Cationic photopolymerization of multifunctional epoxides is very useful for efficient cure at room temperature and has been widely used in coatings and adhesives. Despite excellent properties of the final cured polymers, cationic photopolymerizations of epoxides have seen limited application due to slow reactions (relative to acrylates) and brittleness associated with a highly crosslinked, rigid network. To address these issues, two reaction systems were studied in this thesis: photoinitiated cationic copolymerizations of a cycloaliphatic diepoxide with epoxidized elastomers and acrylate/epoxide hybrid photopolymerizations. Oligomer/monomer structures, viscosity, compositions, and photoinitiator system were hypothesized to play important roles in controlling photopolymerizations of the epoxide-based mixtures. A fundamental understanding of the interplay between these variables for the chosen systems will provide comprehensive guidelines for the future development of photopolymerization systems comparable to the epoxide-based mixtures in this research. For diepoxide/oligomer mixtures, the observed overall enhancement in polymerization rate and ultimate conversion of the cycloaliphatic diepoxide was attributed to the activated monomer mechanism associated with hydroxyl terminal groups in the epoxidized oligomers. This enhancement increased with increasing oligomer content. The mixture viscosity influenced the initial reactivity of the diepoxide for oligomer content above 50 wt.%. Real-time consumption of internal epoxides in the oligomers was successfully determined using Raman spectroscopy. Initial reactivity and ultimate conversion of the internal epoxides decreased with increasing the diepoxide content. This trend was more pronounced for the oligomer containing low internal epoxide content. These results indicate that the reactivity of the hydroxyl groups is higher toward cationic active centers of the diepoxide than those of the internal epoxides in the oligomers. These conclusions are consistent with physical property results. The enhanced fracture toughness and impact resistance were attributed to multimodal network chain-length distribution of copolymers containing the oligomer content between 70% and 80%. For acrylate/epoxide hybrid mixtures, diacrylate oligomers significantly suppressed reactivities of cycloaliphatic mono/diepoxides, which was attributed to high mixture viscosity and highly crosslinked acrylate network. In this case, the dual photoinitiator system did not favor the epoxide reaction. Depending on the monovinyl acrylate secondary functionalities, enhanced reactivity and ultimate conversion of the diepoxide were attributed to a combined effect of a reduced viscosity and the radical-promoted cationic polymerization associated with the dual photoinitiator. The retarded and inhibited diepoxide reactivities with ether and urethane secondary groups were attributed to solvation and nucleophilicity/basicity effects, respectively. The influence of the diepoxide on the acrylate reactivity was attributed to dilution and polarity effects. In this case, high concentration of the free-radical photoinitiator is required for the dual photoinitiator system. Physical properties of hybrid polymers also varied with acrylate structures and monomer composition. Dynamic modulation methods were proposed to enhance the diepoxide reactivity and final properties in the presence of urethane acrylates.

L’avènement des lasers impulsionnels nanosecondes à femtosecondes a permis un développement rapide de techniques permettant de sonder et/ou de transformer les matériaux à l’échelle locale par des processus d’absorption non linéaire. Ce saut technologique a vu l’émergence de nombreuses applications associées au phénomène de confinement spatial. La stéréolithographie 3D par photopolymérisation biphotonique constitue un exemple typique d’application à forte valeur ajoutée qui offre de prometteuses perspectives en terme d’écriture à l’échelle nanométrique. Un enjeu fondamental constitue alors l’élaboration de nouveaux photoamorceurs très réactifs et activables à deux photons. Dans ce contexte, ce manuscrit présente une étude photophysique et photochimique de deux séries de photoamorceurs biphotoniques ‘Donneur/Accepteur’ intégrants des stilbènes comme relais électroniques avec pré-organisation dans des structures bichromophores. Les processus primaires photoinduits, les mécanismes de photoamorçage, la photoréactivité à l’echelle locale sont décrits et étudiés méthodiquement. Enfin, le potentiel appliqué de cette nouvelle génération de photoamorceurs est mis en évidence en microfabrication multiphotonique à travers l’élaboration de structure 3D à l’échelle µm. / The advent of pulsed laser technologies has promoted the rapid growth of new emerging research domains which aim at probing and/or transforming materials at local scale using non linear absorption processes. A large range of applications takes benefit of the inherent spatial containment observed in non linear absorption processes so as to control photoreactions at nm-scale. The field of multiphoton fabrication (or stereolithography) addresses this fundamental issue and has developed rapidly so that it is no longer a rapid prototyping technology but a real manufacturing technique that is commercially available. The development of multiphoton stereolitography also requires highly reactive two-photon activable (2PA) initiators whose design and elaboration are the subject of considerable molecular engineering research. In this context, the present manuscript describes the photophysical and photochemical properties of two series of 2PA initiators. Such novel D--A structures have be designed by associating distinctive Donor and Acceptor groups into stilbene arms used as ‘electron relay’ and organized into a (multi)branched architecture. The photoinduced primary processes, the global photoinitiating mechanisms as well as the photoreactivity are described methodically. We finally demonstrate the applied potential of this new type of two-photon initiators in multiphoton stereolitography.

