A series of 12-, 13-, and 14-membered crown ether rings bearing polymerisable side-chains has been synthesised. The crown ethers were attached to a methacrylate or acrylate polymerisable group either via a short link (Ring-CH(_2)-O-Polymer) or via a spacer group. Both hydrocarbon and ethylene oxide spacer groups were used, giving structures of the form (Ring-CH(_2)-O-(CH(_2))(_6)-O-Polymer) and (Ring-CH(_2)-O-((CH(_2)CH(_2))(_2)O)-Polymer). The ethylene oxide chain can potentially bind to a Li(^+) dopant ion. The relative Li(+) binding affinity of 12-, 13-, and 14-membered mono- and disubstituted crown ethers has been assessed by variable temperature (^13)c and (^7)Li NMR. The crown ether bearing monomers were polymerised using standard free-radical polymerisation methods to yield amorphous materials whose glass transition temperature (T(_g)) was controlled principally by the nature of the spacer group. On doping with lithium triflate (LiCF(_3)SO(_3)), the polymers exhibit high ionic conductivity. The conductivity was primarily dependent on polymer T(_g), but was also found to be higher for 12-crown-4 based systems than for 13-crown-4 and 14-crown-4 based analogues. This behaviour was consistent with the results of the NMR studies, which showed that Li(^+) exchange occurs more readily between 12-crown-4 rings than 13- or 14-crown-4 rings. The NMR studies also showed that 12-crown-4 systems have a higher tendency to form 2:1 (ring : Li(^+)) complexes. Within a polymer matrix, the presence of 2:1 complexes allows Li(^+) migration via an association-disassociation mechanism, avoiding the high energy intermediate state of a free or weakly bound Li(^+) ion. The greater encapsulation provided by 2:1 complexation may also aid in ion pair separation.

Cette thèse s'intéresse au développement de procédés monotopes (en une seule étape) permettant la synthèse accélérée de polymères conducteurs ioniques.Une étude bibliographique sur les poly(liquides ioniques) à base 1,2,3-triazolium (TPILs) a démontré leurs richesses structurale et fonctionnelle inégalées. Leur synthèse requière cependant plusieurs étapes nécessitant l'emploi de catalyseurs, de solvants et d'agents de polymérisation.Une première partie est consacrée au développement d'une voie de synthèse accélérée permettant d'accéder en une seule étape, sans solvant, ni catalyseur à des TPILs de structures variées. Il est en effet aisément possible de moduler les structures chimiques de l'espaceur, du contre-anion et du substituant en position N-3 du groupe 1,2,3-triazolium à partir d'un large choix de monomères a-azoture-?-alcyne et d'agents alkylants.Une seconde partie est consacrée à l'extension de cette voie de synthèse originale à l'élaboration d'une série de réseaux conducteurs ioniques, démontrant ainsi la souplesse du procédé et l'immense possibilité de variation structurale. Ces réseaux possèdent les propriétés uniques des matériaux vitrimères sur la base d'échanges dynamiques des points de réticulation par des réactions de transalkylation des liaisons C-N sous contrainte et température. Ils peuvent ainsi être remis en forme et recyclés sans pertes majeures de leurs propriétés et constituent donc le premier exemple de vitrimère fonctionnel. L'ensemble de ces matériaux de par leurs propriétés ainsi que leur rapidité et leur facilité de synthèse constituent donc une avancée majeure dans le domaine des polymères conducteurs ioniques et leurs applications / This PhD thesis tackles the development of monotopic (or single step) processes enabling the accelerated synthesis of ion conducting polymer materials. A bibliographic study on 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) have demonstrated their unequaled structural and functional richness. However, their syntheses require several synthetic steps and the use of catalysts, solvents and polymerization mediators.A first part is devoted to the development of an accelerated synthetic approach enabling in a single step to access TPILs with broad structural variety without solvent nor catalyst. Indeed the chemical structure of the spacer, the counter-anion and the N-3 substituent of the 1,2,3-triazolium group can be readily tuned from a broad library of a-azide-?-alkyne monomers and alkylating agents.A second part is devoted to the extension of this original synthetic approach to the formation of a series of ion conducting polymer networks, thus demonstrating the flexibility of the process and the broad capacity in structural design. These networks possess the unique properties of vitrimer materials based on dynamic exchanges of the cross-linking points by transalkylation reactions of C-N bonds under strain and temperature. They can thus be reshaped and recycled without significant loss of their properties, which constitute the first example of functional vitrimer.The properties of these materials, as well as the rapidity, the versatility and the flexibility of their syntheses constitute a major breakthrough in the field of ion conducting polymer materials and their applications