Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Water-borne coatings often contain multiple additives including pigments, dispersing agents, rheology modifiers, UV stabilizers and biocides. Due to their low molar mass and endocrinedisrupting properties, many of these additives, upon leaching from the substrate film, with time pollute water systems and become hazardous to the environment and to human health. In this study, I aimed to develop a facile method for the production of a polymeric biocide to serve as alternative to low molar mass biocides used in water-borne coatings. A secondary aim was to show that, without additional modification, the polymeric species can be used in surfactant-free ab initio emulsion polymerizations. Using a two-step process, I modified a commercially available copolymer, poly(styrene-alt-maleic anhydride) (SMA 1000), with mixed amines in order to obtain latexes with inherent antimicrobial activity. In the first step, I reacted SMA 1000 with 3-dimethylamino-1-propylamine and aqueous ammonia to confer antimicrobial activity and water-solubility to the SMA copolymer. In the second step, the copolymer was incorporated into a film-forming styrene-butyl acrylate (STY/BuA) latex. The modified SMA was incorporated into a latex in two ways: (1) post-added to the latex, and (2) used as stabilizer in emulsion polymerization. In both cases, the latex remained stable for up to 11 months, and stability was probably due to steric stabilization of the polymer particles. Antimicrobial activity of the latex film was achieved with both methods. When the modified SMA was post-added, antimicrobial activity was restricted to specific areas on the eventual polymer film, and when modified SMA was used as stabilizer, antimicrobial activity was evenly distributed throughout the polymer film. Fluorescence microscopy showed homogeneous distribution of antimicrobial activity upon inoculation in Gram positive bacteria dispersions when the modified copolymer was used as polymeric stabilizer for the synthesis of STY/BuA latexes. No antimicrobial activity against Gram negative bacteria was achieved. The homogeneous distribution of antimicrobial activity throughout the film was a result of adsorption of polymeric biocide/stabilizer to each individual latex particle. With further commercial development, high molar mass copolymers modified for antimicrobial activity may be a feasible, environmentally-friendly and healthy alternative to be used as stabilizers in emulsion polymerizations to produce water-borne coatings. / AFRIKAANSE OPSOMMING: Waterverf bestaan gewoonlik uit ‘n verskeidenheid bestandele, onder andere: pigmente, verspreiding middels, reologie modifiseerders, UV stabiliseerders en biologies aktiewe verbindings. As gevolg van die lae molêre massa en die endokrien ontwrigtende vermoë van baie van die bestandele hou hulle ‘n bedreiging in vir die omgewing in terme van waterbesoedeling en menslike gesondheid, soos hulle die film oor tyd verlaat. In hierdie studie het ek beoog om ‘n eenvoudige metode vir die vervaardiging van ‘n polimeries biologies aktiewe verbindings daar te stel om sodoende as ‘n alternatief vir die lae molêre massa biologies aktiewe verbindings, wat tans in waterverf gebruik word, te dien. ‘n Sekondêre uitkoms van die studie was om te wys dat, sonder enige adissionele omskakelings, dieselfde polimeer gebruik kan word in seep-vrye emulsie polimerisasie. Deur gebruik te maak van ‘n proses, wat uit twee stappe bestaan, het ek ‘n kommersieel beskikbare kopolimeer, poly(stireen-alt-maleinesuuranhidried) (SMA 1000), met gemengde amiene reageer om ‘n sintetiese lateks van stireen en butiel akrilaat (STY/BuA) met inherente antibakteriële aktiwiteit te verkry. In die eerste stap is SMA 1000 met 3-dimetielamien-1-propielamien en waterige ammoniak reageer om ‘n water oplosbare kopolimeer met inherente anti-bakteriële aktiwiteit te verkry. In die tweede stap is hierdie kopolimeer by ‘n sintetiese lateks gevoeg op twee maniere: (1) deur dit nadat die lateks geproduseer is by te voeg, en (2) deur die kopolimeer as stabiliseerder te gebruik in die vervaardiging van die lateks. In albei gevalle is stabiele latekse verkry vir ‘n tydperk van tot 11 maande. Die stabilisering was van steriese geaardheid. Albei die latekse het gevolglik antibakteriële eienskappe getoon. Daar was nie homogene verspreiding van die aktiwiteit in die geval waar die kopolimeer na die tyd bygevoeg is nie en het veroorsaak dat daar sekere areas van die finale film was wat geen aktiwiteit getoon het nie. Fluoresensie mikroskopie het egter homegene verspreiding van die anti-bakteriële aktiwiteit reg deur die film getoon, na inokulasie met Gram positiewe bakterië suspensies wanneer die kopolimeer as polimerisasie stabiliseerder gebruik was. Geen aktiwiteit teen Gram negatiewe bakterië was egter verkry nie. Die homogene verspreiding was as gevolg van die feit dat die kopolimeer sterk adsorbeer op elke individuele lateks partikel wanneer dit as stabiliseerder gebruik word. Verdere ontwikkeling op ‘n kommersiële basis kan daartoe lei dat polimeries biologies aktiewe verbindings as ‘n lewensvatbare en omgewingsvriendelike alternatief vir heidige stabiliseerders in emulsies vir waterverf gebruik kan word.