Ceria (cerium oxide) nanomaterials, or nanoceria, have commercial catalysis and energy storage applications. The cerium atoms on the surface of nanoceria can store or release oxygen, cycling between Ce3+ and Ce4+, and can therefore act as a therapeutic to relieve oxidative stress within living systems. Nanoceria dissolution is present in acidic environments in vivo. In order to accurately define the fate of nanoceria in vivo, nanoceria dissolution or stabilization is observed in vitro using acidic aqueous environments. Nanoceria stabilization is a known problem even during its synthesis; in fact, a carboxylic acid, citric acid, is used in many synthesis protocols. Citric acid adsorbs onto nanoceria surfaces, capping particle formation and creating stable dispersions with extended shelf lives. Nanoceria was shown to agglomerate in the presence of some carboxylic acids over a time scale of up to 30 weeks, and degraded in others, at pH 4.5 (representing that of phagolysosomes). Sixteen carboxylic acids were tested: citric, glutaric, tricarballylic, α-hydroxybutyric, β-hydroxybutyric, adipic, malic, acetic, pimelic, succinic, lactic, tartronic, isocitric, tartaric, dihydroxymalonic, and glyceric acid. Each acid was introduced as 0.11 M, into pH 4.5 iso-osmotic solutions. Controls such as ammonium nitrate, sodium nitrate, and water were also tested to assess their effects on nanoceria dissolution and stabilization. To further test stability, nanoceria suspensions were subject to light and dark milieu, simulating plant environments and biological systems, respectively. Light induced nanoceria agglomeration in some, but not all ligands, and is likely to be a result of UV irradiation. Light initiates free radicals generated from the ceria nanoparticles. Some of the ligands completely dissolved the nanoceria when exposed to light. Citric and malic acids form coordination complexes with cerium on the surface of the ceria nanoparticle that can inhibit agglomeration. This approach identifies key functional groups required to prevent nanoceria agglomeration. The impact of each ligand on nanoceria was analyzed and will ultimately describe the fate of nanoceria in vivo. In addition, simulated biological fluid (SBF) exposure can change nanoceria’s surface properties and biological activity. The citrate-coated nanoceria physicochemical properties such as size, morphology, crystallinity, surface elemental composition, and charge were determined before and after exposure to simulated lung, gastric, and intestinal fluids. SBF exposure resulted in either loss or overcoating of nanoceria’s surface citrate by some of the SBF components, greater nanoceria agglomeration, and small changes in the zeta potential. Nanocomposites are comprised of a polymer matrix embedded with nanoparticles. These nanoparticles can alter material and optical properties of the polymer. SR-399 (dipentaerythritol pentaacrylate) is a fast cure, low skin irritant monomer that contains five carbon-carbon double bonds (C=C). It is a hard, flexible polymer, and also resistant to abrasion. It can be used as a sealant, binder, coating, and as a paint additive. In this case, metal oxide nanoparticles were added to the monomer prior to polymerization. Titania nanoparticles are known to absorb UV light due to their photocatalytic nature. Titania nanoparticles were chosen due to their high stability, non-toxicity, and are relatively quick, easy, and inexpensive to manufacture. Channels in thin monomer films were created using a ferrofluid manipulated by magnetic fields. The mechanical properties of a microfluidic device by rapid photopolymerization is dependent on the crosslinking gradient observed throughout the depth of the film. Quantitative information regarding the degree of polymerization of thin film polymers polymerized by free radical polymerization through the application of UV light is crucial to estimate material properties. In general, less cure leads to more flexibility, and more cure leads to brittleness. The objective was to quantify the degree of polymerization to approximate the C=C concentration and directly relate it to the mechanical properties of the polymer. Polymerization of C=C groups was conducted using a photoinitiator and an UV light source from one surface of a thin film of a multifunctional monomer. The C=C fraction in the film was found to vary with film depth and UV light intensity. The extents of conversion and crosslinking estimates were compared to local mechanical moduli and optical properties. A mathematical model linking the mechanical properties to the degree of polymerization, C=C composition, as a function of film depth and light intensity was then developed. For a given amount of light energy, one can predict the hardness and modulus of elasticity. The correlation between the photopolymerization and the mechanical properties can be used to optimize the mechanical properties of thin films within the manufacturing and energy constraints, and should be scalable to other multifunctional monomer systems.