Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Microesferas poliméricas magnéticas à base de estireno (STY), divinilbenzeno (DVB), acetato de vinila (VAc) e ferro foram preparadas via polimerização em suspensão e semissuspensão. Foram estudadas as influências da concentração de VAc adicionado na polimerização e a presença de ferro sobre as características das partículas poliméricas obtidas. Estas partículas foram caracterizadas por espectrometria de absorção na região do infravermelho (FT-IR), análise térmica (TGA/DTA), microscopia óptica (MO), microscopia eletrônica de varredura (SEM) e magnetometria de amostra vibrante (VSM). Foram obtidas com sucesso microesferas poliméricas com propriedades magnéticas à base de estireno, divinilbenzeno e acetato de vinila. Estes materiais apresentaram bom controle morfológico, com maior rendimento na faixa de 120 a 75 m. Apresentaram também boas propriedades magnéticas (22,62 a 73,75 emu/g) com comportamento próximo de materiais superparamagnéticos e boa estabilidade térmica (444 C) / Magnetic polymeric microspheres based on styrene (STY), divinylbenzene (DVB), ethylene vinyl acetate (VAc) and iron were prepared via suspension and half suspension polymerization. The influence of the concentration of VAc and iron added to the polymerization on the characteristics of polymeric particles obtained were studied. These particles were characterized by infrared spectrometry (FT-IR), thermal analysis (TGA / DTA), optical microscopy (OM), scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM). Polymeric microspheres with magnetic properties based on styrene, divinylbenzene and vinyl acetate were obtained. These materials showed good morphological control and large yield range from 120 to 75 micrometers. They also showed comparable magnetic properties (from 22.62 to 73.75 emu/g) to superparamagnetic materials and good thermal stability (444 C)

Copolímeros casca-núcleo de poli(acrilato de butila) (núcleo) e poliestireno (casca) foram sintetizados por meio de polimerização em emulsão, conduzida em duas etapas. A adição de ácido itacônico como monômero funcional na polimerização do núcleo foi realizada para verificar seu efeito sobre suas propriedades mecânicas e de processamento. Os copolímeros foram caracterizados por espalhamento dinâmico de luz (DLS), microscopia eletrônica de transmissão (MET), cromatografia de exclusão por tamanho (SEC), espectrometria na região do infravermelho (FTIR) e calorimetria diferencial por varredura (DSC). A incorporação do monômero funcional foi confirmada por DSC e quantificada por titulação. A proporção de poli(acrilato de butila) e poliestireno influenciou diretamente o processamento e as propriedades mecânicas do polímero. Os copolímeros com teores de poliestireno acima de 50% foram processados por compressão e extrusão a temperatura ambiente, apresentando comportamento baroplástico. A presença do monômero funcional não alterou o processamento do polímero e melhorou significativamente sua resistência à tração, aumentando sua tenacidade / Core shell copolymers of poly(butyl acrylate) cores and polystyrene shells were synthesized in a two-stage emulsion polymerization. The addition of itaconic acid as functional monomer in the core polymerization was carried out in order to study its influence on polymer processing and mechanical properties. The copolymers were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The functional monomer incorporation was confirmed by DSC and quantified by titration. The poly(butyl acrylate) and polystyrene proportions had a direct influence on the polymer processing and mechanical properties. Copolymers with polystyrene contents higher than 50% presented baroplastic behavior and they could be processed at room temperature by compression molding and extrusion. The presence of itaconic acid did not affect polymer processing and significantly improved tensile resistance, increasing its toughness

