Le travail de thèse porte sur la synthèse de nouveaux monomères photopolymérisables issus de la biomasse, l’étude de leur photopolymérisation et la caractérisation des matériaux qui en résultent. Les monomères formulés ont été testés dans un procédé d’impression de caractères Braille.Les monomères ont été élaborés en deux étapes en utilisant un chemin réactionnel simple, économique et respectueux de l’environnement. La première étape a consisté à faire réagir des dérivés du glycérol (carbonate de glycérol ou glycidol) avec des acides gras. Dans un deuxième temps, les [alpha]-monoglycérides obtenus ont été fonctionnalisés en vue de les rendre photopolymérisables. Les différents monomères obtenus porteurs de fonctions (méth)acrylate et/ou époxy ont été photopolymérisés en quelques secondes en présence d’un photoamorceur. Les cinétiques de photopolymérisation ont été suivies par spectrométrie IR-TF en mode ATR et différents paramètres tels que la quantité et la nature du photoamorceur, l’intensité d’irradiation et la température ont été optimisés. Les différents matériaux obtenus après photoréticulation ont été caractérisés afin de mettre en évidence leurs principales physico-chimiques. Des relations structure – propriétés ont ainsi été établies.Enfin, une formulation photopolymérisable présentant une viscosité compatible avec le procédé d’impression Braille a été élaborée par ajout de silice nanométrique. Les points Braille obtenus présentent des caractéristiques proches de ceux réalisés par le partenaire industriel. / The work of the PhD deals with the synthesis of polymerizable monomers derived from biomass, the study of their photopolymerization and the characterization of the resulting materials. The formulated monomers were tested in a printing method of Braille characters.The monomers were prepared in a two-steps reaction that is simple, economic and environmentally friendly. The first step comprised a reaction between glycerol derivatives (glycerol carbonate or glycidol) and fatty acids. In the second step, the obtained [alpha]-monoglycerides were functionalized to obtain photopolymerizable monomers. The different obtained monomers that bear (meth)acrylate and/or epoxy groups were photopolymerized in a few seconds in the presence of photoinitiator.The photopolymerization kinetics were followed by FT-IR spectroscopy in ATR mode, and various parameters such as the amount and the nature of the photoinitiator, the irradiation intensity and the temperature were optimized. The different photocured materials were characterized to highlight their main physicochemical properties. Structure-properties relations were then established.Finally, a photopolymerizable formulation having a viscosity compatible with the printing process of Braille characters was developed by adding nanometric silice. The obtained Braille characters exhibited features close those carried out by the industrial partner.

Polyethylene (PE) resins being non-polar in nature and having a high degree of crystallinity have limited miscibility and compatibility when blended with polar polymers. The miscibility and compatibility of these blends are generally worsened when they are prepared by direct injection moulding without a precompounding process. Such situations are commonly encountered in particular by polymer converters when blending colour and/or additive concentrates, commonly known as masterbatches. Typically, masterbatches are mixtures containing high loading of pigments and/or additives predispersed in a suitable solid vehicle (commonly known as carrier) such as a polyethylene resin. These masterbatches are usually used for the colouration of a wide range of polymers and the carrier used must therefore be compatible with these matrix (host) polymers. The preliminary stage of this study involved the investigation of the properties of blends based on high density polyethylene (HDPE) and a range of engineering thermoplastics (ABS, PC, PBT, PA6), prepared by injection moulding. Five different types of compatibilisers namely, ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-glycidyl methacrylate (E-GMA) copolymer, ethylene-methyl acrylateglycidyl methacrylate (E-MA-GMA) terpolymer and maleic anhydride grafted HDPE (HDPE-g-MAH) copolymer were evaluated with respect to their efficiencies in compatibilising HDPE with the four engineering polymers. The pre-compounded HDPE/compatibiliser binary blends at 2 different blend ratios (1:1 and 3:1) were added at 15 wt% concentration to each engineering thermoplastics and test samples were produced directly by injection moulding. Results of mechanical testing and characterisation of the blends showed that glycidyl methacrylate compatibilisers, E-MA-GMA, in particular have the most universal compatibilising effectiveness for a range of engineering thermoplastics including ABS, PC, PBT, and PA6. Blends compatibilised with E-MA-GMA compatibiliser had the best notched impact performance irrespective of matrix polymer type. The presence of an acrylic ester (methyl acrylate) comonomer in E-MA-GMA resulted in increased polarity of the ii compatibiliser leading to improved miscibility with the polar matrix polymers demonstrated by fine blend morphologies, melting point depression and reduction in crystallinity of the HDPE dispersed phase. The second stage of this study involved the reactive modification of HDPE using a low molecular weight di-functional solid diglycidyl ether of bisphenol A (DGEBA) type epoxy resin compatibilised with HDPE-g-MAH in an attempt to improve its compatibility with ABS, PBT and PA6. The maleic anhydride moieties in HDPE-g-MAH served as reactive sites for anchoring the epoxy moieties while the HDPE backbone was miscible with the HDPE resin. An excessive amount of reactive groups resulted in the formation of crosslinked gels while the addition of EVA co-compatibiliser helped in the reduction of gel content and further improved the dispersion of the epoxy. The effectiveness of epoxy grafted HDPE (with and without EVA co-compatibiliser) in compatibilising ABS/HDPE, PBT/HDPE, and PA6/HDPE was investigated by injection moulding of 5 wt% functionalised HDPE with these matrix polymers into test bars for mechanical testing, and characterisation by differential scanning calorimtery (DSC) and optical microscopy. The reactively functionalised HDPE blends, improved the mechanical properties of ABS and PA6 blends especially with EVA as co-compatibiliser. However, the mechanical properties of PBT blends were unmodified by the functionalised HDPE which was believed to be due to end-capping of the PBT chain-ends by ungrafted epoxy resins.