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: New methods are described for the synthesis of polymer/graphite nanocomposites using the miniemulsion polymerization process. Natural graphite was functionalized by oxidation to produce graphite oxide (GO) nanosheets. Poly(styrene-co-butyl acrylate) (poly(St-co-BA)) nanocomposite latices containing GO nanosheets were successfully synthesized using miniemulsion as a one-step nano-incorporation technique. The approach followed included expanding the GO nanosheets in situ during the miniemulsification step and then polymerizing the monomers in the presence of these expanded nanosheets. Styrene (St) and butyl acrylate (BA) were mixed with GO and then emulsified in the presence of a surfactant and a hydrophobe to afford pre-miniemulsion latex particles. The stable pre-miniemulsions were then polymerized to yield poly(St-co-BA)/GO nanocomposite latices. The polymerization proceeded with relatively high monomer conversion and produced stable nanocomposite latex particles. The nanocomposites exhibited mainly an intercalated morphology, irrespective of the percentage of GO filler loading. The synthesis of exfoliated polymer nanocomposites made with modified GO is described. GO was modified with a surfmer (reactive surfactant), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), which widened the gap between the GO nanosheets and facilitated monomer intercalation between its nanogalleries. The AMPS-modified GO was used for the synthesis of poly(St-co-BA)/GO nanocomposite latices using a similar miniemulsion procedure. The obtained nanocomposites had exfoliated morphologies and the GO nanosheets were largely exfoliated (about 2–5 nm thick) in the resultant films obtained from the synthesized nanocomposite latices. The synthesized nanocomposites had enhanced thermal and mechanical properties compared to pure polymer as a result of the presence of AMPSmodified GO. Furthermore, the nanocomposites made with AMPS-modified GO had better thermal and mechanical properties than the unmodified GO. The mechanical properties of the nanocomposites depended on the AMPS-modified GO loading in the nanocomposites. The synthesis of polystyrene/GO (PS-GO) nanocomposites using the reversible additionfragmentation chain transfer (RAFT) mediated polymerization method is also described. The GO was synthesized and immobilized with a RAFT agent to afford RAFT-functionalized GO nanosheets. The RAFT-immobilized GO was used for the synthesis of PS nanocomposites in a controlled manner using miniemulsion polymerization. The molar mass and dispersity of the PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT-mediated polymerization. X-ray diffraction and transmission electron microscopy analyses revealed that the nanocomposites had exfoliated morphology, even at relatively high GO content. The thermal stability and mechanical properties of the PS-GO nanocomposites were better than those of the neat PS polymer. Furthermore, the mechanical properties were dependent on the modified-GO content (i.e., the amount of RAFT-grafted GO). The hydrophobicity and barrier properties of the resulting films prepared from the synthesized poly(St-co-BA)/GO nanocomposite latices to water and water vapor were also investigated. The hydrophobicity of the synthesized nanocomposite films was determined using contact angle measurements. The water permeability was determined by measuring the moisture vapor transmission rate of the films. The GO in the nanocomposites was reduced to its original form (i.e., graphite), and the barrier properties of the obtained nanocomposite films were determined and compared to films containing the unmodified GO (as-prepared GO). Results showed that reduction of GO had a significant impact on the water affinity of the resultant films prepared from the synthesized nanocomposite latices. The presence of reduced-GO (RGO) instead of unmodified GO in the miniemulsion formulation significantly improved the hydrophobicity and barrier properties of the final films to water. However, the barrier properties of the nanocomposites were unaffected by the amount of RGO in the nanocomposites. / AFRIKAANSE OPSOMMING: Nuwe metodes is beskryf vir die sintese van polimeer/grafiet nanosamestellings deur gebruik te maak van die miniemulsie polimerisasieproses. Natuurlike grafiet is gefunksionaliseer dmv oksidasie om grafietoksied (GO) nanovelle te vorm. Polistireen-ko-butielakrilaat (poli[St-ko- BA]) nanosamestellinglatekse wat GO nanovelle bevat is suksesvol gesintetiseer deur gebruik te maak van miniemulsie polimerisasie as ‘n een-stap nano-insluitingstegniek. Die benadering wat gevolg is het die uitbreiding van die GO nanovelle, in situ, gedurende die miniemulsifiseringstap behels, gevolg deur die polimerisasie van die monomere in die teenwoordigheid van hierdie uitgebreide nanovelle. Stireen (St) en butielakrilaat (BA) is met GO gemeng en daarna emulgeer in die teenwoordigheid van ‘n seepmiddel (surfactant) en ‘n hidrofoob om pre-miniemulsielateksdeeltjies te lewer. Die stabiele pre-miniemulsies is gepolimeriseer om poli(St-ko-BA)/GO nanosamestellinglatekse te vorm. Die polimerisasie het met redelike hoë monomeeromskakeling verloop en het stabiele nanosamestellinglateksdeeltjies gelewer. Hierdie nanosamestellings het hoofsaaklik geïnterkaleerde morfologie, onafhanklik van die persentasie GO vullers, getoon. Die sintese van afgeskilferde polimeernanosamestellings berei met gewysigde GO is beskryf. GO is gewysig met ‘n ‘surfmer’ (reaktiewe