Orientador: Liliane Maria Ferrareso Lona / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-13T07:23:03Z (GMT). No. of bitstreams: 1 Machado_PaulaFortedeMagalhaesPinheiroBonassi_D.pdf: 14222039 bytes, checksum: e1250529dcd3d3572615408ed87bb7cf (MD5) Previous issue date: 2009 / Resumo: A utilização de iniciadores químicos com funcionalidade superior a um, na polimerização via radical livre, tem crescido muito no meio acadêmico, científico e industrial. Estes tipos de iniciadores têm a capacidade de aumentar a velocidade da reação sem causar a redução do peso molecular do polímero formado. Além disso, iniciadores com funcionalidade superior a dois (multifuncionais), que não sejam cíclicos, podem ter a capacidade de gerar ramificações nas cadeias, alterando a microestrutura do produto. Existem alguns poucos trabalhos em literatura que abordam, em nível experimental e/ou de simulação, a polimerização via radical livre utilizando-se iniciadores bifuncionais (com dois grupos funcionais). Em Machado (2004), encontram-se modelos matemáticos utilizando iniciadores bifuncionais para a produção de polímeros lineares (poliestireno) e ramificados (poliacetato de vinila), este último, inédito em literatura aberta. O grau de complexidade envolvido no mecanismo cinético aumenta de forma significativa à medida que se aumenta a funcionalidade do iniciador. O objetivo deste trabalho foi estudar a polimerização via radical livre utilizando um iniciador cíclico trifuncional (TRIGONOX 301, T301). Este trabalho foi desenvolvido em nível experimental (polimerização em ampolas) e computacional (desenvolvimento de modelo matemático, modelagem e simulação). Esta pesquisa propôs um mecanismo cinético e um modelo matemático para polimerização via radical livre do estireno utilizando um iniciador trifuncional. O estireno foi escolhido por ser bastante conhecido e por existir muitos dados e informações a seu respeito em literatura aberta. O modelo matemático construído prediz resultados como conversão, peso molecular (Mn e Mw), concentração de radicais e concentração de polímero. A investigação experimental foi realizada para validar os resultados de simulação. O método utilizado foi a polimerização em ampolas. Análises de Cromatografia por Permeação em Gel (GPC), Microscopia Eletrônica por Varredura (MEV), Difração por Raio-X (DRX) e Calorimetria Exploratória Diferencial (DSC) foram realizadas nas amostras obtidas experimentalmente para uma melhor caracterização do polímero final. As validações foram feitas para os resultados de conversão e peso molecular. Os resultados obtidos na parte experimental foram de extrema importância para se obter a validação da parte de modelagem e simulação, bem como para se poder conhecer o comportamento do iniciador trifuncional T301. O modelo de predição apresentou boa concordância com os dados experimentais. Através de seu uso, pode-se explorar a reação de polimerização, podendo verificar o comportamento das várias espécies nela presentes. Além disso, pode-se também estudar os efeitos de algumas variáveis como a temperatura e a concentração de iniciador durante a reação de polimerização e também no produto final. Este estudo se apresenta como uma investigação abrangente da polimerização usando um iniciador trifuncional, fornecendo uma ferramenta que pode simular com confiabilidade a polimerização do estireno via radical livre e, também, apresentando outros tipos de análise que podem ser realizadas no polímero final obtido. Deve-se destacar que através do uso do iniciador trifuncional T301, houve a possibilidade de obtenção de poliestirenos com altos pesos moleculares, simultaneamente com reduzidas polidispersidades (curvas de distribuição de peso molecular estreitas), a altas temperaturas e, como conseqüência, com elevadas taxas de reação. / Abstract: Researchers from industries and universities have investigated the use of initiators with functionality greater than one, in free radical polymerization. These types of initiators are able to increase the polymerization reaction rate with no decrease in molecular weight. Besides, initiators with functionality greater than two (multifunctional initiators), those that do not have a cyclic structure, are able to generate branches in the polymer chains, changing the product microstructure. Experimental studies of initiators with functionality greater than two in free radical polymerization are very few and the modeling of such systems is really scarce. The complexity of the kinetic mechanism increases with the increasing of the initiator functionality. Machado (2004) presents mathematical models using mono- and bifunctional initiators in free radical polymerization of linear (polystyrene) and branched (poly vinyl acetate) polymers. This last case is brand new in open literature. The objective of this work was to study free radical polymerization using a trifunctional cyclic initiator (TRIGONOX 301, T301). This work was developed in experimental level (polymerization in ampoules) and in computational level (development of mathematical model, modeling and simulation). This research proposed a kinetic mechanism and developed a mathematical model to free radical polymerization of styrene using a trifunctional initiator. Styrene was chosen because it is a very well known monomer and there is a lot of data about it. The mathematical model built predicts results as conversion, molecular weight (number average, Mn, and weight average, Mw), radical concentration and polymer concentration profiles. An experimental investigation was also made in order to validate the simulation results. The experimental part followed the method of polymerization in ampoules. The following analyses were performed to characterize the samples of polymers obtained experimentally: Gel Permeation Cromatography (GPC), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). The validation was made to conversion and molecular weights. The experimental results were very important to validate the model and also to investigate the behavior of the trifunctional initiator T301. Model simulations showed good agreement with experimental data. Simulations could explore the polymerization reaction, verifying the behavior of all species present in it. Also, it was possible to study the effects of some variables as temperature and initiator concentration during the reaction and in the final product. This study is a comprehensive investigation of a reaction using a trifunctional initiator, providing a model that simulates accurately the free radical polymerization of styrene and, also, presenting types of different analysis that can be done in the final polymer. It should be noted that the use of the trifunctional initiator T301 in free radical polymerization brought the possibility of obtaining polystyrenes with high molecular weights, simultaneously with reduced polydispersities (narrower MWD profiles), at high temperatures and, as a consequence, at high reaction rates. / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

