Original Fluorinated Copolymers Achieved by Both Azide/Alkyne “Click” Reaction and Hay Coupling from Tetrafluoroethylene Telomers

Aurelien Soules (1) , Bruno Ameduri (1) , Bernard Boutevin (1) , Gérard Calleja (1)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

The synthesis and characterization of an original class of linear poly(alkyl aryl) ethers containing 1,2,3-triazolyl and fluorinated moieties based on oligo(tetrafluoroethylene) telomer are presented. These polymers were prepared, from R,ω-dipropargyl ether bisphenol AF and 1,10-diazido-1H,1H,2H,2H,9H,9H, 10H,10H-perfluorodecane, in 62 % overall yields via the azide/alkyne “click” reaction and/or oxidative coupling of acetylenes (Hay reaction). The latter reactant was produced from the ethylene end-capping of oligo- (tetrafluoroethylene) followed by a nucleophilic substitution with sodium azide. A simple tuning of the reaction conditions allowed us to direct the originally favored “click” reaction toward a competitive homocoupling of the terminal alkynes, thus leading to copolymers with drastically different structures, as evidenced by size exclusion chromatography, DSC, Raman, and UV-vis spectroscopy. Hence, original poly(alkyl aryl) ether copolymers with a high thermal stability (higher than 300 C) that exhibit alternating statistic or block microstructures were obtained.

Mots clés: Fluorinated Copolymers; Azide/Alkyne “Click”; Hay Coupling; Tetrafluoroethylene; Telomers; thermal properties; Raman spectroscopy

Domaines: Polymères

Aurelien Soules, Bruno Ameduri, Bernard Boutevin, Gérard Calleja. Original Fluorinated Copolymers Achieved by Both Azide/Alkyne “Click” Reaction and Hay Coupling from Tetrafluoroethylene Telomers. Macromolecules, 2010, 43, pp.4489-4499. ⟨10.1021/ma100634q⟩. ⟨hal-00477621⟩