seepmiddel), 2-akrielamido-2-metiel-1- propaansulfoonsuur (AMPS), wat die gapings tussen die GO nanovelle vergroot het en die monomeer interkalering tusssen sy nanogange fasiliteer. Die AMPS-gewysigde GO is gebruik vir die sintese van poli(St-ko-BA)/GO nanosamestellinglatekse deur gebruik te maak van ‘n soortgelyke miniemulsie prosedure. Die nanosamestelling sό verkry het ‘n afgeskilferde morfologie getoon en die GO nanovelle was grootendeels afgeskilfer (ongeveer 2–5 nm dik) in die films wat berei is van die gesintetiseerde nanosamestellinglatekse. Laasgenoemde het verhoogde termiese en meganiese eienskappe gehad in vergelyking met die suiwer polimeer, as gevolg van die teenwoordigheid van die AMPS-gewysigde-GO. Die meganiese eienskappe van die nanosamestellings hang af van persentasie AMPS-gewysigde GO vullers in die nanosamestellings. Die sintese van PSt/GO nanosamestellings dmv die omkeerbare-addisie-fragmentasieoordrag- (OAFO-, Eng. RAFT-) bemiddelde polimerisasie metode is ook beskryf. Die GO is berei en geïmmobiliseer met ‘n RAFT verbinding om GO nanovelle met RAFT funksionaliteit te lewer. Die RAFT-geïmmobiliseerde GO is gebruik vir die sintese van PSt nanosamestellings in ‘n gekontrolleerde manier mbv miniemulsie polimerisasie. Die molêre massa en dispersie van die PSt in die nanosamestellings hang af van die hoeveelheid RAFTgeënte GO in die sisteem, in ooreenstmming met die kenmerke van RAFT-bemiddelde polimerisasie. X-straaldiffraksie en transmissie-elektronmikroskopie analises het bewys dat die nanosamestellings, selfs by relatiewe hoë GO inhoud, ‘n afgeskilferde morfologie gehad het. Die termiese stabiliteit en meganiese eienskappe van die PSt-GO nanosamestellings was beter as dié van die suiwer PSt polimeer. Verder was die meganiese eienskappe afhanklik van die gewysigde-GO-inhoud (dws, die hoeveelheid RAFT-geënte-GO). Die hidrofobisiteit en spereienskappe van die films berei vanaf die gesintetiseerde poli(St-ko- BA)/GO nanosamestellinglatekse teenoor water en waterdamp is ook ondersoek. Die hidrofobisiteit is ondersoek deur gebruik te maak van kontakhoekmeting. Die waterdeurlaatbaarheid is bepaal deur die waterdampoordragtempo van die films te bepaal. Die GO in die nanosamestellings is gereduseer tot sy eenvoudigste vorm (grafiet) en die spereienskappe van die nanosamestellingfilms is bepaal en vergelyk met die films wat die ongewysigde GO bevat het. Resultate het getoon dat reduksie van GO ‘n groot invloed gehad het op die wateraffiniteit van die films wat berei is vanaf die gesintetiseerde nanosamestellinglatekse. Die teenwoordigheid van die gereduseerde-GO (RGO) in plaas van die onveranderde GO in die miniemulsie formulasie het die hidrofobisiteit en spereienskappe van die finale films, teenoor water, baie verbeter. Die spereienskappe van die nanosamestellings is egter nie beïnvloed deur die hoeveelheid RGO in die nanosamestellings nie.

Polymere sind zweifelsohne der Werkstoff in unserer Zeit. Ein bedeutender Anteil der heute industriell produzierten Polymere wird durch Emulsionspolymerisation hergestellt. Obwohl die Emulsionspolymerisation breite Anwendung findet, sind die involvierten Mechanismen von Teilchenbildung und -wachstum noch heute Gegenstand heftiger Kontroversen.<br> Ein Spezialfall der Emulsionspolymerisation ist die emulgatorfreie Emulsionspolymerisation. Hierbei handelt es sich um ein scheinbar einfacheres System der Emulsionspolymerisation, weil diese Methode ohne Zusatz von Emulgatoren auskommt.<br><br> Die Teilchenbildung ist ein fundamentaler Vorgang im Verlauf der Emulsionspolymerisation, da sie zur Ausbildung der polymeren Latexphase führt. Detaillierte Kenntnisse zum Mechanismus der Nukleierung ermöglichen eine bessere Kontrolle des Reaktionsverlaufes und damit der Eigenschaften des Endproduktes der Emulsionspolymerisation, dem Polymer-Latex.<br> Wie bereits vorangegangene Arbeiten auf dem Gebiet der emulgatorfreien Emulsionspolymerisation von Styrol sowie Methylmethacrylat und Vinylacetat zeigen konnten, verläuft die Teilchenbildung in diesen Systemen über den Mechanismus der aggregativen Nukleierung. Im Zusammenhang mit den Ergebnissen der genannten Arbeiten tauchte dabei immer wieder ein interessanter Effekt im Bereich der Partikelnukleierung auf. Dieses als JUMBO-Effekt bezeichnete Phänomen zeigte sich reproduzierbar in einem Anstieg der Transmission im Bereich der Teilchenbildung von emulgatorfreien Emulsionspolymerisationen von Styrol, MMA und VAc. Nach der Initiierung der Polymerisation in einer wässrigen Monomerlösung durch Kaliumperoxodisulfat steigt die Durchlässigkeit bei 546 nm auf über 100 % an. Für diese „Abnahme der optischen Dichte“ wurden verschiedene Erklärungsmöglichkeiten vorgeschlagen, jedoch blieb ein Nachweis der Ursache für den JUMBO-Effekt bisher aus. Dieser Mangel an Aufklärung eines offenbar grundlegenden Phänomens in der emulgatorfreien Emulsionspolymerisation bildet den „Nukleus“ für die vorlie¬gende Arbeit.<br><br> Durch die vorliegende Dissertation konnte das Verständnis für Phänomene der Teilchenbildung in der emulgatorfreien Emulsionspolymerisation von Styrol mit KPS erweitert werden. In diesem Rahmen wurde das Online-Monitoring des Polymerisationsvorganges verbessert und um verschiedene Methoden erweitert:<br> Zur simultanen Erfassung von Trübungsdaten bei verschiedenen Wellenlängen konnte ein modernes Spektrometer in Kombination mit einer Lichtleitersonde in die Reaktionsapparatur integriert werden.