Este trabalho teve como objetivo sintetizar e caracterizar uma matriz híbrida estável de poli(estireno-co-divinilbenzeno) magnetizado pela adição de magnetita (Fe3O4) e avaliar seu potencial como suporte para a imobilização de lipases. A matriz híbrida foi sintetizado pela técnica de polimerização em suspensão utilizando dos monômeros de estireno e divinilbenzeno e ao qual foram adicionadas partículas de magnetita preparadas por coprecipitação dos íons Fe+2 e Fe+3. A caracterização foi realizada pelas técnicas de microscopia eletrônica de varredura (MEV), espectroscopia na região do infravermelho por transformada de Fourier (FTIR), difratometria de raios-X (DRX) e magnetização de amostra vibrante (VSM), comparando os materiais magnetizados e não magnetizados. Os biocatalisadores foram preparados pela imobilização da lipase de Candida rugosa (LCR) e lipase PS Burkholderia cepacia (LPS) via adsorção física e foram caracterizados em função da influência de pH e temperatura na atividade hidrolítica, parâmetros cinéticos, estabilidade térmica, estabilidade operacional e estabilidade de estocagem. O derivado de LCR foi aplicado em reações de esterificação e o derivado de LPS em reações de transesterificação. Os resultados obtidos pelas análises de FTIR, DRX e VSM confirmaram que a magnetita foi incorporada ao polímero, gerando atração das partículas por um campo magnético externo. A caracterização bioquímica indicou forte influência do pH na atividade hidrolítica, apresentando ponto ótimo próximo a 8,0 tanto para as lipases livres quanto imobilizadas. Os biocatalisadores magnetizados preparados apresentaram bom desempenho em todos os aspectos, o derivado da lipase de Candida rugosa alcançou conversões entre 89-94% nas reações de esterificação, revelando tempo de meia vida de t1/2=52 dias na estabilidade operacional. O derivado de Burkholderia cepacia atingiu rendimentos próximos a 80% nas reações de transesterificação com t1/2=40 dias. A imobilização aumentou a estabilidade térmica das lipases em 50 vezes no caso da LCR e em 2,3 vezes para a LPS. Estes resultados indicam que o material híbrido magnetizado sintetizado possui grande potencial para ser utilizado como suporte na imobilização de enzimas com aplicação em reações de interesse industrial. / This study aimed to synthesize and characterize a stable hybrid matrix of poly (styrene-codivinylbenzene) magnetized by the addition of magnetite (Fe3O4) and evaluate its potential for application in the immobilization of lipases, by characterization of the prepared biocatalysts. The support was synthesized by the suspension polymerization technique by applying styrene and divinylbenzene monomers and adding magnetite particles synthesized by co-precipitation of Fe + 2 and Fe + 3. The characterization of the material was performed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating sample magnetization (VSM), by comparison of the magnetized and the not magnetized particles. The biocatalysts were prepared by immobilization of lipase from Candida rugosa (CRL) and lipase from Burkholderia cepacia (Lipase PS) via physical adsorption and they were characterized according to the influence of pH and temperature on the hydrolytic activity, kinetic parameters, thermal stability, operational stability and storage stability. The CRL derivative was applied in esterification reactions and the lipase PS derivative was applied in transesterification reactions. The results obtained by the analysis FTIR, XRD and VSM confirmed the magnetite was successfully incorporated into the polymer and generated the atraction for an external magnetic field. Biochemical characterization indicated a strong influence of pH on the hydrolytic activity, showing better results on pH around 8,0 for free and both immobilized lipases. The magnetized biocatalysts prepared had good performance in all respects, derivative from Candida rugosa lipase reached 89-94% conversion in esterification reactions showing half-life of operational stability t1 / 2 = 52 days. The immobilized lipase from Burkholderia cepacia reached yields close to 80% in transesterification reactions presenting t1/2 = 40 days. Immobilization increased the thermal stability of lipase by 50 times in the case of CRL and 2,3 times for Lipase PS. These results indicate that the magnetized hybrid material synthesized has great potential to be used as a support for the immobilization of enzymes for use in reactions of industrial interest.

