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Recherche transversale
(titres de publication, de périodique et noms de colloque inclus)
2013-09-12 - Article/Dans un journal avec peer-review - Anglais - 12 page(s)

Olvera Lilian I., Guzmán-Gutiérrez Maria T., Zolotukhin M. G., Fomine Sergei, Cárdenas Jorge, Ruiz-Trevino Fransico A., Villers Didier , Ezquerra Tiberio A., Prokhorov Evgen, "Novel High Molecular Weight Aromatic Fluorinated Polymers from One-Pot, Metal-Free Step Polymerizations" in Macromolecules, 46, 18, 7245-7256, 10.1021/ma401306s

  • Edition : American Chemical Society, Washington (DC)
  • Codes CREF : Chimie macromoléculaire (DI1315)
  • Unités de recherche UMONS : Laboratoire Interfaces et Fluides complexes (S885)
  • Instituts UMONS : Institut de Recherche en Science et Ingénierie des Matériaux (Matériaux)
  • Centres UMONS : Centre d’Innovation et de Recherche en Matériaux Polymères (CIRMAP)
Texte intégral :

Abstract(s) :

(Anglais) A novel series of linear, high-molecular-weight polymers and copolymers was synthesized by one-pot, metal-free superacid-catalyzed reaction of trifluoromethylalkyl (1a–1c) and trifluoromethylaryl (1d–1h) ketones with the linear, nonactivated, multiring aromatic hydrocarbons biphenyl (A), p-terphenyl (B), and p-quaterphenyl (C). The polymerizations were performed at room temperature in the Brønsted superacid trifluoromethanesulfonic acid (CF3SO3H, TFSA) and in a mixture of TFSA with methylene chloride. Polymerizations of trifluoromethyl ketones (1c, 1f–1h) bearing functional groups gave polymers with reactive lateral groups such as bromomethyl, 4-(N,N-dimethylamino)phenyl-, 3-sulfophenyl-, and 2,3,4,5,6-pentafluorophenyl. The polymers obtained were soluble in most common organic solvents and flexible transparent films could be cast from the solutions. 1H and 13C NMR analyses of the polymers synthesized revealed their linear structure with para-substitution in the phenylene fragments of the main chain. The molecular weights (Mw) of the polymers based on trifluoromethylalkyl ketones and aromatic are very high and reach 1 000 000, while the molecular weights of the polymers based on trifluoromethylaryl ketones and aromatic ranged from 30 000 to 300 000 g/mol. The polydispersity of the polymers is generally less than 2. The polymers also possess high thermostability. Mechanistic aspects of polymerization mechanism have been discussed, and a new approach for monomer design has been proposed.