<br><br> Es wurde ein verbesserter Algorithmus zur Datenbearbeitung für die Partikelgrößenbestimmung mittels faseroptischer dynamischer Lichtstreuung entwickelt.<br> Es wurden Online-Partikelgrößenanalysen mittels statischer Vielwinkellichtstreuung bei Polymerisationen direkt in entsprechenden Lichtstreuküvetten durchgeführt.<br><br> Diese zur Beschreibung des untersuchten Systems eingeführten Methoden sowie ein zeitlich vollständiges Monitoring des gesamten Polymerisationsverlaufes, beginnend mit der Zugabe von Monomer zu Wasser, führten zu neuen Erkenntnissen zur emulgatorfreien Emulsionspolymerisation.<br> Es wurden große Monomeraggregate, die sog. Nanotröpfchen, in wässriger Lösung (emulgatorfrei) nachgewiesen. Diese Aggregate bilden sich spontan und treten verstärkt in entgastem Wasser auf.<br><br> Die Existenz von Nanotröpfchen in Verbindung mit Trübungs- und gaschromatografischen Messungen lässt auf eine molekular gelöste „Wirkkonzentration“ von Styrol in Wasser schließen, die bedeutend geringer ist als die absolute Sättigungskonzentration.<br> Es konnten Hinweise auf eine Reaktion höherer Ordnung im System Wasser/Styrol/KPS gefunden werden.<br><br> Es konnte gezeigt werden, dass eine präzise Einstellung der Nukleierungsdauer über die Zeit der Equilibrierung von Wasser mit Styrol möglich ist.<br> Der JUMBO-Effekt, dem in dieser Arbeit ein besonderes Interesse galt, konnte in gewisser Weise entmystifiziert werden. Es konnte gezeigt werden, dass die Durchlässigkeit der Reaktionsmischung bereits beim Lösen von Styrol in Wasser durch Bildung von Styrolaggregaten abnimmt. Der darauf folgende kurzzeitige Transmissionsanstieg im Zusammenhang mit der Nukleierung erreicht dabei nicht mehr 100 % des Referenzwertes von reinem Wasser. Alle experimentellen Daten sprechen für die Nanotröpfchen als Ursache des JUMBO-Effekts.<br> Wie die Ergebnisse dieser Arbeit zeigen, ist selbst das relativ „einfache“ System der emulgatorfreien Emulsionspolymerisation komplizierter als angenommen. Die Existenz von großen Styrolaggregaten in wässriger Lösung erfordert eine neue Betrachtungsweise des Reaktionssystems, in die auch der Lösungszustand des Monomers mit einbezogen werden muss. / Polymers are doubtless the material of today. Large amounts of industrially produced polymers are made via emulsion polymerization. Although emulsion polymerization is widely used commercially, the mechanisms of particle formation and -growth involved are still intensely controversial.<br><br> A special case of the emulsion polymerization is the emulsifier-free emulsion polymerization. This apparently easier procedure is performed without addition of emulsifier.<br> Particle formation is a fundamental event in the progression of emulsion polymerization because it leads to the formation of a polymeric latex phase. Explicit knowledge concerning the mechanism of nucleation facilitates better control of the reaction process and therefore of the properties of the final polymeric latex product.<br><br> Other contributions in emulsifier-free emulsion polymerization of styrene could already proof that particle formation in the present system proceeds via aggregative nucleation. In the context of the results of these contributions, an interesting effect was always detected in the time range of particle nucleation. This so-called “JUMBO-effect” appeared highly reproducible as an increase of transmittance during nucleation period in the emulsifier-free emulsion polymerization of styrene. After initiation of the polymerization in an aqueous monomer solution with potassiumperoxodisulfate the transmittance at 546 nm increases to more than 100 %. For this “decrease in optical density” various possible explanations have been suggested, but a proof for any of them is still to be found. This lack of insight into an apparently fundamental phenomenon in emulsifier-free emulsion polymerization arises as the “nucleus” of the present thesis.<br><br> Within this work the understanding of the phenomena of particle formation in emulsifier-free emulsion polymerization of styrene with potassiumperoxodisulfate could be enhanced. In this frame the online monitoring of the polymerization process could be improved and expanded to several methods:<br><br> For the simultaneous recording of UV-spectra respectively turbidity data at various wavelengths a modern spectrometer in combination with a fibre optical probe could be integrated into the reaction vessel.<br> An improved algorithm for data treatment of particle size determination via fibre optical dynamic light scattering was developed.<br> We implemented online particle size determinations via multi angle laser light scattering directly in light scattering cuvettes.<br><br> These newly introduced methods, in combination with temporally complete monitoring of the whole polymerization progression, starting with the addition of monomer to water, lead to novel insight into emulsifier-free emulsion polymerization of styrene:<br> Big monomer aggregates, so called “nano droplets”, could be detected in an aqueous solution of styrene. These aggregates form spontaneously and appear especially in degassed water. Polymerisation as the origin of the nano droplets can be excluded.