Journal
POLYMER
Volume 52, Issue 19, Pages 4208-4220Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.polymer.2011.07.030
Keywords
Sulfonated polynorbornene; Ionic transport; Monomer reactivity
Categories
Funding
- National Council for Science and Technology of Mexico (CONACYT)
- CONACYT-SEMARNAT
- ICyTDF [23432, 4312]
- CICYT [MAT2008-06725-C03-01]
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The N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide (1a) and N-phenyl-exo-endo-norbornene-5,6-dicarboximide (1b) monomers were synthesized and copolymerized via ring opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II). Experiments, at distinct monomer molar ratios, were carried out using catalyst I in order to determine the copolymerization reactivity constants by applying the Mayo-Lewis and Fineman-Ross methods. Moreover, both catalysts were used to produce random and block high molecular weight copolymers of 1a with 1b and la with norbornene (NB) which were further hydrogenated using a Wilkinson's catalyst. Then, the saturated copolymers underwent a nucleophilic aromatic substitution by reacting with sodium 4-hydroxybenzenesulfonate dihydrate to generate new polynorbornene ionomers bearing fluorinated pendant benzenesulfonate groups. A thorough study on the electrochemical characteristics involving electromotive forces of concentration cells and proton conductivity of cation-exchange membranes based on a block copolymer of norbornene dicarboximides containing structural units with phenyl and fluorinated pendant benzenesulfonate moieties is reported. The study of electromotive forces (emf)of concentration cells with the sulfonated membrane of copolymer 8 separating electrolyte solutions of different concentration indicate that the membranes exhibit high permselectivity to protons and sodium ions at moderately low concentrations. In principle, these results suggest that the membranes can be considered candidates for ionic separation applications. (C) 2011 Elsevier Ltd. All rights reserved.
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