Neste trabalho, dois macro-agentes de transferência de cadeia para polimerizações via RAFT, à base de poli(óxido de etileno), isto é, PEO-CPADB e PEO-CPP, foram sintetizados via duas rotas químicas e utilizados como estabilizantes coloidais e como agentes de controle de massa molecular na polimerização em miniemulsão do estireno. Látices de poliestireno (PS), estabilizados estericamente pelos segmentos de PEO, foram obtidos utilizando 2,2\'-azobis(isobutironitrila) como iniciador e hexadecano como co-estabilizador. O consumo de monômero foi determinado via análise gravimétrica. O tamanho de partícula e a distribuição de tamanhos de partículas (PSD) foram determinados por espalhamento de luz (LS). As massas moleculares e a distribuição de massas moleculares (nwMM) dos polímeros foram determinadas por cromatografia de exclusão de tamanho (SEC). Os resultados mostraram que o diâmetro das gotas e das partículas de polímero, assim como a estabilidade coloidal dos látices são fortemente dependentes do tipo e da quantidade de agente de transferência de cadeia utilizado nas polimerizações. Deslocamentos das curvas de distribuição de massas moleculares para massas moleculares maiores, em função da conversão, indicaram que a maioria das cadeias poliméricas apresentava características de cadeias vivas. Análises de GPC também mostraram que a polimerização foi bem controlada quando uma quantidade do macro-agente RAFT PEO-CPP, igual a 4,4 x 10-3 mol.L-1 foi utilizada, o que foi indicado pelo baixos índices de polidispersão obtidos (1,05-1,42). / In this work, two poly(ethylene oxide)-based macro-RAFT agents, ie, PEO-CPADB and PEO-CPP, were synthesized via two chemical routes and used as a stabilizer and a control agent in the miniemulsion polymerization of styrene. Polystyrene (PS) latexes sterically stabilized by the PEO segments were obtained using 2,2?-azobis(isobutyronitrile) as initiator and hexadecane as co-stabilizer. Monomer consumption was monitored by gravimetric analysis. The latex particle size and the particle size distribution (PSD) were measured by light scattering (LS). Molar masses and molar mass distributions (nwMM) of the polymers were determined by size exclusion chromatography (SEC). The results showed that the droplet/particle sizes and the latexes stability are strongly dependent on the type and on the amount of macro-RAFT agent used in the polymerizations. Shifts of the SEC chromatograms toward higher molar masses with conversion indicated that the majority of the polymer chains are living chains. Size Exclusion Chromatography (SEC) analysis also showed that polymerization was well controlled when an amount of macro-RAFT PEO-RAFT agent equal to 4.4 x 10-3 mol. L-1 was used, since low polidispersity indices (1.05-1.42) was achieved.

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.

