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Article dans une revue
1,4-Polybutadienes with Pendant Hydroxyl Functionalities by ROMP: Synthetic and Mechanistic Insights
Abstract : The reactivity of cis-3,4-bis(hydroxymethyl)cyclobutene derivatives bearing free and protected hydroxyl groups during ring-opening metathesis polymerization (ROMP) was investigated using ruthenium-based initiators. It was found that the ROMP of cis-4-benzyloxymethyl-3-hydroxymethylcyclobutene (1) using highly reactive initiators containing N-heterocyclic carbenes as nonlabile ligands leads to well-defined polymers while cis-3,4-bis(hydroxymethyl)cyclobutene (2) was reluctant to polymerize under the same conditions. Kinetic studies were performed to assess a number of critical reaction parameters: initiator structure, solvent, and temperature. The results demonstrate that Grubbs’ second- and third-generation catalysts are the best initiators to prepare well-defined 1,4-polybutadienes containing simultaneously free and protected hydroxyl side groups with predictable molecular weights (up to 40 000 g mol–1) and narrow molecular weight distributions. Besides, low values of kp/ki (the ratio of the rate constant of propagation to the rate constant of initiation) were found for the ROMP of monomer 1 with Grubbs’ second-generation catalyst in chloroform or THF as the solvent, demonstrating a living process. The so-obtained polymers having hydroxyl side groups are an ideal platform to prepare original well-defined graft copolymers through the grafting-from strategy.
https://hal-univ-lemans.archives-ouvertes.fr/hal-01905398
Contributeur : Laurent Fontaine Connectez-vous pour contacter le contributeur
Soumis le : jeudi 25 octobre 2018 - 17:11:55
Dernière modification le : mardi 14 décembre 2021 - 10:26:03
Contributeur : Laurent Fontaine Connectez-vous pour contacter le contributeur
Soumis le : jeudi 25 octobre 2018 - 17:11:55
Dernière modification le : mardi 14 décembre 2021 - 10:26:03