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Polymer properties along with recycling processes remain a constant challenge for post-recycled polymers. In this study, the development of recycling feasibility, monomers reactivity, and the chemical-recycled polymer properties from polycarbonate (PC) waste were demonstrated. Through selective aminolysis under mild conditions, the reduced molecular-weight products (or monomer mixtures) with newly incorporated flexible-ether linkages as building blocks were realized. By using the commodity monomers such as isocyanate reagents, monomer mixtures were readily to be re-connected into polyurethanes in one-pot process without prior purification of the recycled monomer mixtures. Due to the presence of urethane groups, the enhanced reactivity of the terminal phenolic hydroxyl groups of the monomer mixtures toward isocyanate groups would afford high molecular weights over ~80,000 g/mol for thermoplastic polyurethanes (TPUs). Moreover, by taking advantage of low melting point polyether-type polyols along with optimizing processing conditions, the TPUs exhibited a unique phase separation morphology with domain sizes ranging from ~10 nm to ~25 nm as investigated by using small angle X-ray scattering (SAXS) measurements. This work demonstrate that the PC waste was fully transformed into TPUs which exhibited improved elastomeric properties. This work demonstrates that the PC waste was depolymerized to monomer mixtures and subsequently transformed into recyclable thermoplastic polyurethanes exhibiting robust elastomeric properties. Image 1 • Monomer mixtures derived from the aminolysis of polycarbonates. • Thermoplastic polyurethane elastomers prepared from recycled monomer mixtures. • Diphenolic carbamates as hard segments for TPUs. • Ｍicrophase separation and semi-crystallinity morphologies. • Tensile properties comparable with those of TPUs prepared from pristine raw materials. [ABSTRACT FROM AUTHOR]

Over the years, the manipulation of polymer microphase separation associated with molecular architectures has been holding great promise for rendering structure-property relationship. A series of poly (urea/malonamide) dendrons bearing rigid adamantanes in the periphery were developed to serve as branching hard segments (HS) for thermoplastic polyurethanes (TPUs) either in end-capping or pendant manner. Thermal properties, crystalline structures, and mechanical properties of the TPUs were investigated by DSC, X-ray scattering, and DMA, respectively. The introduction of the branching units with bulky adamantanes would expectedly hinder the crystallization of HS. Intriguingly, the dendrons not only accelerate the crystallization of the soft segment (SS, based on polycaprolactone polyol (PCL)), but promote the phase separation between HS and SS to form distinct microdomains as well. These enhanced effects revealed a size-dependent relationship with growing size (or generation) of the branching HS. With the high SS crystallinity that can freeze the chain mobility and the robust HS domains that work as the physical crosslinking points, the resulting TPUs incorporated with adamantane-bearing units show superior shape memory behaviors. This work demonstrates that the molecular engineering on the architectures can significantly tailor the microstructures and properties of thermal plastic polymers. Image 1 • Preparation of dendrons bearing rigid adamantanes in periphery. • Adamantane-containing dendrons as hard segments for TPUs. • The crystallization of hard segments in TPUs hindered by bulky branching units. • The crystallization of the soft segment accelerated by the presence of bulky dendrons. • Shape memory properties enhanced by distinct microphase separation in TPUs. [ABSTRACT FROM AUTHOR]

In this study, novel dendritic urethane acrylate polymers were developed for the fabrication of robust honeycomb-like surfaces after exposure to a UV-crosslinking process. Through iterative synthesis based on a highly selective intermediate of 4-isocyanate-4′-(3,3-dimethyl-2,4-dioxo-azetidine)-diphenylmethane, poly(urea/malonamide) dendrons bearing peripheral methyl methacrylate end groups with well-defined structures were realized. A coating solution was prepared by the combined use of 30–70 wt% UA dendron acting as dendritic diluents and dendritic UA copolymers acting as amphiphiles that can fabricate honeycomb-like surfaces via a breath figure self-assembly process using water droplets as templates. The resulting film can be cured under UV light to achieve a robust honeycomb-like structure with a hexagonal structure exhibiting solvent-resistant properties in ethanol. Consequently, this solvent-resistant porous array can act as a substrate for the detection of vanishingly low concentrations of analytes that are aqueous insoluble via surface-enhanced Raman scattering analysis. • Novel synthesis of dendritic urethane acrylate copolymers • Development of UV-curable polymer surface with honeycomb-like structure • Realization of robust polymer surfaces with solvent resistance properties • Detection of aqueous insoluble analytes via surface-enhanced Raman scattering analysis [ABSTRACT FROM AUTHOR]