Des glycopolymères greffés et dibloc, amphiphiles et photosensibles, à base de poly(acrylate d'o-nitrobenzyle) (PNBA) hydrophobe et photoclivable et de dextrane hydrophile ont été préparés avec succès en utilisant notammennt une réaction d'Huisgen (Cycloaddition Azoture-Alcyne catalysée par le Cuivre (I) - CuAAC chimie click). Dans un premier temps, la polymérisation de l'acrylate d'o-nitrobenzyle a été contrôlée avec succès grâce aux développements récents de la polymérisation radicalaire vivante par transfert d'un seul électron (SET-LRP). Nous avons alors obtenu un PNBA fonctionnalisé à son extrémitié par un brome. Ce brome a ensuite été substitué par un groupe azido. En parallèle, le dextrane a été modifié pour y introduire plusieurs fonctions alcyne (dextrane alcyne) ou une seule sur son extrémité réductrice (dextrane α-alcyne). Nous avons ensuite fait réagir ces dérivés de dextrane avec le PNBA-N3 pour obtenir respectivement les glycopolymères greffés et dibloc. Tous les glycopolymères ont été caractérisés par chromatographie d'exclusion stérique (SEC), Résonnance Magnétique Nucléaire 1H, 13C, 2D DOSY 1H et par spectrométrie FT-IR. Dans un deuxième temps, nous avons optimisé les conditions pour obtenir des nanoparticules peu disperses à partir des précédents glycopolymères. Dans certains cas, des nanoparticules ont également été obtenues en utilisant le dextrane alcyne et le PNBA-N3 dans un procédé d'émulsion/évaporation de solvant organique. La stabilité de toutes les nanoparticules vis-à-vis de solutions aqueuses de diverses forces ioniques ou d'un tensioactif compétitif a été étudiée. Enfin, l'effet de la lumière sur ces nanoparticules photosensibles a été mis en évidence à l'aide de la lampe UV. Plus précisément, nous avons pu suivre la destruction des nanoparticules par spectroscopie de fluorescence et diffusion de lumière dynamique en encapsulant le Rouge du Nil (sonde fluorescente) au sein de ces particules / Photosensitive grafted and diblock amphiphilic glycopolymers based on hydrophobic photosensitive poly(o-nitrobenzyl acrylate) (PNBA) and hydrophilic dextran were successfully prepared via grafting onto techniques through a Huisgen-type Copper(I) catalyzed Azide-Alkyne Cycloaddition (CuAAC click chemistry). Firstly, recent developments in the single-electron transfer–living radical polymerization (SET–LRP) provided us an access to control the o-nitrobenzyl acrylate polymerization and we obtained PNBA with bromide end function. Then, this bromide end function was replaced by azido (N3) group. In a parallel way, we modified dextran by introducing several alkyne groups all long the polysaccharide chain (alkynated dextran) or only one group at the reducing end-chain (α-alkyne dextran). In the second step, alkynated dextran and α-alkyne dextran were reacted with PNBA-N3 by CuAAC to obtain grafted or diblock glycopolymers. All glycopolymers were characterized by Size Exclusion Chromatography, 1H, 13C, 2D DOSY 1H NMR and FT-IR spectroscopy. Secondly, conditions to formulate nanoparticles from the previous glycopolymers were optimized. In some case, we also carried out an emulsion/evaporation process using dextran alkynated and PNBA-N3 to produce nanoparticles. Then, stability of nanoparticles were studied over rang of ionic strengths as well as stability in presence of a competitive surfactant. Finally, the effect of light on these photosensitive nanoparticles was studied using UV-lamp. More precisely, we loaded these nanoparticules by Nile Red fluorescent dye and followed thier destruction by using fluorescence spectroscopy and Dynamic Light Scattering

