A mechanically clamped liquid-poly(ethylene oxide) electrolyte that combines high ionic conductivity and dimensional integrity of a solid material is designed.

Materials. All chemicals were purchased from Acros or Aldrich and were of highest purity grade. All chemicals were used as received unless otherwise specified. 2,2'-azobis(isobutyronitrile) (AIBN) was recrystallized from diethyl ether. S-1-dodecyl-S'-(α,α'-dimethyl-α"-acetic acid)trithiocarbonate (DDMAT) was synthesized as described elsewhere and recrystallized two times in n-hexane. 1 Terpyridine modified S-1-dodecyl-S'-(α,α'-dimethyl-α"-acetic acid)trithiocarbonate (DDMAT-tpy) chain transfer agent was synthesized as reported elsewhere. 2 Nisopropylacrylamide (NIPAAm) was recrystallized from n-hexane. Styrene (S) was passed through a short column filled with activated basic aluminum oxide (Brockmann I) before use. 2 N,N-dimethylformamide (DMF) and dichloromethane (DCM) were distilled over calcium hydride.

We study in the melt the linear viscoelastic properties of supramolecular assemblies obtained by adding different amounts of nickel ions to linear entangled poly(ethylene oxide) (PEO) building blocks end-functionalized by a terpyridine group. We first show that the elasticity of these supramolecular assemblies is mainly governed by the entanglement dynamics of the building blocks, while the supramolecular interactions delay or suppress their relaxation. By adjusting the amount of metal ions, the relaxation time as well as the level of the low-frequency plateau of these supramolecular assemblies can be controlled. In particular, the addition of metal ions above the 1:2 metal ion/terpyridine stoichiometric ratio allows secondary supramolecular interactions to appear, which are able to link the linear supramolecular assemblies and thus, lead to the reversible gelation of the system. By comparing the rheological behavior of different linear PEO samples, bearing or not functionalized chain-ends, we show that these extra supramolecular bonds are partially due to the association between the excess of metal ions and the oxygen atoms of the PEO chains. We also investigate the possible role played by the terpyridine groups in the formation of these secondary supramolecular interactions.

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This work studies the linear viscoelastic properties of a series of low-dispersity poly(n-butyl acrylate) chains endfunctionalized with 2,2′;6′,2″-terpyridine, able to self-associate by metal−ligand coordination. Depending on the architecture and functionality of the chains, the polymers self-assemble into different metallo-supramolecular bulk structures once metal ions are added. Linear building blocks (monofunctional or bifunctional) form longer chains while four-arm stars form networks. The properties of the obtained materials can be finely tuned depending on the length of the polymer chains and the type of metal. In this respect, enhanced control is gained over the dynamics of this class of metallo-supramolecular assemblies. Hence, they are extremely interesting for specific applications such as adhesives or mechanosensors.

Thiol- and yne-functionalized beads were manufactured in a simple microfluidic setup. While CuAAC and thiol-yne reactions were performed on yne-functionalized beads, 9 different thiol-X reactions were compared, in terms of kinetics and conversion, on thiol-functionalized beads.

Associating polymers constitute a fascinating class of materials because of the richness in their rheological behaviors. They may find application in numerous areas, provided that their mechanical properties can be tailored to fulfill specific requirements. In this context, this study aims to control the magnitude of the viscoelastic response of coordination micellar hydrogels built through the hierarchical assembly of heterotelechelic poly(N-isopropylacrylamide). The influence of different variables on the rheological properties of those materials is investigated and discussed in term of cross-linking density. In this respect, two distinct regimes are distinguished that correspond to the well percolated network, with a high cross-linking density, and the weakly percolated network, with a low cross-linking density.