No description available.

<p> A computer model is developed to simulate the emulsion copolymerization of styrene/butadiene in perfectly stirred batch, semi-batch or continuous flow reactors. The model considers free radical initiation by a redox mechanism, micellar particle nucleation, radical concentration as -a function of particle size, radical entry rate and termination rate and diffusion controlled termination and propagation reactions. It predicts conversion, copolymer composition, particle number, number and mass average molecular masses and tri- and tetra-functional branch frequencies. A simple method of estimating the particle size distribution is included in the model. Heat balances over the reactor and cooling jacket are considered and proportional-integra control of the reactor temperature is simulated.</p> <p> The model is used to simulate SBR copolymerization and styrene homopolymerization experimental data from the literature. These simulations tested only certain parts of the model and it is concluded that a more complete verification of the model can only be achieved by running a series of designed experiments. Qualitatively, the molecular mass, particle size distribution and reactor temperature predictions appear to be reasonable. The lack of appropriate temperature dependent rate constants currently limits the molecular mass predictions to isothermal conditions.</p> <p> A comparison of semi-batch operating policies designed to control copolymer composition is presented to illustrate the potential application of the model.</p> / Thesis / Master of Engineering (ME)

<p> This dissertation describes an investigation into the free radical polymerization of styrene in continuous stirred tank reactors (CSTR's). The aim was to develop a steady state polymerization model which would accurately predict conversion and molecular weight distribution (MWD) up to high conversion. </p> <p> The dissertation is divided into three self-contained parts. Part I describes the testing and development of polymerization kinetics using a single CSTR. The single CSTR model is described. Theoretical and experimental conversions and MWD's are compared and discussed. </p> <p> Part II describes the development of a model for a system of CSTR's. It is based upon the single CSTR model and the kinetics developed in Part I. Theoretical and experimental results for a three reactor system are compared and discussed. </p> <p> Part III describes the development of gel permeation chromatography (GPC) for measuring MWD. Molecular weight and resolution calibration data are presented and discussed. Four methods of chromatogram interpretation that correct for imperfect resolution are compared. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

Polymers containing less than 10 mol % of ions (ionomers) have been studied in depth for their potential in producing polymers with tailored properties for specific applications. A small molar percentage of ions can be incorporated into a polymer to drastically enhance the properties of the polymer. An ionomer that has been studied is that of isoprene copolymerized with sodium styrene sulfonate (poly(I-co-NaSS)). Research has been performed relating to the synthesis and chemical characterization of the copolymers. However, an in depth study of the way the physical properties are affected by a change in ion concentration has not been presented. Thus, it is the goal of this thesis to synthesize a series of poly(I-co-NaSS) copolymers with varying levels of sulfonated styrene and characterize their physical properties. The poly(I-co-NaSS) polymers, containing a range of 1.15 to 4.74 mol % NaSS, were polymerized using free radical emulsion polymerization. The copolymer compositions were confirmed using combustion sulfur analysis. Dynamic light scattering indicated that large aggregates were present in solution. These aggregates were large enough that capillary intrinsic viscosities could not be measured. Small angle x-ray scattering (SAXS) and thermal analysis showed little change as the ion concentration was increased, while tensile, stress relaxation and adhesion properties were improved. The absence of changes in the SAXS patterns indicated that there was an absence of a well-defined ionic aggregate, while the mechanical properties showed evidence of electrostatic interactions. This can be at least partially attributed to ionic interactions on a smaller scale (doublets, triplets). / Master of Science / This research pertains to the creation of a series of polymers containing small amounts of ionic groups that allow tailoring the properties of the materials. The main component of the polymer is polyisoprene, which is also referred to as “natural rubber”. This material is elastic and can be used as a rubber (gloves) or can be manipulated to create a strong adhesive through addition of ionic groups. The polymers were synthesized with varying levels of ionic groups, creating a series of six polymers. These polymers were tested for their chemical composition (the chemical make-up of the polymers), morphological properties (their phase structure and self-assembly of the polymers on a nanometer to micron scale), and their mechanical properties (the strength, elasticity, and adhesive properties of the polymer). It was determined that in terms of the morphology, the polymer remained mostly unchanged as the ion content was increased, but the mechanical properties improved dramatically. As the concentration of ionic groups increased, the strength of the polymer as well as the adhesive properties of the polymer, also increased. Understanding the structure-property relationships of these copolymers can allow researchers to tailor their structures to fit a desired application.