Ce travail de thèse décrit l'élaboration de copolymères amphiphiles obtenus par couplage de deux homopolymères. La synthèse des copolymères s'est effectuée en deux étapes. Dans un premier temps, des homopolymères de type poly(2-méthyl-2-oxazoline) (P(MOx)) et poly(acrylate de tert-butyle) (P(At-Bu)) ont été préparés par polymérisation par ouverture de cycle cationique (CROP) et par polymérisation radicalaire contrôlée de type RAFT ou ATRP, respectivement. Puis les copolymères amphiphiles diblocs ont finalement été obtenus par une réaction de couplage polymère-polymère de type cycloaddition de Huisgen. Une étude physico-chimique de ces copolymères dans l'eau a mis en évidence la présence d'agrégats qui présentent une morphologie sphérique, des tailles inférieures à 100 nm et des concentrations d'agrégation critique de l'ordre de 10-6 mol.L-1.Les connaissances acquises sur la synthèse et l'étude des copolymères à blocs amphiphiles ont également permis le développement de copolymères greffés amphiphiles poly(-caprolactone)-g-poly(2-méthyl-2-oxazoline) (PCL-g-P(MOx)), constitués d'un bloc hydrophobe PCL sur lequel des chaînes hydrophiles P(MOx) ont été greffées. L'étude du comportement de ces copolymères dans l'eau montre la formation d'agrégats avec des caractéristiques proches de celles obtenues pour les copolymères diblocs amphiphiles. Un autre point intéressant est que la P(MOx) permet de solubiliser la PCL dans l'eau.Ces deux études illustrent l'apport de la chimie macromoléculaire pour la préparation de structures amphiphiles parfaitement définies qui s'organisent en phase aqueuse en agrégats. Ces derniers pourraient notamment être utilisés dans le domaine biomédical. / This manuscript deals with the synthesis of amphiphilic diblock copolymers obtained by the coupling of both hydrophobic and hydrophilic homopolymers. The copolymers were achieved in two steps. On the one hand, homopolymers poly(2-methyl-2-oxazoline) P(MOx)s and poly(tert-butyl acrylate)s (P(At-Bu) were synthesized by cationic ring opening polymerization (CROP) and by Reversible Addition-Fragmentation Transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP), respectively. Finally, amphiphilic diblock copolymers were achieved by Huisgen's cycloaddition. Physical chemistry studies in water proved the formation of aggregates. The latter had a spherical morphology, sizes below 100 nm and critical aggregation concentration around 10-6 mol.L-1.Knowledge acquired on the synthesis and the study of amphiphilic block copolymers led to the development of poly(-caprolactone)-g-poly(2-methyl-2-oxazoline) (PCL-g-P(MOx)) amphiphilic graft copolymers, made of a hydrophobic PCL grafted with hydrophilic P(MOx) moieties. The study of aqueous solution of such copolymers showed the formation of aggregates with characteristics close from those obtained for the diblock copolymers. Another interesting point is that P(MOx) permitted the solubilization of PCL in water.The reported work illustrated the importance of macromolecular chemistry for the obtaining of amphiphilic copolymers with controlled molecular weight and narrow molar mass distributions which self-assemble in water. Such kind of materials could be used in the biomedical field.

