization process enhances the overall sustainability of lactide/vinyl‐based copolymers and demonstrates the synergistic potential of integrating multiple deconstruction pathways into a single system. This report elaborates on the design of advanced, degradable copolymers, contributing to the further development of sustainable polymer materials.« less
  3. N2O deconstruction of polycyclooctene to generate carbonyl-functionalized macromonomers

    Deconstruction of polyolefins into functionalized macromonomers presents a compelling strategy for polyolefin upcycling by creating macromonomers through dehydrogenation/depolymerization. We show that nitrous oxide (N2O), a greenhouse gas waste product from the production of nylon, mediates the deconstruction of polycyclooctene (PCOE) and generates carbonyl-functionalized macromonomers. Carbonyl incorporation and macromonomer molar mass were well controlled by reaction time, and subsequent hydrogenation readily removed residual carbon-carbon double bonds. Here, we also demonstrated that the reaction could progress efficiently with substrates of moderate levels of unsaturation, closely mimicking partially dehydrogenated polyethylene. Such carbonyl-functionalized macromonomers could serve as feedstock for preparing vitrimers and other functionalmore » polymers.« less
  4. Chemically recyclable polyolefin-like multiblock polymers

    Polyolefins are the most important and largest volume plastics produced. Unfortunately, the enormous use of plastics and lack of effective disposal or recycling options have created a plastic waste catastrophe. Here in this work, we report an approach to create chemically recyclable polyolefin-like materials with diverse mechanical properties through the construction of multiblock polymers from hard and soft oligomeric building blocks synthesized with ruthenium-mediated ring-opening metathesis polymerization of cyclooctenes. The multiblock polymers exhibit broad mechanical properties, spanning elastomers to plastomers to thermoplastics, while integrating a high melting transition temperature (Tm) and low glass transition temperature (Tg), making them suitable formore » use across diverse applications (Tm as high as 128°C and Tg as low as –60°C). After use, the different plastics can be combined and efficiently deconstructed back to the fundamental hard and soft building blocks for separation and repolymerization to realize a closed-loop recycling process.« less
  5. Lignocellulose deconstruction in the biosphere

    Microorganisms have evolved different and yet complementary mechanisms to degrade biomass in the biosphere. The chemical biology of lignocellulose deconstruction is a complex and intricate process that appears to vary in response to specific ecosystems. These microorganisms rely on simple to complex arrangements of glycoside hydrolases to conduct most of these polysaccharide depolymerization reactions and also, as discovered more recently, oxidative mechanisms via lytic polysaccharide monooxygenases or non-enzymatic Fenton reactions which are used to enhance deconstruction. It is now clear that these deconstruction mechanisms are often more efficient in the presence of the microorganisms. In general, a major fraction ofmore » the total plant biomass deconstruction in the biosphere results from the action of various microorganisms, primarily aerobic bacteria and fungi, as well as a variety of anaerobic bacteria. Beyond carbon recycling, specialized microorganisms interact with plants to manage nitrogen in the biosphere. Understanding the interplay between these organisms within or across ecosystems is crucial to further our grasp of chemical recycling in the biosphere and also enables optimization of the burgeoning plant-based bioeconomy.« less
  6. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

    Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation give rise to a complex, 3D network of lignin that displays randomly branched topology and fractal properties. Attempts at isolating lignin, analogous to archaeology, are instantly destructive and nonrepresentative of in planta. Lack of plant ligninases ormore » enzymes that hydrolyze specific bonds in lignin-carbohydrate complexes (LCCs) also frustrate a better grasp of lignin. Supramolecular self-assembly, nano-mechanical properties of lignin-lignin, ligninpolysaccharide interactions and association-dissociation kinetics affect biomass deconstruction and thereby cost-effective biofuels production.« less

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