<br> In context with turbidity and gas chromatographic measurements, the existence of nano droplets leads us to conclude that there is a molecularly dissolved “effective” concentration of styrene in water which is much lower than the absolute concentration reported in the literature.<br> We could find some hints for a higher reaction order in the system water/styrene/potassiumpersulfate. The induced decomposition of the peroxodisulfate ion in the presence of styrene and ethylbenzene shows an additional reaction of the initiator with aromatic compounds besides the thermolytical cleavage.<br> Furthermore it could be shown that it is possible to precisely adjust the duration of nucleation with the solubilisation time of styrene in water. This kind of control can be useful for other applications.<br> The JUMBO-effect, which was a major topic of this thesis, could be partly de-mystified. It could be shown that the turbidity of the reaction mixture already increases during the dissolution process of styrene due to the formation of aggregates. The turbidity decrease which is depicted by the JUMBO-effect in the time range of nucleation never reaches 100 % of the reference water. An interference of the used measuring wavelength with the domain size of density fluctuations according to the theory of spinodal decomposition could not be verified. The experimental data suggest rather the nano droplets as origin of the JUMBO-effect.<br> The results of the present thesis show clearly that the relatively “simple” system of the emulsifier-free emulsion polymerisation (water/styrene/potassiumpersulfate) is more complex than expected. The existence of big styrene aggregates in aqueous solution requires a new approach of the reaction system, which also includes the solution state of the monomer.

High performance liquid chromatography (HPLC) is one of the major techniques in separat-ion sciences. Faster separation and higher efficiency are required to meet ever-growing demands. Despite numerous studies and achievements on improving mass transfer in particulate packings discontinuity seems to be the cornerstone drawback in their development. Macroporous continuous beds or monoliths are therefore a promising alternative to the particle medium. This thesis deals with preparation of new monoliths used as carrier for HPLC. Two different approaches were developed for two polymer systems. One was based on polycondensation of epoxy resins and polyamines which were components of an oil-in-water emulsion. An epoxy resin mixture was dispersed in aqueous polyamine phase with the aid of a surfactant. The other involved a traverse of a ready-made polymer solution around its upper critical solution temperature (UCST). In other words, linear polyamides, non-covalently crosslinked polymers, dissolved in a solvent at temperature higher than their UCST followed by slow cooling to below the critical temperature to precipitate the polymers. Partly re-established hydrogen bonds resulted in the formation of crystallites that interconnected into a network structure. Factors controlling morphology and porosity of final products were investigated. The study also deals with surface modifying for chromatographic applications. Functionalization pathways attempted in the thesis were quaterization of inherent amine of the epoxy-based monoliths and grafting tentacle ion groups via glycidyl methacrylate by atom transfer radical polymerization (ATRP) for ion exchange chromatography (IEC).

La synthèse et l’assemblage de particules colloïdales de morphologie et de fonctionnalité originale permet d’envisager la fabrication de matériaux aux propriétés électromagnétiques innovantes. Au cours de ce travail, nous nous sommes intéressés à la synthèse de colloïdes hybrides silice/polystyrène par un processus de polymérisation en émulsion du styrène ensemencé par des germes de silice préalablement fonctionnalisés en surface par des groupements méthacrylate. Ces particules hybrides, composées d’une particule centrale de silice entourée d’un nombre contrôlé de nodules de polystyrène, ont été utilisées comme moules afin de synthétiser des nanocages d’or de morphologie contrôlée. Ces nanocages d’or ont été caractérisées structuralement et optiquement. Nous nous sommes également intéressés à l’assemblage des particules hybrides silice/polystyrène via la génération d’interactions entre les nodules de polystyrène grâce au contrôle de qualité du solvant pour le polystyrène. Les particules présentant un nodule de polystyrène s’assemblent en petits clusters alors que celles présentant deux nodules de polystyrène forment des chaînes. / The synthesis and the assembly of colloidal particles with original morphology and functionality should allow the fabrication of next-generation materials. This study deals with the synthesis of hybrid silica/polystyrene particles by an emulsion polymerization of styrenes eeded by surface functionalized silica particles. These particles, made by a silica coredecorated by a controlled number of polystyrene nodules, has been used as templates for thesynthesis of goldnanocages morphologically controlled. Theses gold nanocages has been characterized structurally and optically. We have also investigated the self-assembly of hybrid silica/polystyrene particles by generating interaction between polystyrene nodules due to the control of the solvent quality for polystyrene. Particles with one polystyrene nodule self assemble in little clusters and particle with two nodules in chains.