Ce travail de thèse a porté sur le développement de revêtements organiques/inorganiques photopolymérisables superhydrophobes à partir de procédés d’élaboration simples associés à des produits commerciaux largement diffusés. Pour cela, des revêtements à matrice polyuréthane acrylate (PUA), intrinsèquement hydrophiles, incluant différents composés à base de silicium ont été élaborés par enduction ou pulvérisation. L’objectif a été d’apporter en surface des revêtements une structuration multi-échelle et une chimie à caractère hydrophobe nécessaires pour atteindre la superhydrophobie, c’est-à-dire un angle de contact avec l’eau supérieur à 150° et une hystérésis de mouillage inférieure à 10°. L’introduction de molécules de polysilsesquioxane polyédrique (POSS), présentant un ligand acrylate et sept ligands isobutyle, a apporté une nanostructuration et un comportement hydrophobe aux revêtements PUA à des concentrations très faibles (≤ 1% en masse.). Cependant, la rugosité apportée se révèle trop faible et cette stratégie ne peut aboutir à la superhydrophobie des revêtements. L’introduction de particules de silice pyrogénée, modifiées en surface par des chaînes polydiméthylsiloxane, a permis d’établir une structuration multi-échelle et une chimie à caractère hydrophobe à la surface des revêtements PUA, leur conférant ainsi la superhydrophobie. De plus, le procédé d’élaboration a joué un rôle majeur sur les modifications physico-chimiques de surface des revêtements : la superhydrophobie est obtenue à une concentration relativement élevée de 30 et 60% en masse de silice pyrogénée respectivement par pulvérisation et enduction. Afin de diminuer ces concentrations, la combinaison des deux stratégies précédentes, c’est-à-dire l’introduction simultanée de POSS et de silice pyrogénée, a été considérée. Ceci a permis d’exacerber le caractère hydrophobe des revêtements tout en préservant la rugosité établie par la silice pyrogénée. Cette approche a conduit à la diminution de la concentration de silice nécessaire pour obtenir la superhydrophobie dans le cas des revêtements élaborés par pulvérisation. / This work deals with the development of organic/inorganic superhydrophobic UV-curable coatings manufactured through simple processes and from commercially available products. To achieve this goal, a hydrophilic polyurethane acrylate matrix (PUA) was used, in which several silicon-based compounds were introduced. The coatings were deposited using either bar- or spray-coating. The main objective was to structure the surface thanks to a multiscale roughness, while bringing a hydrophobic character, two properties needed to obtain a superhydrophobic coating (defined by a water contact angle superior to 150° and a water contact angle hysteresis inferior to 10°). The introduction of polyhedral oligomeric silsesquioxane molecules (POSS), presenting one acrylate and seven isobutyl ligands, brought a nanostructuration and a hydrophobic behavior to PUA coatings, even at low concentrations (≤ 1%wt.). However, the roughness obtained was not sufficient to bring the superhydrophobicity to the coatings.The introduction of fumed silica particles, functionalized by PDMS chains, established multiscale roughness and hydrophobic behavior at the surface, leading to superhydrophobic coatings. Moreover, the process had a high influence on physico-chemical modifications at the coatings’surface: superhydrophobicity is obtained for a relatively high concentration of fumed silica, 30%wt. and 60%wt. respectively for spray and bar-coating. In order to decrease these concentrations, we tried the combination of the two previous strategies: introduction of POSS molecules and fumed silica particles. This path raised the hydrophobic behavior of the coatings while keeping intact the roughness brought by fumed silica particles. This approach allowed to decrease the silica concentration needed to obtain superhydrophobicity for spray-coated coatings.

The development of organic-inorganic hybrid materials is of great interest in thermoelectrics for its potential to combine the desirable characteristics of both classes of materials. Thermoelectric materials must combine low thermal conductivity with high electrical conductivity, but in most materials, thermal and electrical conductivity are closely related and positively correlated. By combining the low thermal conductivity, flexibility, facile processing, and low cost of organic components with the high electrical conductivity and stability of inorganic components, materials with beneficial thermoelectric properties may be realized. Here, we describe the synthesis and characterization of anthracene-containing organic-inorganic hybrid materials for thermoelectric purposes. Specifically, POSS-ANT was synthesized when aminopropylisobutyl-POSS was functionalized with a single anthracene unit via DCC-mediated amide formation. Acrylate-POSS was functionalized with multiple anthracene units in a Heck coupling reaction to synthesize System 1. System 2 was developed through a two-step synthetic process. In the first reaction, (3- acryloxypropyl)methyl dimethyoxy silane was functionalized with anthracene at the 9- position through a Heck coupling reaction. The second reaction was a base-catalyzed solgel process to form polymeric nanoparticles. Finally, System 3 was synthesized through a similar process to System 2, though polymers formed in the initial step. The System 3 precursor was to be developed through a potassium carbonate-catalyzed ether synthesis from 3-(bromopropyl)trimethoxysilane and 9-anthracene methanol, followed by a basecatalyzed sol-gel process to form nanoparticles. The precursor was never isolated because of premature polymerization during the precursor synthesis step, and polymeric nanoparticles were obtained for System 3 during the sol-gel process. These materials were characterized by TEM to reveal the nanostructures that formed upon evaporation from solution. Future work will focus on the characterization of thermoelectric parameters and incorporation into thermoelectric devices.