No / Core-shell particles have been prepared by surfactant-free emulsion polymerisations of butyl methacrylate in the presence of either linear or highly branched poly(acrylamidomethylpropane sulphonate)s (L-PAMPS or HB-PAMPS) with dithioate end groups: using a "shell-first" approach. In this method the water soluble PAMPS shells were anchored to the cores by polymerisation of BMA from the chain ends. The linear PAMPS produced non-crosslinked poly(AMPS-BMA) particles but the multiple chain ends of the highly branched PAMPS led to crosslinked particles. The particles were loaded with vascular endothelial growth factor or platelet derived growth factor, both of which are cytokines that are known to be important in the production of new blood vessels. The release of the growth factors was shown to be controlled by the architecture of the shell and we propose a mechanism that involves both ionic interaction of the PAMPS with the heparin-binding domains of the growth factors and size exclusion mediated diffusion.

This study investigated the dry sliding of Acrylonitrile Butadiene Styrene (ABS) in a polymer-on-polymer configuration. The effect of several material and system parameters were investigated to determine their influence on the frictional behavior of the ABS materials. These parameters included: the time dependence of friction under static load, friction-normal load relationships, surface roughness, internal lubrication, friction-velocity relationships, and system stiffness. Four basic types of frictional behavior were observed - steady sliding, a single stick followed by steady sliding, non-sustained stick-slip oscillations that decayed after several oscillations, and stick-slip oscillations lasting several minutes. Several observations were made regarding the experimental results. It was observed that increasing surface roughness decreases the unstable behavior of the materials. Also, decreasing normal load decreased unstable behavior. A relationship between the friction-velocity curve, stick-slip, and the critical velocity at which stick slip disappeared was observed. Finally, an attempt was made to explain the observed behavior in light of existing theories. / M.S.

O uso de asfaltos modificados com polímeros tem crescido significativamente nas últimas décadas em função do aumento da densidade de tráfego, da carga por eixo nos veículos e da pressão dos pneus. Estes ligantes proporcionam o aumento a vida útil e a redução do custo de manutenção das rodovias. Os polímeros mais utilizados na modificação de asfalto são os copolímeros em bloco de estireno-butadienoestireno. Esta tese avaliou os efeitos de diferentes agentes compatibilizantes (óleos) e agentes de ligação no comportamento reológico de misturas asfálticas modificadas com copolímeros de estireno-butadieno-estireno, bem como a influência da sua estrutura, se linear ou radial. Para isto foram realizados análises convencionais e testes em reômetro de cisalhamento dinâmico. Os dados obtidos permitiram evidenciar a eficácia do óleo de xisto como agente compatibilizante, proporcionando excelente dispersão do polímero na matriz asfáltica e estabilidade a estocagem a altas temperaturas. Este óleo apresenta-se como uma opção tecnicamente viável para o óleo aromático atualmente em uso no mercado. Foi também verificado que o uso de enxofre como agente de ligação tem um efeito altamente positivo nas propriedades do ligante modificado, com significativa redução da tan ō, da deformação após aplicação de cargas cíclicas e elevação do módulo complexo, o que contribui para obtenção de pavimentos com maior resistência a deformação e ao trincamento por fadiga. / The use of polymer modified asphalts has grown significantly in the last decades due to the increase in traffic density, axle loading in vehicles and tyre pressure. These binders favor the increase of pavement life and the reduction of its maintenancement costs. The most used polymer for asphalt modification is styrene-butadiene-styrene blocked copolymers. This thesis evaluated the effects of different compatibilizers and crosslinkers on rheological behavior of styrene-butadiene-styrene copolymer modified asphalt binders, as well as the influence of its structure, linear or radial. Binder’s characteristics were determined by conventional analysis and tests in dinamic shear rheometer. Data obtained provided evidence of the positive effect of sulfur as crosslinker in modified binders properties, with high tan ō reduction, complex modulus increase and deformation reduction after application of cyclic loads, characteristics that turn possible the existence of pavements with greater rutting and fatigue resistance. It was also verified the shale oil efficacy as a compatibilizer agent, providing an excellent polymer dispersion inside asphalt matrix and a stable storage binder at high temperatures. This oil can be considered as a technical available option to aromatic oil presently in use at pavement industry.