From glycidyl carbonate to hydroxyurethane sidegroups in alternating fluorinated copolymers

Roukaya Hamiye (1) , A. Alaaeddine (2) , M. Awada (1) , Benjamin Campagne (2) , Sylvain Caillol (2) , Sophie M. Guillaume (1) , Bruno Ameduri (2) , Jean-François Carpentier (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

Fluoropolymers bearing five-membered cyclocarbonate pendant groups were synthesized by radical coor ter-polymerization of chlorotrifluoroethylene (CTFE) with various vinyl ethers [glycerol carbonate vinyl ether (GCVE), ethyl vinyl ether (EVE) and 2-chloroethyl vinyl ether (CEVE)] in good yields. Poly[(CTFE-alt- EVE)-co-(CTFE-alt-GCVE)] and poly[(CTFE-alt-CEVE)-co-(CTFE-alt-GCVE)] terpolymers feature higher molecular weights than poly(CTFE-alt-GCVE) copolymers. Then, the first examples of fluorinated polymers bearing hydroxyurethane moieties (PFHUs) were prepared by the chemoselective reaction of the pendant cyclocarbonates with isopropylamine, leading to primary and secondary hydroxyl dangling groups. The chemical structure of these PFHUs was confirmed by FTIR analysis and 1D (1H, 13C, 135DEPT/ APT) and 2D (COSY, HMQC) NMR spectroscopies. Size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and thermogravimetric (TGA) analyses of the PFHUs revealed a higher molecular weight and a decrease in the glass transition and decomposition temperatures, as compared to the parent cyclocarbonate polymers.

Mots clés: alternating copolymers; cyclocarbonate; fluorinated urethanes; glycidyl carbonate; hydroxyurethane; chlorotrifluoroethylene; fluoropolymers

Domaines: Polymères

Roukaya Hamiye, A. Alaaeddine, M. Awada, Benjamin Campagne, Sylvain Caillol, et al.. From glycidyl carbonate to hydroxyurethane sidegroups in alternating fluorinated copolymers. Polymer Chemistry, 2014, 5 (17), pp.5089-5099. ⟨10.1039/c4py00547c⟩. ⟨hal-01053918⟩