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Cyanate ester (PT-15, Lonza Corp) composites containing the inorganic-organic hybrid polyhedral oligomeric silsesquioxanes (POSS), octaaminophenyl(T8)POSS (C6H4NH2)8(SiO1.5)8, cyanopropylheptacyclopentyl(T8)POSS, (C5H9)7(SiO1.5)8(CH2) 3CN or TriSilanolPhenylPOSS (C42H38O12Si7), were synthesized respectively. These PT-15/POSS composites were characterized by FT-IR, X-ray diffraction (XRD), small-angle neutron scattering (SANS), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and three-point bending flexural tests. XRD, TEM and IR data are all consistent with molecular dispersion of octaaminophenyl(T8)POSS and TriSilanolPhenylPOSS due to the chemical bonding of the POSS macromer into the continuous cyanate ester network phase. In contrast to octaaminophenyl(T8) POSS and TriSilanolPhenylPOSS, cyanopropylheptacyclopentyl (T8)POSS has a low solubility in PT-15 and does not react with the resin before or during the cure. The TriSilanolPhenylPOSS (C42H38O12Si7) was incorporated into the aliphatic epoxy (Epoxy 9000, Clearstream Products, Inc.) in 99/1, 97/3, 95/5, 90/10 and 85/15 w/w ratios and cured. This same epoxy resin was also blended with an equal weight (50/50 w/w) of cyanate ester resin (PT-15, Lonza Corp) and TriSilanolPhenylPOSS was added in resin/POSS weight ratios of 99/1, 97/3, 95/5, 90/10 and 85/15 and cured. Both sets of composites were characterized by FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), dynamic mechanical thermal analysis (DMTA) and three-point bending flexural tests. TriSilanolPhenyl-POSS was first thoroughly dispersed into the uncured liquid epoxy resin or the epoxy/PT-15 blend. XRD and X-EDS measurements after curing were consistent with partial molecular dispersion of the POSS units in the continuous matrix phase, while the remainder forms POSS aggregates. TEM and SEM show that POSS?enriched nanoparticles are present in the matrix resins of both the epoxy/POSS and epoxy-PT-15/POSS composites.

Ce projet s’est focalisé sur l’ajout de nouvelles propriétés à des papiers grâce à l’utilisation de nanocelluloses fonctionnelles. Ces nanocelluloses sont des nanoparticules extraites du bois qui peuvent être divisées en deux catégories : les nanofibrilles de cellulose (CNFs) et les nanocristaux de cellulose (CNCs). Ce travail s’est essentiellement penché sur l’utilisation des CNFs. Leur réactivité chimique a été utilisée afin de les fonctionnaliser avec des organotrialkoxysilanes. C’est aussi leur fort enchevêtrement ainsi que la grande viscosité de ces CNFs en suspension qui ont été utilisés afin de synthétiser des petites particules de silsesquioxane pour rendre le matériau final antimicrobien et (super)hydrophobe. Les connaissances obtenues à travers l’étude sur des films modèle de CNFs ont ensuite été appliquées au couchage du papier. Ces CNFs fonctionnelles ont donc été évaluées pour le développement d’un papier possédant une surface antimicrobienne, anti-adhérente, barrière aux graisses ou superhydrophobe. / The aim of this work is to implement new properties to a paper based material via the use of functional nanocelluloses. Nanocelluloses are nanoparticles extracted from wood and distinguished in two categories: Cellulose Nanofibrils (CNFs) and Cellulose Nanocrystals (CNCs). This work has only been carried out with CNFs. The chemical reactivity of CNFs was used to functionalize them with organotrialkoxysilanes. The entangled network and highly viscous suspension of CNFs was also used to synthesize silsesquioxane particles with limited size to impart (super)hydrophobic and antimicrobial properties. Knowledge obtained through the study of model CNFs films was then applied to paper based material coating. The functional CNFs were evaluated for its use in an antimicrobial, anti-adherent, greaseproof or superhydrophobic paper surface.