Foi estudada a enxertia de estireno induzida por radiação gama em filmes de poli(fluoreto de vinilideno) (PVDF) com espessura de 0,125 mm com doses entre 1 e 100 kGy em presença de soluções de estireno/N,Ndimetilformamida (DMF) (1:1, v/v) e estireno/tolueno (1:1, v/v) com taxa de dose de 5 kGy.h-1 por meio do método simultâneo de irradiação sob atmosfera de nitrogênio e em temperatura ambiente, usando raios gama de uma fonte de Co- 60. Depois de enxertados, os polímeros foram sulfonados em soluções de ácido clorossulfônico/1,2-dicloroetano (2 e 10 %). Os filmes foram caracterizados antes e depois de cada modificação com o cálculo do Grau de enxertia, (DOG), espectrometria no infravermelho (FT-IR), microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC) e termogravimetria (TG/DTG). Os resultados do grau de enxertia mostraram que a enxertia aumenta com o aumento da dose e varia enormemente de acordo com o solvente utilizado, com enxertias cerca de 20 vezes maiores quando do uso da DMF em relação ao do tolueno. Foi possível confirmar a enxertia do estireno por FT-IR graças ao aparecimento de novos picos característicos e por TG/DTG e DSC por meio das alterações do comportamento térmico dos materiais enxertados/sulfonados. Os materiais sulfonados ainda foram caracterizados por suas capacidades de troca iônica (IEC), que mostraram que tanto os aumentos do grau de enxertia quanto os da concentração do ácido clorossulfônico aumentam o IEC. Os resultados mostraram que é possível obter materiais com capacidades de troca iônica com possibilidade de aplicação como compósitos ionoméricos de metal-polímero. / Gamma-radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses from 1 to 100 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and styrene/toluene (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere at room temperature, using gamma rays from a Co-60. After grafting reactions, the polymer was then sulfonated in chlorosulfonic acid/1,2-dichloroethane (2 and 10%) for 3 hours. The films were characterized before and after modification by calculating the degree of grafting (DOG), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). DOG results show that grafting increases with dose, and varies enormously depending on the solvent used, with DOGs about 20 times greater in DMF than in toluene. It was possible to confirm the grafting of styrene by FT-IR due to the appearance of the new characteristic peaks and by the TG and DSC which exhibited changes in the thermal behavior of the grafted/sulfonated material. Sulfonated material was also characterized by ion exchange capacity (IEC) showed that both DOG and sulfonic acid concentration increase IEC values. Results showed that it is possible to obtain materials with ion exchange capacity of possible application as ionic polymer-metal composites.

<p>Strukturiranje elastomernih kompozita dodavanjem različitih vrsta nanopunila je dovelo do značajnog pobolj&scaron;anja njihovih primenskih svojstava, a samim tim i do povećanja njihove potencijalne primene kao pogodnih materijala za specijalne namene. U ovom radu, dobijene su dve grupe elastomernih hibridnih materijala za specijalne namene (na osnovu stirenbutadienskog elastomera i na osnovu termoplastičnih poliuretana).<br />U prvom delu istraživanja, veliki doprinos u razvoju industrije gume je postignut strukturiranju stirenbutadienskih nanokompozita primenom nanočestica punila silicijum(IV)oksida različitih morfolo&scaron;kih svojstava, dobijenih hidrotermičkom i termičkom obradom, primenom tri eksperimentalno modelovana punila silicijum(IV)oksida (dobijena taloženjem iz Na-vodenog stakla sa sumpornom kiselinom), kao i hibridnog punila (kombinacije čestica aktivne čađi i SiO₂ optimalnih svojstava). Izvr&scaron;ena je analiza uticaja strukture, povr&scaron;ine i povr&scaron;inske aktivnosti nanopunila na ojačanje elastomera, kao i provera koncepata, modela i teorija ojačanja na neumreženim i umreženim sistemima stirenbutadienskih elastomera ojačanih modifikovanim punilima SiO₂. Primenom mnogobrojnih metoda karakterizacije, sveobuhvatno je ispitan uticaj nanopunila na karakteristike me&scaron;anja, reolo&scaron;ka svojstva pripremljenih hibridnih nanokompozita, sposobnost umrežavanja u neumreženom materijalu, kao i na toplotna, dinamičko-mehanička i mehanička svojstva umreženih nanokompozita, radi projektovanja i optimizovanja sastava SBR hibridnih materijala za razvoj modelnog protektora sa optimalnim svojstvima za ekolo&scaron;ke ili &quot;zelene pneumatike&quot;. Drugi deo istraživanja je bio posvećen dobijanju segmentiranih poliuretanskih elastomernih nanokompozita primenom alifatičnih polikarbonatnih diola i nanočestica bentonita, koji nalaze primenu u medicini, građevinarstvu, u industriji name&scaron;taja i sportske opreme. Primenom mnogobrojnih metoda za karakterizaciju, ispitan je složen mehanizam uticaja tvrdih segmenata, termodinamičke nekompatibilnosti i prisustva nanočestica punila bentonita na strukturu i morfologiju, kao i na toplotna i dinamičko-mehanička svojstva pripremljenih poliuretanskih termoplastičnih elastomera. Dobijeni podaci o obrazovanju vodoničnih veza, termičkoj stabilnosti i termičkoj dekompoziciji, kao i o temperaturama prelaska u staklasto stanje i oblasti raskidanja čvorova fizičkih veza, predstavljaju značajan doprinos napretku strukturiranja poliuretanskih elastomera i nanokompozita na osnovu alifatičnih polikarbonatnih diola, i omogućavaju primenu ovih materijala za specijalne namene.</p> / <p>The structuring of elastomeric composites by addition of different nanofillers has led to a significant improvement of their end-use properties, and therefore, to their potential application as suitable materials for special applications. In this work, two types of elastomeric hybrid materials for special purposes were obtained (based on styrene-bustadiene elastomer or on segmented thermoplastic polyurethanes).<br />In the first part of the study, a major contribution to the development of the rubber industry was achieved by structuring styrene-butadiene nanocomposites, applying silica nanoparticles of various morphological properties: prepared by hydrothermal or thermal treatment, three experimentally prepared SiO2 fillers (obtained by precipitation from sodium silicate with sulfuric acid), as well as a hybrid filler (combination of carbon black and SiO2 fillers with optimal properties). The analysis of the influence of the nanoparticles structure, surface and surface activity on the reinforcment of SBR elastomers, as well as the verification of concepts, models and reinforcement theories on non-cross-linked and cross-linked systems of styrene-butadiene nanocomposites was performed. Using the numerous characterization methods, the influence of nanofillers on the mixing characteristics, the rheological properties of the prepared hybrid nanocomposites, as well as the thermal, dynamic-mechanical and mechanical properties of cross-linked SBR nanocomposites was studied, in order to design and optimize the composition of SBR hybrid materials for development of environmental friendly or &quot;green&quot; tyre protector model.<br />The second part of the research was devoted to the preparation of segmented polyurethane elastomeric nanocomposites using aliphatic polycarbonate diols and bentonite nanoparticles, that have found the significant application in the medicine, construction, the furniture and sports equipment industry. Applying numerous characterization methods, a complex mechanism of the influence of the hard segments, thermodynamic incompatibility and the presence of bentonite filler on the structure and morphology, as well as on the thermal and dynamic-mechanical properties of the synthesized thermoplastic elastomers was studied. The obtained data on the hydrogen bonds formation, thermal stability and thermal decomposition, as well as the glass transition temperature and physical crosslink disruption temparature range, makes a significant contribution to the progress in structuring of polycarbonate-based polyurethane elastomers and their hybrid materials, and improves their potential applications for the special purposes.</p>

