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Article Dans Une Revue Angewandte Chemie International Edition Année : 2019

High Glass‐Transition Temperature Polymer Networks Harnessing the Dynamic Ring Opening of Pinacol Boronates

Résumé

Differential scanning calorimetry of high molar mass poly(4-vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120°C, resulting in a high glass transition temperature of 220°C. We hypothesize a ring-opening reactivity of pinacol boronates involving a nucleophilic attack on the sp 2 boron and subsequent bridging by interconnected pinacol moieties to form a densely crosslinked network with high-Tg. FTIR, solid-state NMR investigations and rheology studies on the polymer as well as double-tagging analyses on molecular model structures and theoretical calculations further support this hypothesis and indicate an entropy-driven ring opening inducing crosslinking. When diluted in an apolar solvent such as toluene, the polymer network can be resolubilized via ring closing thus recovering the entropically-favoured linear chains featuring cyclic boronate esters. The introduction of boron reactivity in polymer chains may open a path to a new class of dynamic polymer networks with uncommon and exciting thermodynamics.

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Polymères
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Dates et versions

hal-03006422 , version 1 (16-11-2020)

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Juliette Brunet, Franck Collas, Matthieu Humbert, Lionel Perrin, Fabrice Brunel, et al.. High Glass‐Transition Temperature Polymer Networks Harnessing the Dynamic Ring Opening of Pinacol Boronates. Angewandte Chemie International Edition, 2019, 58 (35), pp.12216-12222. ⟨10.1002/anie.201904559⟩. ⟨hal-03006422⟩
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