Le présent travail vise la synthèse d’organosilices nano-structurées à partir de briques élémentaires de silsesquioxanes polyédriques fonctionnalisées (T8-POSS) de structure cube (RSiO1,5)8. L’assemblage de briques fonctionnelles T8-POSS a été étudié selon deux voies : par des interactions fortes en formant des liaisons covalentes et par des interactions faibles en formant des liaisons hydrogène.La première partie décrit la formation de réseaux hybrides covalents à partir de structure T8 POSS portant huit fonctions aldéhydes. La synthèse et la structure cristalline de ces « cubes » fonctionnalisés sont décrites et la réactivité des fonctions aldéhydes est examinée. La formation de liaisons C=N par réaction d’amines conduit à des réseaux tridimensionnels grâce à la formation de ponts organiques bis-imines joignant les unités silsesquioxanes. Bien que la formation d’imine soit réversible, les solides obtenus ne présentent pas d’ordre à longue distance. La formation de liaisons C=C, dans des conditions de synthèse non réversibles, par réaction de bis-ylures de phosphonium avec les aldéhydes a également été étudiée. Ces réactions de type Wittig engendrent la formation de réseaux hybrides amorphes contenant des sous-structures phenylène-vinylènes dotées de propriétés de fluorescence. La deuxième partie décrit la synthèse de nouvelles molécules de T8-POSS, possédant des fonctions organiques amines ou acides carboxyliques capables d’interactions intermoléculaires grâce à des liaisons hydrogène. Ces interactions permettent l’assemblage des dérivés du T8-POSS fonctionnalisés par huit fonctions acides carboxyliques en un réseau 3D ordonné. Les briques élémentaires T8- POSS s’auto-assemblent par dimérisation des fonctions acides pour engendrer des silices hybrides cristallines. Les structures ont été déterminées par diffraction de rayons X. Les fonctions acides carboxyliques sont intéressantes non seulement par leur capacité à former des liaisons hydrogènes mais également par leur aptitude à former des carboxylates métalliques. Ces derniers ouvrent des perspectives pour la formation de réseaux d’oragnosilices incorporant des métaux. / The present work aimed at synthesising nano-structured organosilicas using polyhedral silsesquioxane building blocks (T8-POSS) having a cube structure. The assembly of T8-POSS building blocks to form a 3D network was studied in two ways: first by formation of strong covalent bonds and secondly by formation of weak hydrogen bonds.The first part described the formation of covalent hybrid networks from T8-POSS structures with eight aldehyde functional groups. The synthesis and crystal structure of these functionalised silsesquioxane cubes is described and the reactivity of the aldehyde groups is studied. The formation of C=N bonds upon reaction with amines lead to tree-dimensional networks upon formation of bis-imine bridges linking the silsesquioxane units. Despite the imine formation was reversible, the resulting solids were amorphous materials and exhibited no long distance order. The formation of C=C bonds, under non-reversible reaction conditions, was achieved by reaction of phosphonium bis-ylides. The Wittig type reactions generated amorphous hybrid networks containing bridging phenylene-vinylene substructures with fluorescence properties.The second part described the synthesis of new functionalised T8-POSS cubes with eight amine or carboxylic acid functions capable of intermolecular interactions by hydrogen bonding. It allowed the assembly of the octa-carboxylique acid cubes to form an ordered 3D hybrid network. The T8-POSS building blocks self-assembled upon dimerization of the acid groups and generated crystalline hybrid silicas. The crystal structures were determined by X-ray diffraction. The use carboxylic acid groups is interesting because of its ability to form hydrogen bonds and also because of its ability to form metal carboxylate derivatives. It could lead to hybrid metal organic silica frameworks.