<p>In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).</p>

In risk assessment of risk chemicals, variability in susceptibility in the population is an important aspect. The health hazard of a pollutant is related to the internal exposure to the chemical, i.e. the target dose, rather than the external exposure. The target dose may be calculated by physiologically based pharmacokinetic (PBPK) modeling. Furthermore, variability in target dose may be estimated by introducing variability in the physiological, anatomical, and biochemical parameters of the model. Data on these toxicokinetic model parameters may be found in the scientific literature. Since the early seventies, a large number of experimental inhalation studies of the kinetics of several volatiles in human volunteers have been performed at the National Institute for Working Life in Solna. To this day, only very limited analyses of these extensive data have been performed. A Bayesian analysis makes it possible to merge a priori knowledge from the literature with the information in experimental data. If combined with population PBPK modeling, the Bayesian approach may yield posterior estimates of the toxicokinetic parameters for each subject, as well as for the population. One way of producing these estimates is by so-called Markov-chain Monte Carlo (MCMC) simulation. The aim of the thesis was to apply the MCMC technique on previously published experimental data. Another objective was to assess the reliability of PBPK models in general by the combination of the extensive data and Bayesian population techniques. The population kinetics of methyl chloride, dichloromethane, toluene and styrene were assessed. The calibrated model for dichloromethane was used to predict cancer risk in a simulated Swedish population. In some cases, the respiratory uptake of volatiles was found to be lower than predicted from reference values on alveolar ventilation. The perfusion of fat tissue was found to be a complex process that needs special attention in PBPK modeling. These results provide a significant contribution to the field of PBPK modeling of risk chemicals. Appropriate statistical treatment of uncertainty and variability may increase confidence in model results and ultimately contribute to an improved scientific basis for the estimation of occupational health risks.