La société CASCADE a été créée pour industrialiser des technologies dites à « cascades lumineuses ». Le principe de ces « cascades lumineuses » consiste à réaliser un ou plusieurs décalages de fréquences lumineuses (ou électromagnétiques) en dopant une matrice polymère transparente par intégration de molécules optiquement actives (MOA), permettant d’adapter le spectre solaire à la photosynthèse et à la fonction chlorophyllienne des plantes. Un intérêt majeur pour les cultures sous serres d’utiliser des films agricoles dopés avec les MOA est de favoriser la précocité des récoltes ou d’accroître la quantité en poids des végétaux récoltés, sans en altérer leur qualité. Les polymères utilisés aujourd’hui dans les films agricoles sont le polyéthylène (PE) et le copolymère poly(éthylène-co-acétate de vinyle) (EVA) dans lesquels les MOA ne sont pas suffisamment stabilisées pour une application industrielle. L’objectif de la thèse vise donc à améliorer la tenue temporelle des MOA dans les matrices polymères PE/EVA par différentes stratégies : (i) l’étude de l’influence de la nature et de la topologie de la matrice polymère, (ii) l’optimisation des formulations existantes par ajout d’additifs ou de compatibilisants et (iii) l’encapsulation des MOA dans des particules de PMMA (non)-réticulées. / The CASCADE company was founded to develop technology said to “light cascades”. These “light cascades” consist of incorporating an appropriate combination of optically active molecules (OAM) into host materials allowing wavelength-shifting effects to optimize the quality and quantity of direct and diffuse sunlight. When such OAM combination is introduced into greenhouse films, an increase of agronomic yields and early crop are observed. Such behavior is due to the fact that OAM allow to adapt the solar spectrum to the photosynthesis and the chlorophyll function of plants. Greenhouse films are based on polyethylene (PE) and/or poly(ethylene-co-vinyl acetate) (EVA) copolymers. When OAM are introduced within such host polymers, their optically efficiency is limited for long term industrial applications. Therefore, the thesis goal is to improve the OAM lightfastness into PE/EVA polymer matrix by different strategies: (i) the study of polymer matrix nature and topology influence, (ii) the optimization of current formulations by additives or compatibilizers adding and (iii) the OAM encapsulation into (un)-crosslinked PMMA particles.

Orientador: Lucia Helena Innocentini Mei / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-11T12:29:46Z (GMT). No. of bitstreams: 1 Oliveira_JorgeMayerde_M.pdf: 2881095 bytes, checksum: e00a73f8e95aefd825ead7bdff943f4d (MD5) Previous issue date: 2008 / Resumo: A indústria de tintas é uma grande consumidora de látex obtido pela técnica da polimerização em emulsão. Os surfactantes, essenciais à estabilidade do látex, exercem um papel fundamental na produção e na aplicação destes polímeros, pois agem de forma a estabilizar as gotas de monômero na forma de emulsão. Eles são necessários para a formação de micelas, onde ocorre a polimerização, e para a estabilidade coloidal das partículas, durante e após a polimerização. Contudo, podem também produzir efeitos adversos nas propriedades do produto em razão de sua adsorção física às partículas de polímero. Os surfactantes não ligados podem migrar através do filme para as interfaces, formando agregados que podem aumentar a sensibilidade à água e afetando desta forma as propriedades de barreira, que são um dos requisitos principais em aplicações para tintas e outros revestimentos protetores. Um caminho promissor para minimizar este efeito dos surfactantes convencionais tem sido o uso de surfactantes polimerizáveis, ou reativos, que estão covalentemente ligados ao polímero e, desta forma, não podem ser dessorvidos e migrarem durante a formação do filme. Neste trabalho foram preparados látices de acetato de vinila ¿ vinil neodecanoato (VeoVa 10 ®), estabilizados com surfactantes não-iônicos convencionais e reativos, e avaliado o desempenho das dispersões e dos filmes poliméricos obtidos a partir destes látices. Foi observado que os látices estabilizados com surfactantes não-iônicos polimerizáveis em combinação com surfactantes aniônicos conduzem a dispersões estáveis com melhor resistência à permeabilidade à água e ao vapor de água. Contudo, os resultados obtidos sugerem que o principal fator de sucesso no uso de surfactantes não-iônicos polimerizáveis é sua incorporação à superfície da partícula de látex através de copolimerização com os monômeros principais. Foi também observado que para sintetizar látices utilizando um surfactante polimerizável no lugar de um convencional, mantendo propriedades similares tais como o tamanho de partícula, a estabilidade mecânica e eletrolítica, bem como a sensibilidade à água do filme formado, os produtores de látex terão de ajustar a quantidade e a reatividade do surfactante reativo no processo de polimerização / Abstract: The paint industry is a huge consumer of latex from emulsion polymerization. The surfactants, essential to the stability of the latex, play a crucial role in the production and application of emulsion polymers. They act to stabilize the monomer droplets in the emulsion form and are required for the formation of micelles, where the polymerization will occur, they are also essential for the colloidal stability of the polymer particles, during and after the polymerization process. However, they can also have adverse effects on the product properties due to their physical adsorption on the polymer particles. The unbound surfactants can