Materiais naturais nanoestruturados, tipo smectita, têm sido amplamente usados em nanocompósitos poliméricos, com ganhos expressivos em muitas propriedades. Porém, devido a sua natureza polar, seu uso em nanocompósitos de poliolefinas apresenta uma série de problemas. Entre esses problemas está a dificuldade de esfoliação na matriz, o que geralmente resulta um sistema não nano-estruturado e, por conseqüência, com pouco ou nenhum ganho em propriedades. Para tentar resolver esse problema, materiais tipo esmectita têm sido modificados com sais de amônio quartenário. Esses, por sua vez, possuem características tóxicas, impedindo seu uso em embalagens de alimentos. Com o objetivo de estudar uma nova alternativa que contorne esses problemas, dois materiais lamelares nano-estruturados, tipo esmectita, contendo grupos alquila ligados por ligação sigma com a rede inorgânica, foram sintetizados. Ambos apresentaram excelente ordem mesoestrutural. Um dos materiais sintetizados, formado por um Alsilsesquioxano lamelar, contendo alto teor de cadeia alquila entre as lamelas inorgânicas, foi usado na formação de compósito de polietileno. Comparativamente, uma argila natural, modificada com sais de amônio quaternário (Cloisite 15A), foi usada para fins comparativos. Os compósitos, então obtidos, foram caracterizados para avaliar diferenças microestruturais, morfológicas e mudanças em suas propriedades mecânicas e reológicas. Comparativamente à argila comercial Cloisite 15A, os compósitos contendo os materiais sintéticos apresentaram reologia diferenciada, melhor resistência ao impacto e ao Tensofissuramento Acelerado pelo Ambiente (ESCR). / Nanostructured natural materials, as smectites, have been widely used in polymeric nanocomposites, with significant gains in many properties. However, due to its polar nature, the use in nanocomposites of polyolefins presents a series of drawbacks. Among these problems, its difficulty exfoliation in the matrix, which generally results in a system not nanostructured and, consequently, with little or no gain on properties. To try to resolve this problem, materials type smectite have been modified with quaternary ammonium salts. These salts, in turn, have toxic characteristics, preventing its use in food packaging. In order to study a new alternative that bypasses these problems, two lamellar nanostructured materials, like smectite, with alkyl groups containing sigma links connected to lamellar inorganic network, were synthesized. Both materials had excellent mesostructural order. One of the synthesized materials, formed by a lamellar Al-silsesquioxane, containing high levels of alkyl chain between the inorganic lamella, was used in the formation of a polyethylene composite. Commercial natural clay, modified with quaternary ammonium salts (Cloisite 15A), was used for comparative purposes. The composites then obtained, were characterized to assess microstructural differences, morphological change, and its mechanical and rheological properties. Comparatively to commercial clay (Cloisite 15A), the composites containing synthetic materials, showed differented rheologics properties, better impact resistance and better Environmental Stress Cracking Resistance (ESCR).

This research involved the synthesis and characterisation of a range of optically active polyhedral oligomeric silsesquioxane (POSS) compounds. POSS precursor compounds containing functional groups required for subsequent attachment of the desired functional groups have been synthesised. Examples of such precursor compounds include mono-functionalised POSS compounds with periphery aldehyde, azide, amino and pyridyl functional groups. A variety of POSS compounds, functionalised with a range of optical functionalities, including optical limiters such as fulleropyrrolidine and iminofullerene, and dyes and pigments, including naphthalene, biphenyl, perylene, pyrene and porphyrin have been synthesised. The reaction of mono-functionalised POSS aldehydes with fullerene (C60) in the presence of N-methylglycine yielded the desired POSS fulleropyrrolidines, whilst reaction of mono-functionalised POSS azide with C60 yielded POSS iminofullerenes. All POSS fullerene compounds were characterised by power limiting measurements, exhibiting comparable power limiting to that of parent C60. The microwave condensation of mono-amino POSS with a range of mono- and bis-anhydrides yielded the POSS imide compounds, which were characterised by UV-Vis and fluorescence spectrophotometry. The perylene POSS imide derivative was further characterised by single crystal x-ray crystallography. The naphtha and biphenyl POSS imides exhibited extremely weak fluorescence, whilst the perylene ii POSS imide displayed particularly strong fluorescence, with a quantum yield approaching unity. The incorporation of a pyridyl group on the periphery of a mono-functionalised POSS cage allowed for the synthesis of the first porphyrin functionalised POSS compound. Mono-porphyrin POSS exhibited comparable absorption properties to other pyridyl ligated ruthenium porphyrins. Mono-functionalised pyrene POSS compounds were prepared through the reaction of 1-pyrene acid chloride with mono(3-aminopropyl)POSS. This synthetic pathway offered a convenient route to mono-functionalised pyrene POSS, in preference to the multi-substitution associated with Heck coupling. Mono-pyrene POSS was determined to be strongly fluorescent, exhibiting a high quantum yield of fluorescence