High‐performance adhesives are of great interest in view of industrial demand. We herein identify a straightforward synthetic strategy towards universal hydrogen‐bonded (H‐bonded) polymeric ...adhesives, using a side‐chain barbiturate (Ba) and Hamilton wedge (HW) functionalized copolymer. Starting from a rubbery copolymer containing thiolactone derivatives, Ba and HW moieties are tethered as pendant groups via an efficient one‐pot two‐step amine‐thiol‐bromo conjugation. Hetero‐complementary Ba/HW interactions thus yield H‐bonded supramolecular polymeric networks. In addition to an enhanced polymeric network integrity induced by specific Ba/HW association, the presence of individual Ba or HW moieties enables strong binding to a range of substrates, outstanding compared to commercial glues and reported adhesives.
A straightforward synthetic strategy towards strong supramolecular adhesives is reported, based on a side‐chain barbiturate (Ba) and Hamilton wedge (HW) functionalized polymer. Specific Ba/HW interactions serve as cohesive domains to maintain polymeric network integrity, while molecular configuration of individual Ba or HW moieties linked onto substrates via diverse H‐bonding interactions, form adhesive domains and endow strong adherence.
The contribution of supramolecular chemistry to polymer science opens new perspectives for the design of polymer materials exhibiting valuable properties and easier processability due to the dynamic ...nature of non‐covalent interactions. Hydrogen bonding polymers can be used as supramolecular units for yielding larger assemblies that possess attractive features, arising from the combination of polymer properties and the responsiveness of hydrogen bonds. The post‐polymerization modification of reactive end‐groups is the most common procedure for generating such polymers. Examples of polymerizations mediated by hydrogen bonding‐functionalized precursors have also recently been reported. This contribution reviews the current synthetic routes toward hydrogen bonding sticker chain‐end functionalized polymers.
This Review summarizes recent advances in the design of hydrogen bonding chain‐end functionalized polymers through post‐polymerization functionalization or introduction of binding motifs in the course of the polymerization.
The toughness of a high-performance thermosetting epoxy network can be greatly improved by generating polyether sulfone-based macro- to nano-scale morphologies. Two polyethersulfones (PES) which only ...differ by their chain-end nature have been successively investigated as potential tougheners of a high-T
thermoset matrix based on a mixture of trifunctional and difunctional aromatic epoxies and an aromatic diamine. For a given PES content, morphologies and toughness of the resulting matrices have been tuned by changing curing conditions and put into perspective with PES chain-end nature.
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•Various potentially biobased methacrylates are evaluated as styrene replacement in UPRs.•Volatility, viscosity, miscibility are first evaluated.•Thermomechanical and mechanical ...properties are presented and discussed as a function of network structure.
Several potentially bio-based methacrylate derivatives, namely (with mol.% of bio-based carbon), butanediol dimethacrylate (BDDMA) (33%), isobornyl methacrylate (IBOMA) (71%), lauryl methacrylate (LMA) (75%) have been evaluated as alternatives to styrene as reactive diluent of unsaturated polyester (UPR). First the compatibility of these compounds with SMC/BMC processes has been studied in terms of volatility, miscibility with UPR and viscosity. Based on these preliminary experiments, butanediol dimethacrylate (BDDMA) was selected as sole reactive diluent. The thermo-mechanical and mechanical properties of the resulting network were found to be very different from the ones of a UPR/MMA network prepared as a reference. Consequently, mixtures constituted of BDDMA and one monomethacrylate derivative (MMA, IBOMA and LMA) were then used as reactive diluents to yield networks owning a large range of mechanical behaviours.
Among the various challenges in medicine, diagnosis, complete cure, and healing of cancers remain difficult given the heterogeneity and complexity of such a disease. Differing from conventional ...platforms with often unsatisfactory theranostic capabilities, the contribution of supramolecular interactions, such as hydrogen‐bonds (H‐bonds), to cancer nanotheranostics opens new perspectives for the design of biomedical materials, exhibiting remarkable properties and easier processability. Thanks to their dynamic characteristics, a feature generally observed for noncovalent interactions, H‐bonding (macro)molecules can be used as supramolecular motifs for yielding drug‐ and diagnostic carriers that possess attractive features, arising from the combination of assembled nanoplatforms and the responsiveness of H‐bonds. Thus, H‐bonded nanomedicine provides a rich toolbox that is useful to fulfill biomedical needs with unique advantages in early‐stage diagnosis and therapy, demonstrating the promising potential in clinical translations and applications. Here the design and synthetic routes toward H‐bonded nanomedicines, focus on the growing understanding of the structure‐function relationship for efficient cancer treatment are summarized. A guidance for designing new H‐bonded intelligent theranostic agents is proposed, to inspire more successful explorations of cancer nanotheranostics and finally to promote potential clinical translations.
Hydrogen‐bonds (H‐bonds) bridge artificial and biological sciences, implementing dynamic properties into materials and (macro)molecules, which cannot be achieved via purely covalent bonds. In this review, the current state‐of‐the‐art for designing novel H‐bonded nanomedicines for precise diagnosis, and targeted therapeutic drugs delivery are highlighted.
Supramolecular miktoarm stars (AB2 type) composed of poly (methyl methacrylate)-polystyrene2 (PMMA-PS2), poly(isoprene)-polystyrene2 (PI-PS2), and poly(vinyl acetate)-polystyrene2 (PVAc-PS2) were ...successfully synthesized by assembling reversible addition−fragmentation chain transfer (RAFT)-polymerized chains bearing hydrogen-bonding heterocomplementary associating units. To this end, thymine and diaminopyridine-functionalized chain transfer agents were designed to efficiently mediate the polymerization of vinyl acetate, methyl methacrylate, isoprene, and styrene. The selective associations of the resulting hydrogen-bonding macromolecular building blocks PVAc/PS, PI/PS, and PMMA/PS were demonstrated by 1H NMR in CDCl3 solutions. Miktoarm stars formation in the bulk was also confirmed by transmission electronic microscopy.
Supramolecular poly(vinyl acetate) PVAc 3‐arms stars were successfully generated by Reversible Addition–Fragmentation chain Transfer (RAFT)‐polymerized chains bearing hydrogen‐bonding ...heterocomplementary associating units. Chain Transfer Agents (CTA) bearing thymine‐ and diaminopyridine‐based units were first synthesized and proved to mediate efficiently the polymerization of VAc. The binding ability of the chains in solution was then demonstrated by 1H NMR and GPC measurements, proving the formation of the supramolecular stars.
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