Fluorinated polymers of substantial high performance such as perfluorocyclobutyl (PFCB) and fluorinated aryl vinyl ether (FAVE) polymers can readily be synthesized by thermal [2+2] cyclopolymerization as a melt or by classical polycondensation. These fluoropolymers naturally possess high thermal and chemical resistance, low conductivity properties, and other mechanical properties. In this work, a method using 0th order kinetics is proposed and thermal degradation studies were conducted on six different aromatic ether-based polymers to gauge trends in activation energy barrier and differences in thermal stability by 0th order degradation kinetics. The activation barrier (E_a) obtained can give accurate insight into the stability of the polymer based only on structure for external applications. Activation energies ranging from 17 to 41 kcal/mol were obtained for the various polymers. Overall, this study provides an established method using TGA for thermal stability studies through 0th order kinetics that can be potentially used for future lab applications.

Ce manuscrit de thèse décrit la synthèse et la caractérisation d'ionomères conducteurs protoniques pour une application en tant que membrane pour pile à combustible. La stratégie adoptée pour la synthèse de ces polymères repose sur la polycondensation directe de monomères fonctionnels. Pour ce faire, et dans le cadre d'un travail important de chimie organique, la synthèse de trois monomères sulfonés ainsi que de trois monomères phosphonés a été réalisée. Différents polymères perfluorés (polyperfluorocyclobutane (PFCB) et polyaryléthers (PAE) (Polyétheréther cétone (PEEK) et Polysulfone (PS), ont été obtenus par polycondensation directe de ces monomères fonctionnalisés. Il a été possible de synthétiser des copolymères séquencés (à blocs) et comportant un ou deux types de fonctions conductrices protoniques. Afin d'établir d'éventuelles relations structure-propriété pour ces polymères et l'influence du solvant dans la morphologie de la membrane, une étude de la morphologie a été réalisée à partir de plusieurs séries de polymères PAE et leurs analogues « statistiques ». Les valeurs de conductivité des polymères à blocs sont, en général, supérieures à celles de leurs analogues « statistiques ». Un PAE obtenu est particulièrement intéressant, il possède à la fois une conductivité (216 mS.cm 1) nettement supérieure au Nafion® et un gonflement plus faible. Le polymère perfluoré (PFCB) obtenu est également très prometteur : la conductivité enregistrée pour ce ionomères est de 138 mS/cm. Ce travail de thèse est, à notre connaissance, le premier exemple de synthèse d'un PFCB sulfoné par polymérisation directe d'un monomère fonctionnel mais il constitue également le premier exemple de synthèse de poly(aryléther)s à blocs sulfonés / phosphonés par copolymérisation directe de deux types de monomères fonctionnels / This thesis describes the synthesis and characterization of proton conducting polymers for application as membrane for fuel cells (PEMFC). The approach for the synthesis of polymers consists in creating polymers from direct polycondensation of functional monomers, in order to better control their final IEC. Three sulphonated monomers and three phosphonated monomers have been first synthetized. Different types of polyarylethers (one of them is both sulphonated and phosphonated) and one perfluorinated polymer (PFCB) have been synthetised by direct polycondensation of functional monomers. In order to explain the influence of the solvent in the final morphology of the membrane, and the relation between its structure and properties, one morphological study has been realized to the obtained polymers but also to their analogues “statistical” polymers. In general, the blocks polymers obtained the highest values of conductivity. One polyarylether seems particularly interesting, because its conductivity value is much higher than Nafion®’s, and has a smaller swelling value. The perfluorinated polymer has also an interesting conductivity value (138 mS/cm). This thesis work is, to the best of our knowledge, the first example of the synthesis of a sulphonated PFCB obtained by direct polycondensation but also the first example of synthesis of a both sulfonated/phosphonated polyarylethers by direct copolymerisation of to types of functional monomers

The strength and durability of proton exchange membranes for use in fuel cells has received much attention recently due to the increased push for sustainable alternatives to the internal combustion engine. To be viable, these alternatives must have comparable lifetimes and power outputs to the internal combustion engines they replace. Chemical degradation was once viewed as the most common culprit of early fuel cell failure, but as membranes and catalysts improved, mechanical failure became an important factor. As a result, fundamental research on the mechanically-induced failure mechanisms of fuel cell membranes, coupled with development and processing of less expensive membranes, has become an important topic. The use of the blister test geometry, along with digital image correlation of the deformed shape, creates a self-contained analysis tool useful for measuring the biaxial strength of membranes. In this work, blister tests are used to measure biaxial stress and strain for fuel cell membranes subjected to ramped pressure loading to form stress-strain curves that indicate the onset of yielding under biaxial stress conditions. Stress-life curves are developed experimentally for Gore-Selec? series 57 members using data collected under constant pressure conditions. These results are used to predict blister failure under ramped and fatigue loadings. A newly implemented hydrocarbon membrane system is evaluated with constant-pressure-to-leak blister testing. Improved strength following an isothermal hold at 100°C (pretreatment) is shown to occur. Ramped pressure testing indicates that the material after the pretreatment is stiffer and has a higher yield stress than the material before treatment. Morphological and constitutive characterization indicated differences in the materials that are consistent with the improved performance. / Master of Science

3-Diazonium- 4-(trifluorovinyloxy) - perfluorobutanesulfonyl benzenesulfonimide zwitterionic monomer (see figure 1) is proposed to be polymerized and further act as a new electrolyte for Polymer exchange membrane fuel cells (PEMFCs). One reason is that, the aromatic trifluorovinyl aryl ether (TFVE) group can easily be homopolymerized to aromatic perfluorocyclobutane (PFCB) polymer. Furthermore, the diazonium moiety in the monomer is expected to covalently attach the electrolyte to the carbon electrodes support. The perfluoroalkyl(aryl) sulfonimide (PFSI) pendant provides good chemical and mechanical stability as well as better proton conductivity. Several multi-step synthetic schemes are designed to obtain such monomer from perfluoroalkyl(aryl) sulfonimide (PFSI). Among them, the purified coupling product 4-OCF2CF2Br-3-NO2-PhSO2(M) SO2C4F9 from the first approach was successfully completed. The next stages of the work will involve dehalogenation, reduction, and diazotization to achieve the targeting monomer. All the intermediates were characterized by 1H and 19F NMR and FT-IR spectroscopy.