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Thesis submitted in partial fulfillment of the requirements for the degree of Master of Science (Polymer Science) at University of Stellenbosch. / ENGLISH ABSTRACT: The preparation of poly(acrylonitrile/methyl acrylate) [poly(AN-co-MA)] copolymers and poly(AN-co-MA)/clay nanocomposites, via emulsion polymerization, their characterisation, and the relationships between their molecular structures and physical properties are described. The copolymer composition was varied, and the properties of the products were analysed and correlated to copolymer composition. The free volume properties of the copolymer were dependent on the glass transition temperature (Tg), which is dependant on the copolymer composition. The copolymer crystallinity decreased with increasing MA content. The decrease in crystallinity and increase in both o-Ps lifetime and o-Ps intensity with decreasing Tg was caused by the enhanced chain mobility brought about by the incorporation of methyl acrylate. The poly(acrylonitrile-co-methyl acrylate)/clay nanocomposites with 60% AN:40% MA (mol:mol) ratio were prepared using montmorillonite clay modified via adsorption, using 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), via in-situ intercalation polymerization. The poly(AN-co-MA)/clay nanocomposites with different clay loadings showed no difference in morphology. They exhibited improved thermomechanical properties and higher thermal stability than the neat copolymers. The melt rheology results of these nanocomposites showed an improved storage modulus as well as increased shear thinning behaviour with increasing clay content. However, the nanocomposites exhibited long-time relaxation behaviour and their chemical structures evolved during analysis. This was attributed to cyclisation reactions taking place at the temperature used during the oscillatory tests. The sorption isotherms of water vapour in these nanocomposites followed a dualmode sorption behaviour (BET type II mode). Hysteresis was observed in sorption/desorption isotherms of these nanocomposites. The equilibrium water uptake was higher in the nanocomposites compared to the neat copolymers, and it increased with increasing clay content, especially at high water activities (0.8). Although diffusion and permeability decreased with increasing clay content the solubility increased due to the hydrophilic nature of the clay. Despite the decrease in diffusion and permeability parameters the free volume hole radius of the nanocomposites remained constant, but a slight decrease in free volume hole number was observed. / AFRIKAANSE OPSOMMING: Die bereiding van poli(akrilonitriel/metielakrilaat) [poli(AN-ko-MA)] kopolimere en poli(AN-ko-MA)/klei nanosamestellings deur middel van emulsiepolimerisasie, hul karakterisering asook die ooreenkoms tussen hul molekulêre strukture en fisiese eienskappe is beskryf. Die kopolimeersamestelling is gevarieer, en eienskappe is geanaliseer en dan gekorreleer met die kopolimeersamestelling. Die vrye-volume eienskappe van die kopolimeer was afhanklik van die glasoorgangstemperatuur (Tg) wat weer afhanklik is van die kopolimeersamestealling. Die kristalliniteit van die kopolimeer het verminder met die hoeveelheid MA teenwoordig. Die afname in kristalliniteit en toename in beide die o-Ps leeftyd en o-Ps intensiteit met afname in Tg is veroorsaak deur die beter kettingbeweegbaarheid wat veroorsaak is deur die byvoeging van metielakrilaat. Die poli(akrilonitriel-ko-metielakrilaat)/klei nanosamestellings met 60% AN:40% MA (mol:mol) verhouding is berei deur die gebruik van montmorillonietklei, gemodifiseer deur die adsorpsie van 2-akrielamido-2-metiel-1-propaansulfoonsuur (AMPS) deur middel van 'n in-situ interkaleringspolimerisasie. Die poli(AN-ko-MA)/klei nanosamestellings het, ten spyte van die verskillende hoeveelhede klei wat gebruik is, geen verandering in morfologie getoon nie. Hulle het wel beter termodinamiese eienskappe en hoër termiese stabiliteit as die oorspronklike kopolimere getoon. Die smeltreologie resultate van hierdie nanosamestellings het ‘n beter stoormodulus getoon, sowel as toenemende skuifverdunningsgedrag met 'n verhoogde klei inhoud. Tog het die nanosamestellings lang tyd-ontspanningsgedrag getoon en die chemiese struktuur het verander tydens analise. Dit word toegeskryf aan die sikliese reaksies wat plaasvind by die temperatuur wat gebruik is tydens die ossillatoriese toetse. Die sorpsie isoterme van waterdamp in hierdie nanosamestellings het ‘n dubbel-styl sorpsiegedrag gevolg (BET tipe II styl). Histerese is waargeneem in sorpsie/desorpsie isoterme van hierdie nanosamestellings. Die ewewig in wateropname van die nanosamestellings was hoër as vir dié van die oorspronklike kopolimere en dit het toegeneem met 'n toenemende klei inhoud, veral by hoë humiditeit (0.8). Al het die diffusie en deurlaatbaarheid afgeneem met 'n toename in die klei inhoud, het die oplosbaarheid toegeneem as gevolg van die hidrofiliese karakter van die klei. Ten spyte van die afname in diffusie en deurlaatbaarheidsparameters, het die radius van die vryevolume openinge van die nanosamestellings konstant gebly, maar ‘n klein afname in die aantal vrye-volume openinge is gevind.