Liquid chromatography is an analytical technique that is constantly facing new challenges in the separation of small molecules and large biomacromolecules. Recently the development of ultra high pressure liquid chromatography has increased the demand on sturdy particles as stationary phase. At the same time the particle size has decreased to sub-2 µm and packed into shorter analytical columns. This thesis deals with the development of new ways of preparing particulate polymer materials using divinylbenzene (DVB) as crosslinker. It includes a novel procedure for synthesizing monodisperse polymer particles by photoinitiated precipitation polymerization. A 150 W short arc xenon lamp was used to initiate the polymerizations. The synthesized particles are monodisperse and have an average particle size ranging from 1.5 to 4 μm depending on reaction conditions and have subsequently been used as grafting templates. The surface of DVB particles contains residual vinyl groups that serve as anchoring points for further functionalization via a variety of grafting schemes. Copolymerization with incorporation of 2,3-epoxypropyl methacrylate yielded pendant oxirane groups on the particle surface. Atom transfer radical polymerization (ATRP) was used to graft methacrylates from the surface resulting in a core-shell type material. A “grafting to” scheme was used to attach pre-made sulfopropyl methacrylate telomers onto particles containing oxirane rings. / Populärvetenskaplig sammanfattning på svenska: Vätskekromatografi är en analytisk kemisk teknik som ständigt står inför nya utmaningar när det gäller att separera allt från små organiska föreningar till stora makro¬molekyler. Denna avhandling beskriver tillverkning av polymera partiklar med exceptionellt jämn storleksfördelning och ytmodifiering av dessa, för användning som stationärfas i kromatografi¬kolonner. Polymeriserings¬tekniken som används är utfällnings¬polymerisering där lösningen UV-bestrålas av en 150 W xenonlampa. Monomeren (byggstenen) löses tillsammans med en intiator i ett lösningsmedel och efterhand som polymeriseringen fortskrider faller polymerpartiklarna ut. Polymerpartiklarna är gjorda av monomeren divinylbensen som fungerar som en tvärbindare, dvs att den länkar ihop flera kedjor till ett hårt litet nystan. Partiklarna växte till en storlek på 1,5 till 4 µm under två till fyra dygn. Efter tillverkningen är partiklarnas yta täckta av vinylgrupper som kan användas för att fästa funktionella polymerkedjor. Genom att tillföra monomeren 2,3-epoxipropyl¬metakrylat i polymeriseringen kunde man desutom få en partikelyta som innehöll epoxigrupper. Epoxigrupperna användes för att fästa positivt laddade polymerkedjor av bestämd längd. Materialet packades i en kromatografikolonn och användes för att separera en testlösning bestående av fyra proteiner. Partiklarna användes även som bas för ymppolymerisering där den vinyltäckta ytan fått reagera med vätebromid. Detta gör att partiklarna blir stora makroinitiatorer som kan användas för att på ett kontrollerat sätt låta polymerkedjor växa från ytan. I en undersökning ympades 2,3-epoxypropylmetakrylat från ytan på partiklarna och resultatet blev ett tjockt ytskikt. Epoxigrupperna kunde sedan hydrolyseras till dioler vilket gjorde partiklarna mer hydrofila.

En este trabajo se ha realizado el diseño del proceso de purificación deestireno mediante adsorción en alúmina. Esta purificación consiste básicamente enla separación de agua y el inhibidor de la polimerización, 4-terc-butil catecol (TBC),presentes en el estireno como etapa previa en la obtención del caucho sintético, yaque la presencia de estos compuestos dificulta y encarece dicha operación.Para determinar las condiciones experimentales de trabajo, se ha tomadocomo referencia un proceso operativo actualmente a escala industrial en la plantade fabricación de caucho sintético que la empresa Dynasol Elastómeros posee enGajano (Cantabria). Así mismo, se ha empleado el estireno que esta empresautiliza como materia prima que posee alrededor de 150 mg/kg de agua y 15 mg/kgde TBC.En primer lugar, se ha procedido a la determinación de los equilibrios deadsorción agua-alúmina y TBC-alúmina. A continuación, se ha efectuado una seriede experimentos dinámicos a escala de laboratorio en los que se han obtenido laevolución de la concentración de cada uno de los