Several approaches have been used to develop carbon nanotube (CNT) based electrochemical supercapacitors. These approaches include the following: (a) stabilization and carbonization of ternary composites of polyacrylonitrile (PAN), poly (styrene co-acrylonitrile) (SAN) copolymer, and single wall carbon nanotubes (SWNTs); (b) SWNT membranes functionalized with aryl chloride, sodium sulfonate, aryl sulfonic acid, bis(3,5-di-tert-butylphenyl)5-aminobenzene-1,3-dioate, and 4,4 -methylenedianiline; and (c) pyrrole treated SWNTs. In addition nitric acid functionalized and heat-treated SWNT membranes have been studied. The electrochemical supercapacitor behavior of these membrane electrodes has been characterized by cyclic voltammetry, constant current charging-discharging, and impedance analysis in aqueous and ionic liquid electrolytes. Long term performance of selected electrodes has been evaluated. The surface area and pore size distribution was quantified by N2 gas adsorption/desorption and correlated with capacitance performance. The surface functional groups have been characterized by X-ray photoelectron spectroscopy. CNT electrode/electrolyte interaction has been characterized using contact angle measurements. Electrolyte absorption by the electrodes has also been characterized. Carbonized PAN/SAN/SWNT ternary composites exhibit double layer capacity of over 200 μF/cm2. By comparison, the double layer capacity of classical meso-porous carbons is in the range of 10-50 μF/cm2. The capacitance of functionalized SWNTs is up to 2 times that of the control bucky paper made from unfunctionalized SWNTs. Energy density of functionalized electrodes when evaluated in an ionic liquid is as high as 28 kJ/kg. High capacitance (up to 350 F/g) was obtained for pyrrole-treated functionalized SWNT membranes in 6 M KOH. This value is almost seven times that of the control bucky paper. Correlating the capacitance with surface area and pore size distribution, it was observed that macropores (pore width greater than 50 nm) play an important role for achieving high capacitance.

Chiral bisphosphinites are well-documented alternatives for chiral bisphosphines as ligands that can be exploited in various asymmpetric syntheses. Particularly, vicinal biarylphophinite ligands give a seven membered chelate ring similar to the successful DIOP on coordination to the metal. RajanBabu and coworkers have described asymmetric bisphosphinites obtained by functionalization of sugars and have shown their utility in enantioselective hydrogenation, hydrovinylation and hydrocynation reactions. Despite the interesting reactions demonstrated by bisphosphinites, not much attention has been paid to their synthesis and catalysis. This is probably due to the known moisture and oxygen sensitivity that makes their use limited. In the present thesis, a series of C1 an C2 symmetric bisphosphinite complexes of Pd(II) and Pt(II) have been synthesized directly from various naturally occurring chiral alcohols using a modified template method. A number of asymmetric catalytic reactions have been developed such as allylation of imines, allylation of aldehydes, allylic allylation, allylic alkylation, hydrosilylation of alkenes and regioselective allylation of oxiranes. Allylation of imines was carried out in essentially neutral conditions using Pd(II) catalysts and water was shown to accelerate the reaction. Interestingly acetic acid was required as a promoter in asymmetric allylation of cinnamaldehyde in the Pt(II) catalyzed reaction whereas water was a deterrent. Hydrosilylation reaction was carried out in solvent free conditions with high turnover numbers (.1000). Ascorbic acid based complexes produced the highest enantioselectivity for the asymmetric allylic alkylation reaction (97 % ee) and hydrosilylation of styrene (98% ee). These enantioselectivity results are the best obtained using ligands directly prepared from natural products.

No description available.

Las esmectitas como hectorita o saponita, son silicatos laminares. Tienen múltiples aplicaciones (catálisis, nanocomposites, adsorbentes) e interesa tener un material reproducible y sin impurezas. Los métodos convencionales de síntesis comportan tratamientos largos o a altas temperaturas. La introducción del microondas puede disminuir ambos. El objetivo de esta tesis es estudiar la síntesis de hectorita y saponita con microondas y su aplicación como soportes catalíticos de Ni en la hidrogenación de óxido de estireno para la obtención de 2-feniletanol (componente principal de la esencia de rosas) y en la preparación de composites con poliuretano. Se obtienen hectoritas y saponitas reproducibles. Cuando se emplean como soportes de catalizadores de Ni se obtienen conversión y selectividad total hacia el 2-feniletanol. Cuando se utilizan las arcillas obtenidas en preparación de composites sus propiedades son comparables a los de la bibliografía. / Smectites like hectorite or saponite, are phyllosilicates. They can be applied for many purposes (catalysis, nanocomposites, adsorbents) but a reproducible, pure material is necessary. Classical methods of synthesis involve long synthesis times at high temperatures. The use of microwaves can be an interesting alternative. The scope of this thesis is to study the synthesis of hectorites and saponites with microwaves and their application as supports of Ni catalysts in the hydrogenation of styrene oxide to obtain 2-phenylethanol (main component of rose oil) and in the preparation of composites with polyurethane. We obtained reproducible hectorites and saponites. When used as supports of Ni catalysts we obtained total conversion and selectivity to 2-phenyethanol. When obtained clays were used in the preparation of polyurethane composites, their properties were comparables to those of the bibliography