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.

This thesis focuses on the development of new stationary phases for use in hydrophilic interaction liquid chromatography using TRIS-based and phosphorylcholine typed monomers and porous silica particles as starting substrates. In this thesis, several ways of polymerizing highly hydrophilic mono­mers onto pore surfaces of silica supports are described, based on several “grafting from” schemes. “Controlled/living” radical polymerizations including atom transfer radical polymerization (ATRP) and iniferter-mediated polymerization in conjunction with conventional free radical polymerization are demonstrated to be successful tools for grafting different hydrophilic monomers (polyhydroxyl and phosphorylcholine [meth]acrylamide/acrylates) onto the silica surfaces. Reaction solvents are proven to play an essential role to achieve efficient graft polymerization of activated silica surfaces with these amphiphilic vinylic monomers, which is difficult because of their restricted access to the activated surface in solvents that can be used because of solubility constraints. Two tentacle TRIS-based polymer grafted silica, namely TRIS-WAX – TRIS functionality bonded to silica via a C–N–C imine bond and TRIS-Amide – TRIS bonded to silica via an amide bond, prove to be useful as stationary phases for hydrophilic interaction chromatography (HILIC).The TRIS-WAX exhibits a mixed mode hydrophilic partitioning and weak anion exchange (HILIC/WAX) retention mechanism while retention by hydrophilic partitioning is the dominant mechanism on the neutral TRIS-Amide phase which lacks weak anion exchange (WAX) properties. Interestingly, both these phases have selectivities that are radically different from most commercial HILIC stationary phases. Finally, a method is demonstrated for synthesizing a stratified (graft-copolymerized) silica material based on N,N′-methylenebisacrylamide and 2-methacryloyloxyethyl phosphorylcholine (MPC) using a “controlled/living” photoiniferter-mediated polymerization from the N,N-diethyldithiocarbamate iniferter moiety immobilized silica surfaces. This polymerization method proves to be successful for graft-blockcopolymerization of different highly hydrophilic monomers onto the activated surfaces of porous silica. In this way, silica surfaces are grafted with a cross-linked amide-based hydrogel, on top of which a tentacle zwitterionic phosphorylcholine-typed layer is synthesized. The resulted material proves to be useful for HILIC separations and possesses different selectivity for the tested organic acids compared to that of commercial ZIC-cHILIC stationary phase.

In this study, the effects of organoclay loading, compatibilizer loading and polyethylene type on the morphology, rheology, thermal properties and mechanical properties of polyethylene/compatibilizer/organoclay nanocomposites were investigated. As compatibilizer, terpolymer of ethylene-methacrylate-glycidyl methacrylate (Lotader&reg / AX8900), as organoclay Cloisite&reg / 15A were used. All samples were prepared by a co-rotating twin screw extruder, followed by injection molding. Considering ternary nanocomposites, highest impact strength results were obtained with 10% compatibilizer plus 2% organoclay / highest yield stress, elastic modulus, flexural strength, flexural modulus were obtained with 5% compatibilizer plus 4-6% organoclay. DSC data indicated that addition of organoclay and compatibilizer did not change the melting point remarkably / on the other hand it affected the crystallinity. The organoclay used had no nucleation effect on polyethylene, and the compatibilizer decreased the crystallinity of the matrix. X-ray diffraction showed that in all ternary nanocomposites and in binary nanocomposite of high density polyethylene with organoclay, layer separation associated with intercalation of the clay structure occurred,. The highest increase of interlayer gallery spacing was obtained with 10% compatibilizer plus 2% organoclay, which were 25%, 28% and 27% for HDPE, LLDPE and LDPE matrices respectively.