adsorbatos en el estireno a lasalida de la columna de adsorción en función del tiempo. Posteriormente, se hallevado a cabo el desarrollo del modelo matemático para lo que se han analizadolas distintas etapas en el proceso de transferencia de materia, así como susconsecuentes resistencias, y se han obtenido los parámetros correspondientes.A continuación, se ha realizado un análisis del cambio de escala, para lo quese ha procedido a la construcción de una planta piloto en la propia factoría queproduce el caucho sintético, en la que se han realizado diversos experimentos quehan sido contrastados con las simulaciones que predecía el modelo matemático. Lacomparación ha permitido validar el modelo y los parámetros cinéticos.Finalmente, utilizando el modelo y los parámetros obtenidos en las etapasanteriores se ha simulado el proceso de purificación de estireno operativo a escalaindustrial. / In this work, the design of the purification process of styrene by adsorptiononto activated alumina, has been carried out. The purification consists basically ofremoving water and a polimerisation inhibitor, 4-terc-butyl catechol (TBC), as aprevious step in the manufacture of synthetic rubber.To determine the experimental working conditions, a real process thatoperates on industrial scale in a factory which produces synthetic rubber in Spain(Dynasol Elastómeros) has been taken as reference. The styrene used in this workis the industrial raw material and contains approximately 150 mg/kg of water and 15mg/kg of polimerisation inhibitor.First, adsorption equilibrium water-alumina and TBC-alumina have beenstudied. Then, some dynamic experiments on laboratory scale have been carriedout in order to obtain breakthrough curves for both adsorbates. A mathematicalmodel that describes the mass transfer process has been developed analysing thepossible resistances, and the corresponding parameters have been obtained.To analise the scale-up of the adsorption process a pilot plant has been builtin the synthetic rubber factory and the experimental results have been comparedwith the results predicted by the mathematical model. Finally, thanks to themathematical model, the parameters that have been obtained during the laboratoryscale experiments and its validation on pilot plant scale, a model that can describethe industrial process and can be useful to find the best operation conditions hasbeen developed.

An introduction is given to the background theory and scientific literature of the major subject areas of interest in this thesis, namely the chemistry of free radical and anionic polymerisation, molecular weight control in each type of polymerisation, polymerisation reactors, computer simulation of polymerisation processes and polymer characterisation by gel permeation chromatography. A novel computer model has been devised, based on the analysis of the polymerisation process in terms of the reaction extent of each reactant and the use of generation functions to describe the concentration of living and dead polymeric species, for the free radical, solution polymerisation of methylmethacrylate in a CSTR. Both heat and mass balance expressions have been described. Conversion, Mn and Mw were monitored. To test the model a reactor was designed and constructed. A detailed description of the reactor and the experimental conditions used for the validation of the model are given. The results of these studies are presented and excellent agreement is shown between model predictions and experiments up to 30% conversion for Mn w and % conversion. A similar study is described for the anionic polymerisation of styrene in tetrahydrofuran as solvent, in a CSTR. In this work the computer model becomes 'stiff' when realistic rate constants are introduced in the kinetic expressions. Experimental difficulties were encountered in obtaining reproducible results in the anionic work. A new approach of using 'scavengers' as protecting agents for the living chains is described. A scavenger was successfully employed in the preparation of block copolymers using a tubular reactor. Block copolymerisation, in addition to providing a means of checking the number of the 'living' chains inside the reactor, is of interest in its own right. All the experimental findings are discussed in relation to the currently accepted views found in the scientific literature.