migrate through the film toward the interfaces forming aggregates which increase water sensibility of the film, affecting in this way barrier properties which is one of the main requirements in applications for paints and other protective coatings. A promising way to reduce the negative effects of the conventional surfactants is to use polymerizable or reactive surfactants (surfmers) that are covalently linked to the polymer which avoid its desorption and migration towards the interface during the film formation. For this work, vinyl acetate ¿ vinyl neodecanoate (VeoVa 10 ®) latexes stabilized with conventional and reactive nonionic surfactant were prepared and the performance of dispersions and films obtained was compared. It was seen that the latexes stabilized with nonionic polymerizable surfactants in combination with anionic surfactant lead to stable dispersions with better resistance to water and water vapor permeability. However the results obtained suggested that the main factor of success for the use of nonionic polymerizable surfactants is its incorporation at the surface of the latex particle by copolymerization with the main monomers. It was also observed that to synthesize similar latexes by using a reactive surfactant instead of a conventional one, maintaining the same properties such as the particle size, the electrolyte and mechanical stability as well as the water sensibility of the formed film, latex producers will have to adjust the amount and the reactivity of the reactive surfactant in the emulsion polymerization process / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Orientador: Liliane Maria Ferrareso Lona / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T13:42:42Z (GMT). No. of bitstreams: 1 ChaparroMontezuma_GermanGiovanny_M.pdf: 3877380 bytes, checksum: 8f8924d77c55a7ec361451caa074630e (MD5) Previous issue date: 2011 / Resumo: A Polimerização radicalar mediada por nitróxido (NMRP) é uma técnica da polimerização controlada com a habilidade de produzir polímeros com um alto controle da sua microestrutura, estreita distribuição de massa molar e baixos valores de polidispersidade (muito próximos a um). As características do polímero obtidas na polimerização controlada têm aumentado o interesse de levar essa técnica para um nível industrial, no entanto a polimerização controlada ainda apresenta desafios como, por exemplo, desenvolver com sucesso a NMRP em emulsão, a baixas temperaturas e usando nitróxidos de baixo custo e disponíveis comercialmente, como 2,2,6,6-tetrametil-1-piperidiniloxi (TEMPO). A NMRP em emulsão de estireno a temperaturas inferiores a 100 ° C foi realizada com sucesso neste trabalho. TEMPO foi utilizado como agente controlador ainda que este nitróxido normalmente opere a temperaturas acima de 120 °C, sendo demonstrado o controle da massa molar e da polidispersidade, juntamente com uma rápida taxa de polimerização em um sistema de emulsão / Abstract: Nitroxide-mediated radical polymerization (NMRP) is a controlled polymerization technique with the ability to produce polymers with a highly controlled microstructure, narrow molecular weight distribution and low polydispersity values (very close to one). The polymer characteristics obtained in controlled radical polymerization have increased the interest of bringing this technique to an industrial level, however there are still some challenges to be faced, like, successfully develop NMRP in emulsion at low temperatures (lower than 100 °C) with inexpensive nitroxides commercially available, as 2,2,6,6- tetramethyl-1-piperidinyloxy (TEMPO). In this work NMRP of styrene in emulsion at temperatures below to 100 °C was carried out successfully. TEMPO was used as controller agent although this nitroxide usually works at temperatures above 120 °C. It was demonstrated an optimal control of molecular weights and polydispersities, together with a fast polymerization rate in an emulsion system / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Dans le cadre de ce travail de thèse, la polymérisation de type RAFT a été exploitée pour synthétiser des particules de latex magnétiques décorées de polymères stimulables. Cinq (co)polymères hydrophiles ont tout d'abord été préparés via la (co)polymérisation RAFT en solution d'acide acrylique (AA) et de méthacrylate de 2-diméthylaminoéthyle (MADAME). Les agents macromoléculaires obtenus (macroRAFT) : des homopolymères de PAA ou PMADAME ainsi que des copolymères P(AA-co-MADAME), présentent une sensibilité au pH et à la température. Ces macroRAFT hydrophiles ont ensuite été utilisés dans des réactions d’extension de chaîne avec du styrène conduisant à la formation de copolymères à blocs amphiphiles bien définis. Puis, des dispersions aqueuses d’agrégats (clusters) de nanoparticules d’oxyde de fer (OF) ont ensuite été préparées via un procédé de mini-émulsification/évaporation de solvant, en utilisant les copolymères à blocs comme stabilisants. Après optimisation des conditions expérimentales (sonication, concentration de macroRAFT, pH), des agrégats de taille contrôlée (45 à 300 nm) ont pu être obtenus. Ces clusters ont ensuite été utilisés comme semence lors de la polymérisation en émulsion du styrène, conduite en présence d’un agent de réticulation. Les clusters d'OF ont été individuellement encapsulés par une couche de polymère, formant des particules magnétiques stabilisées par le segment hydrophile des copolymères à blocs. Enfin, les particules magnétiques décorées de copolymères de P(AA-co-MADAME) ont été utilisées avec succès pour la capture et le relargage de bactéries grâce à la modulation de leurs