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Article Dans Une Revue Macromolecules Année : 2015

1,4-Polybutadienes with Pendant Hydroxyl Functionalities by ROMP: Synthetic and Mechanistic Insights

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Résumé

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.
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Dates et versions

hal-01905398 , version 1 (25-10-2018)

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Flavien Leroux, Sagrario Pascual, V. Montembault, Laurent Fontaine. 1,4-Polybutadienes with Pendant Hydroxyl Functionalities by ROMP: Synthetic and Mechanistic Insights. Macromolecules, 2015, 48 (12), pp.3843 - 3852. ⟨10.1021/acs.macromol.5b00696⟩. ⟨hal-01905398⟩
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