Activated Carbon was produced from strong cation-exchange resins, sulphonated styrene divinylbenzene copolymers originally in H+ form, by means of carbonization and steam activation in an electrical furnace. One macroporous resin produced by BAYER Chemicals Inc., Lewatit MonoPlus SP 112 H, was used in the research. Products of carbonization and activation were characterized by using BET, Mercury Porosimetry, Helium Pycnometry and SEM techniques. The effect of carbonization time and temperature on the BET surface areas of the resins were also investigated. Two sets of carbonization experiments (Set 1 and 2) were performed in which time and temperature were varied in order to study their effects on the BET surface areas of the products. In activation experiments (Set 3), carbonized ion-exchangers (600 oC, 1 hr) were activated with steam at 900&deg / C, changing the time of activation and the steam flow rate. The temperatures of the water bath used for steam generation were selected as 60&deg / C, 80&deg / C and 90&deg / C. The pore structures of activated carbons were determined by proper techniques. The volume and area of macropores in the pore diameter range of 8180-50 nm were determined by mercury intrusion porosimetry. Mesopore (in the range of 50-2 nm) areas and volumes were determined by N2 gas adsorption technique at -195.6oC, BET surface areas of the samples were also determined, in the relative pressure range of 0.05 to 0.02, by the same technique. The pore volume and the area of the micropores with diameters less than 2 nm were determined by CO2 adsorption measurements at 0oC by the application of Dubinin Radushkevich equation. In the experiments of Sets 1 and 2, the BET surface area results of the six different carbonization times ranging from 0.5 to 3 hours gave almost the same value with a maximum deviation of 5% from the average showing almost no effect on the areas of the products. In the experiments of Set 3 , the sample activated at 800&deg / C for 6 hrs had the highest BET area, 2130 m2/g, and the one activated at 800&deg / C for 1 hr had the lowest BET area 636 m2/g. N2 adsorption/ desorption isotherms showed no distinct hysteresis indicating a cylindrical geometry of the pores. Adsorption isotherms further indicated that the pores are both highly microporous and mesoporous. N2 (BET) and CO2 (D-R) surface areas of the samples were in the range of 636-2130m2/g and 853-1858 m2/g, respectively. Surface areas of the samples consisted of about 8-53% mesopores and 47-92% micropores.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-08-30T16:14:19Z No. of bitstreams: 1 Tese de Doutorado - Sérgio Botelho de Oliveira.pdf: 18232715 bytes, checksum: b87397cefa6c939563af6c9f1aeaa634 (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-02T15:22:42Z (GMT) No. of bitstreams: 1 Tese de Doutorado - Sérgio Botelho de Oliveira.pdf: 18232715 bytes, checksum: b87397cefa6c939563af6c9f1aeaa634 (MD5) / Made available in DSpace on 2016-09-02T15:22:42Z (GMT). No. of bitstreams: 1 Tese de Doutorado - Sérgio Botelho de Oliveira.pdf: 18232715 bytes, checksum: b87397cefa6c939563af6c9f1aeaa634 (MD5) / Resinas de estireno e divinilbenzeno são materiais atrativos para muitos propósitos por causa das suas propriedades, variedade de grupos funcionais na superfície e porosidade, que podem ser controlados na síntese. Essas características também favorecem a produção de suportes e catalisadores baseados em carvão, com elevada áreas superficiais específicas e com grupos funcionais na superfície, que podem agir como sítios ativos. Eles podem ser usados em muitas reações, entre elas, a desidrogenação do etilbenzeno para produzir estireno. Esse monômero é comercialmente produzido pela desidrogenação do etilbenzeno em presença de vapor de água, mas este processo possui um custo elevado e, portanto, há a necessidade de novas alternativas de produção. A substituição do vapor pelo dióxido de carbono é uma das opções mais atrativas para diminuir o custo energético e, dessa forma, muitos estudos têm sido conduzidos para obter novos catalisadores para essa reação. Com este objetivo, neste trabalho foi descrita a preparação de catalisadores de cobre suportado em carvão ativado polimérico, assim como sua avaliação na desidrogenação do etilbenzeno em presença de dióxido de carbono. O carvão ativado polimérico foi preparado a partir do copolímero estireno e divinilbenzeno sulfonado, seguido da calcinação (250 oC), carbonização (900 oC) e ativação (800 oC). Os