propriétés de surface en fonction du pH / In this work reversible addition-fragmentation chain transfer (RAFT) polymerization was exploited to synthesize magnetic latex particles decorated with stimuli-responsive polymer brushes. First, five hydrophilic (co)polymers with various compositions were successfully prepared by RAFT solution (co)polymerization of acrylic acid (AA) and 2-dimethylaminoethyl methacrylate (DMAEMA) for different AA to DMAEMA molar ratios. The obtained macromolecular RAFT agents (macroRAFTs), PAA or PDMAEMA homopolymers and P(AA-co-DMAEMA) copolymers, displayed interesting pH- and thermo-responsive properties. These hydrophilic macroRAFTs were then chain extended with styrene leading to the formation of well-defined amphiphilic block copolymers. An aqueous dispersion of iron oxide clusters was next prepared using a strategy based on emulsification/solvent evaporation in which the block copolymers were used as stabilizers. By varying the experimental conditions (sonication power, macroRAFT concentration and pH of the medium), the cluster size could be controlled from 45 up to 300 nm. These clusters were then used as seeds in styrene emulsion polymerization in the presence of a crosslinker. The iron oxide clusters were individually encapsulated into a polymer shell generating latex particles, stabilized by the hydrophilic segment of the block copolymers, and displaying interesting magnetic properties. At last, these magnetic beads were evaluated as carriers in the magnetic separation of bacteria. The magnetic latex particles decorated with P(AA-co-DMAEMA) copolymers were successfully employed for the capture and trigger release of bacteria, allowing their concentration in a biological sample

Ce travail de thèse décrit l'élaboration de latex hybrides oxyde de fer (OF)/polymère par polymérisation en émulsion sans tensioactif. Des nanoparticules d'OF cationiques ont été tout d'abord synthétisées par co-précipitation de sels de fer dans l'eau. Des latex hybrides magnétiques ont été ensuite obtenus par deux voies de polymérisation. La première consiste en la synthèse de particules de latex de morphologie 'carapace' par polymérisation en émulsion Pickering du styrène et du méthacrylate de méthyle (MMA). Un comonomère auxiliaire (acide (méth)acrylique ou acide 2-acrylamido-2-méthyl-1-propane sulfonique) a été utilisé pour favoriser l'adsorption des OF à la surface des particules de polymère produites. Les analyses par MET indiquent la présence d'OF à la surface des particules de polymère (structure carapace). L'analyse thermogravimétrique a permis de quantifier l'efficacité d'incorporation des OF, i.e. la fraction d'OF initialement introduits effectivement adsorbés à la surface des particules. L'efficacité d'incorporation augmente avec la quantité de comonomère auxiliaire, le pH et la concentration en OF et dépend de la nature du monomère hydrophobe. Dans la deuxième voie, les OF ont été encapsulés par polymérisation radicalaire contrôlée par transfert de chaîne réversible par addition-fragmentation (RAFT) en émulsion aqueuse. La stratégie utilisée repose sur l'utilisation de macroagents RAFT amphiphiles comportant des groupements acide carboxylique connus pour interagir avec la surface des OF. L'interaction entre les macroRAFTs et les OF a été étudiée à travers le tracé de l'isotherme d'adsorption. Des analyses SAXS et DLS indiquent la formation de clusters d'oxyde de fer. Ces derniers ont été ensuite engagés dans la polymérisation en émulsion du styrène ou d'un mélange de MMA et d'ABu (ratio massique : 90/10) pour former une écorce de polymère à leur surface. Les particules carapace et les OF encapsulés affichent un comportement superparamagnétique / This work describes the elaboration of polymer/iron oxide (IO) hybrid latexes through surfactant-free emulsion polymerization. Cationic iron oxide nanoparticles stabilized by nitrate counterions were first synthesized by the co-precipitation of iron salts in water. Magnetic hybrid latexes were next obtained by two polymerization routes carried out in the presence of IO. The first route consists in the synthesis of polymer latexes armored with IO via Pickering emulsion polymerization of methyl methacrylate (MMA) or styrene (St). An auxiliary comonomer (namely methacrylic acid, acrylic acid or 2-acrylamido-2-methy-1- propane sulfonic acid) was used to promote IO particle adhesion to the surface of the generated polymer particles. TEM showed the presence of IO at the surface of the polymer particles and the successful formation of IO-armored polymer particles. TGA was used to quantify the IO incorporation efficiency, which corresponds to the fraction of IO effectively located at the particle surface. The incorporation efficiency increased with increasing the amount of auxiliary comonomer, suspension pH and IO content or with increasing monomer hydrophobicity. In the second route, IO encapsulation was investigated via reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization. The developed strategy relies on the use of water-soluble amphipathic macromolecular RAFT agents containing carboxylic acid groups, designed to interact with IO surface. The interaction between the macroRAFT agents and IO was investigated by the study of the adsorption isotherms. Both DLS and SAXS measurements indicated the formation of dense IO clusters. These clusters were then engaged in the emulsion polymerization of St or of MMA and nbutyl acrylate (90/10 wt/wt) to form a polymer shell at their surface. Both IO-armored latex particles and polymer-encapsulated clusters display a superparamagnetic behavior