Synthesis and ionic transport of sulfonated ring-opened polynorbornene based copolymers

• Published in: Polymer (Guilford) Vol. 52; no. 19; pp. 4208 - 4220
• Main Authors: Santiago, Arlette A., Vargas, Joel, Cruz-Gómez, Javier, Tlenkopatchev, Mikhail A., Gaviño, Rubén, López-González, Mar, Riande, Evaristo
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01.09.2011; Elsevier
• Subjects: Applied sciences; Block copolymers; Catalysts; cation exchange; composite polymers; Copolymerization; Copolymers; electrochemistry; electrolytes; Electrolytic cells; Exact sciences and technology; Ionic transport; ions; Membranes; molecular weight; Monomer reactivity; Monomers; Organic polymers; Physicochemistry of polymers; polymerization; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; protons; ruthenium; Sodium; Sulfonated polynorbornene; Monomer reactivity; Ionic transport; Sulfonated polynorbornene; Fluorine containing copolymer; Norbornene derivative copolymer; Nyquist diagram; Polymer solid electrolyte; Etherification; Hydrogenation; Bode diagram; Sulfonate copolymer; Sulfonate; Imide; Proton conductivity; Unsaturated copolymer; Chloro complex; Norbornene copolymer; Rhodium complex; Electrical properties; Mechanical properties; Electromotive force; Surface topography; Tricyclic compound; Experimental study; Complex catalyst copolymerization; Reactivity ratio; Saturated copolymer; Random copolymer; Chemical modification; Cation exchange capacity; Metathesis polymerization; Preparation; Cation exchange membrane; Phenols; Ring opening copolymerization; Block copolymer
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2011.07.030

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 1a 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. [Display omitted]