íons cobre foram adsorvidos nesse sólido por diversos métodos. O efeito dos metais alcalinos (magnésio e sódio) nas propriedades texturais e catalíticas dos sólidos foi também estudado. As amostras foram caracterizadas por espectrofotometria de absorção atômica, espectroscopia de infravermelho com transformada de Fourier, medidas de área superficial específica e de porosidade, difração de raios X, microscopia eletrônica de varredura e espectroscopia de energia dispersiva. Os catalisadores foram avaliados na desidrogenação do etilbenzeno em presença de dióxido de carbono, a 1 atm e em diversas temperaturas (400, 500 e 600oC). Foram obtidos sólidos com diferentes propriedades texturais e catalíticas, dependendo do método de preparação, assim como da presença de metais. O uso de uma razão de estireno/divinilbenzeno de 15/85 levou à produção de um carvão ativado com a elevada área superficial específica, capaz de adsorver grandes quantidades de cobre, devido aos grupos funcionais gerados na superfície. As propriedades texturais e catalíticas do carvão ativado com cobre foram fortemente dependentes do método de incorporação do cobre. O catalisador mais ativo foi produzido quando o cobre foi adsorvido no carvão ativado previamente oxidado por quatro vezes sucessivas, utilizando-se uma mistura de oxigênio em nitrogênio. Em ambos os sólidos CA e CON, o cobre e os grupos funcionais superficiais no carvão ativado foram ativos na reação. A adição do magnésio aumentou a seletividade a estireno, devido à neutralização de sítios ácidos residuais. O catalisador produzido foi mais ativo do que uma amostra de um catalisador comercial avaliado na presença de vapor, mostrando que o catalisador é promissor para fins industriais / Styrene and divinylbenzene resin is an attractive material for several purposes because of its properties, such as the variety of surface functional groups and porosity, which can be controlled during the synthesis. These characteristics also favor the production of carbon-based supports and catalysts with high specific surface areas and with functional groups on the surface, which can act as active sites. They can be used for several reactions, among them, the ethylbenzene dehydrogenation to produce styrene. This monomer is commercially produced by the ethylbenzene dehydrogenation in the presence of steam but it is a high cost process and thus new alternatives are much needed. The replacement of steam by carbon dioxide is one of the most attractive options to decrease the energy cost and thus several studies have been carried out to find new catalysts for this reaction. With this goal in mind, the preparation of catalysts based on polymeric activated carbon-supported copper, as well as their evaluation in ethylbenzene dehydrogenation in the presence of carbon dioxide, was described in this work. The polymeric activated carbon was prepared from sulfonated styrene- divinylbenzene copolymer, followed by calcination (250 oC), carbonization (900 oC) and activation (800 oC). Copper ions were adsorbed in these solids by several methods. The effect of alkaline metals (magnesium and sodium) on the textural and catalytic properties of the solids was also studied. Samples were characterized by atomic absorption spectrometry, Fourier transform infrared spectroscopy, specific surface area and porosity measurements, X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. The catalysts were evaluated in ethylbenzene dehydrogenation in the presence of carbon dioxide at 1 atm and several temperatures (400, 500 and 600 oC). Solids with different textural and catalytic properties were obtained depending on the preparation method as well as on the presence of metals. The use of a styrene to divinylbenzene ratio of 15/85 leads to the production of an active carbon with the highest specific surface area, which is also able to adsorb a large amount of copper, due to the surface functional groups generated. The textural and catalytic properties of the activated carbon- supported copper largely depended on the method of the copper incorporation. The most active catalyst was produced when copper was adsorbed on activated carbon previously oxidized four times successive with a gas mixture of oxygen in nitrogen. In these solids CA and CON, both copper and the surface functional groups on the activated carbon were active for the reaction. The addition of magnesium increased the selective to styrene, due to the neutralization of the acidic sites on the surface, active for the production of toluene and benzene. The further rising of the catalyst with a sodium hydroxide solution increased the selectivity even more, due to the neutralization of the residual acidic sites. The catalyst produced was more active than a commercial sample evaluated in t

Le développement de techniques de suivi in situ de réactions de polymérisation en émulsion est un véritable enjeu, motivé par le désir d’établir des relations entre structure, propriétés physico-chimiques et propriétés d’usage du latex final. Par ailleurs, ces techniques fournissent des informations sur les phénomènes chimiques et physico-chimiques mis en jeu qui contribuent à une meilleure compréhension. Des études récentes montrent que la spectroscopie Raman peut être une technique adaptée à cette problématique, de par sa simplicité de mise en œuvre (transportabilité, adaptabilité de l’appareillage, etc.), la performance de la mesure (temps d’acquisition de l’ordre de la seconde) et la richesse des informations fournies (de l’échelle moléculaire à celle du matériau). L’objectif de notre travail a été de déterminer le potentiel de la spectroscopie Raman quant au contrôle de la polymérisation en macroémulsion du styrène tant au niveau du bon déroulement de la réaction (conversion…) qu’au niveau des propriétés du latex formé (stabilité…). Pour réaliser ce travail expérimental, un pilote de polymérisation a été installé pour la première fois au sein du laboratoire des Matériaux Optiques, Photonique et Systèmes (LMOPS). La particularité de notre système est qu’il a été conçu pour conserver le maximum de liberté pour la réalisation de l’étude spectroscopique (montages optiques). La première partie de notre projet a donc été de déterminer un protocole adapté à ce pilote, tant au niveau de la réalisation de la synthèse de latex de polystyrène stabilisé qu’au niveau de l’acquisition de données spectroscopiques. Par la suite, nous avons démontré que la spectroscopie Raman était une technique adaptée au suivi in situ de la cinétique de polymérisation du styrène en macroémulsion. Le suivi du taux de conversion du styrène en polystyrène a été réalisé selon deux méthodes qui reposent sur des principes différents : la première basée sur la variation de l’aire de bandes spécifiques est une approche classique de la quantification de cette grandeur alors que la deuxième, basée sur la modification de la position d’une bande commune au monomère et à son polymère est une méthode innovante. A partir de ces données expérimentales et grâce à une méthode de filtrage adaptée, la quantification de la vitesse de polymérisation a été proposée pour la première fois. Ces données expérimentales ont été comparées à la théorie mécanistique et cinétique de référence de ce procédé, ainsi qu’à de précédents résultats expérimentaux, obtenus par d’autres techniques. Alors que les résultats expérimentaux s’accordent, ils montrent tous une déviation par rapport à la théorie. Enfin, par l’étude approfondie de la variation de l’aire d’une bande de référence, commune au monomère et au polymère, nous avons démontré que la spectroscopie Raman était sensible au phénomène de diffusion élastique, diffusion du faisceau laser par les éléments dispersés dans le milieu réactionnel. Cela se traduit par une modification de l’intensité du signal collecté et permet donc de détecter une transition caractéristique du procédé de polymérisation étudié : la disparition des gouttelettes réservoir de monomère, qui apparaît vers 40% de conversion dans le cas du styrène / The development of in situ monitoring techniques of emulsion polymerization reactions is a real current challenge. First, it may help establish relations between the structure, the physicochemical properties and the performance properties of final latexes. Moreover, it brings a better understanding of chemical and physicochemical phenomenon that happened. Easy installation, performance of measures and abundance of information gathered (from molecular to material scales) make the Raman spectroscopy an adequate technique for this kind of issue, as shown in recent studies. The main goal of that work was to demonstrate the capacity of the Raman spectroscopy to control the polymerization of styrene via macroemulsion process, in terms of smooth reaction process (conversion, …) and final properties of the latex (stability, …). This work was carried in the laboratoire des Matériaux Optiques, Photonique et Systèmes (LMOPS) where a polymerization pilot was implemented for the first time. The latest has been designed in order to ensure a maximum freedom for spectroscopic measurements (optical setup). Because of this special design, the first part of this work was to adapt experimental conditions, in terms of polymer latex synthesis and spectroscopic data acquisition. Thereafter, we proved that Raman spectroscopy could be a suitable technique for real time in situ conversion monitoring in the case of the polymerization of styrene via macroemulsion process. The monomer conversion monitoring has been realized in two different methods: the first one is well-known and is based on monitoring changes in the normalized Raman signal of specific band and the second one is an innovative method that is based on the Ramanshift of a common band of styrene and polystyrene. On the basis of these experimental data and using a suitable smoothing method, the polymerization rate was quantified for the first time. The results were compared to the theory of this polymerization process and previous experimental results from other experimental techniques. Whereas experimental results show similarities, they all show a deviation from the theory. Finally, an in-depth study of the impact of the heterogeneity of the reaction media on the Raman signal has been made. We have demonstrated that this latest was sensitive to elastic scattering of light by dispersed particles. The influence of elastic scattering on the intensity of the collected Raman signal makes the Raman spectroscopy a suitable method to detect a specific transition of the polymerization process: the disappearance of monomer droplets around 40 % of conversion in case of styrene

150f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-01T15:55:02Z No. of bitstreams: 1 Tese final Danns Barbosa 08,02,11.pdf: 6113429 bytes, checksum: 69ec8ea24d6f9bf83f16a0221337ec76 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-24T17:03:41Z (GMT) No. of bitstreams: 1 Tese final Danns Barbosa 08,02,11.pdf: 6113429 bytes, checksum: 69ec8ea24d6f9bf83f16a0221337ec76 (MD5) / Made available in DSpace on 2013-04-24T17:03:41Z (GMT). No. of bitstreams: 1 Tese final Danns Barbosa 08,02,11.pdf: 6113429 bytes, checksum: 69ec8ea24d6f9bf83f16a0221337ec76 (MD5) Previous issue date: 2011 / CAPES / O amplo uso de fertilizantes nitrogenados, bem como os sistemas de saneamento rudimentares e as atividades pecuárias, têm aumentado a contaminação das águas subterrâneas e, portanto, da água potável. Devido aos graves riscos das espécies nitrato para a saúde humana, tem sido dispensada muita atenção para o desenvolvimento de tecnologias para removê-las da água. Dessa forma, neste trabalho foram preparados catalisadores bimetálicos de paládio e estanho ou índio suportados em estireno-divinilbenzeno (Sty-DVB) sulfonado, a fim de desenvolver catalisadores eficientes para a remoção das espécies nitrato da água. O suporte foi sintetizado por polimerização em suspensão, enquanto os catalisadores bimetálicos foram preparados por dois métodos: impregnações sucessivas e redução catalítica. Foram obtidos catalisadores com 5% m/m de paládio e vários teores (0,5, 2 e 4% m/m) de estanho ou índio, que foram caracterizados por espectroscopia no infravermelho com transformada de Fourier, adsorção de nitrogênio, análise química elementar, difração de raios X, termogravimetria e microscopia eletrônica de varredura. Os catalisadores foram avaliados na redução das espécies de nitrato na água, na presença e na ausência de dióxido de carbono. Verificou-se que o suporte não adsorve nitrato, nitrito e amônia e não apresenta atividade na redução das espécies nitrato. Os catalisadores com índio foram mais ativos na redução de espécies nitrato, e menos seletivos a nitrogênio, do que os catalisadores com estanho. Além disso, os catalisadores com estanho e preparados por redução catalítica foram mais ativos do que aqueles preparados por impregnações sucessivas. Um comportamento inverso foi observado com os catalisadores contendo índio. Com a maioria das amostras, o dióxido de carbono aumentou a atividade, reduziu a seletividade a nitrito e aumentou a produção das espécies amônio. Os melhores desempenhos catalíticos foram apresentados pelas amostras 5%Pd2%Sn/Sty-DVB, (atividade=15,2 cmol. min-1.g-1; seletividade a nitrogênio = 98%) e 5%Pd0,5%In/Sty-DVB (atividade= 18,8 cmol.min-1.g-1; seletividade a nitrogênio = 89%), preparadas por impregnações sucessivas e redução catalítica , respectivamente. / Salvador