O poli(cloreto de vinila) PVC é o segundo termoplástico mais consumido no mundo devido a sua versatilidade e seu amplo espectro de utilização. O desenvolvimento de modelos matemáticos representativos é de grande importância para o projeto, análise e otimização de processos de polimerização. A determinação das condições de operação ótimas para um reator de polimerização levando em conta as restrições operacionais e de qualidade do polímero produzido poderia, em princípio, ser realizada de maneira empírica. Entretanto, pode ser feita de maneira muito mais eficiente, econômica e segura através da solução de um problema de otimização. Para tanto, é imprescindível dispor de um modelo matemático representativo do processo de polimerização, confiável e validado experimentalmente em condições tão amplas quanto possível. Dentro deste panorama, o presente trabalho buscou desenvolver, a partir de modelos previamente descritos na literatura, um modelo matemático do processo de polimerização em suspensão de cloreto de vinila. Parâmetros do modelo referentes às limitações difusionais das constantes de terminação e propagação foram ajustados. As previsões do modelo foram comparadas com dados experimentais obtidos na literatura, referentes a diferentes tipos de iniciador, e diferentes condições operacionais. Verificou-se que o modelo desenvolvido foi capaz de representar adequadamente todos os dados experimentais testados quando ajustado individualmente para cada ensaio. Quando aplicada uma correlação generalizada para os parâmetros ajustáveis, o modelo representou de forma satisfatória, tanto qualitativa como quantitativamente, a maioria dos dados experimentais. As possíveis causas para as discrepâncias encontradas em alguns casos foram discutidas e recomendações para melhoramento do modelo foram apresentadas. / Poly (vinyl chloride) PVC is the second-largest thermoplastic that is consumed in the world because of its versatility and comprehensive series of application. The development of representative mathematical models is important for the design, analysis and optimization of polymerization processes. The determination of the optimal operational conditions for a polymerization reactor taking into account operational constraints and quality of the polymer produced could be, in principle, achieved by empirical trial-and-error procedure. However, this can be made in a much more efficient, economic, and safe way through the solution of an optimization problem for which it is required a representative mathematical model of the polymerization process. Such model should be reliable and validated over as wide a range of experimental conditions as possible. In this scenario, the objective of the present work was to develop a mathematical model for suspension polymerization of vinyl chloride, with the abovementioned features, from the models previously described in literature. Model parameters for the diffusion-controlled termination and propagation rate constant were estimated. The model predictions were compared with experimental data taken from the literature, covering different kinds of initiators and different operational conditions. It was found that the model was able to suitably represent all the experimental data tested when fitted for each run. When a general correlation for the adjustable parameters was obtained and included in the model, the model predictions reproduced satisfactorily most of the experimental data in both qualitative and quantitative fashions. Possible causes for the discrepancies found in some cases were discussed and recommendations for model improvement were suggested.

O poli(cloreto de vinila) PVC é o segundo termoplástico mais consumido no mundo devido a sua versatilidade e seu amplo espectro de utilização. O desenvolvimento de modelos matemáticos representativos é de grande importância para o projeto, análise e otimização de processos de polimerização. A determinação das condições de operação ótimas para um reator de polimerização levando em conta as restrições operacionais e de qualidade do polímero produzido poderia, em princípio, ser realizada de maneira empírica. Entretanto, pode ser feita de maneira muito mais eficiente, econômica e segura através da solução de um problema de otimização. Para tanto, é imprescindível dispor de um modelo matemático representativo do processo de polimerização, confiável e validado experimentalmente em condições tão amplas quanto possível. Dentro deste panorama, o presente trabalho buscou desenvolver, a partir de modelos previamente descritos na literatura, um modelo matemático do processo de polimerização em suspensão de cloreto de vinila. Parâmetros do modelo referentes às limitações difusionais das constantes de terminação e propagação foram ajustados. As previsões do modelo foram comparadas com dados experimentais obtidos na literatura, referentes a diferentes tipos de iniciador, e diferentes condições operacionais. Verificou-se que o modelo desenvolvido foi capaz de representar adequadamente todos os dados experimentais testados quando ajustado individualmente para cada ensaio. Quando aplicada uma correlação generalizada para os parâmetros ajustáveis, o modelo representou de forma satisfatória, tanto qualitativa como quantitativamente, a maioria dos dados experimentais. As possíveis causas para as discrepâncias encontradas em alguns casos foram discutidas e recomendações para melhoramento do modelo foram apresentadas. / Poly (vinyl chloride) PVC is the second-largest thermoplastic that is consumed in the world because of its versatility and comprehensive series of application. The development of representative mathematical models is important for the design, analysis and optimization of polymerization processes. The determination of the optimal operational conditions for a polymerization reactor taking into account operational constraints and quality of the polymer produced could be, in principle, achieved by empirical trial-and-error procedure. However, this can be made in a much more efficient, economic, and safe way through the solution of an optimization problem for which it is required a representative mathematical model of the polymerization process. Such model should be reliable and validated over as wide a range of experimental conditions as possible. In this scenario, the objective of the present work was to develop a mathematical model for suspension polymerization of vinyl chloride, with the abovementioned features, from the models previously described in literature. Model parameters for the diffusion-controlled termination and propagation rate constant were estimated. The model predictions were compared with experimental data taken from the literature, covering different kinds of initiators and different operational conditions. It was found that the model was able to suitably represent all the experimental data tested when fitted for each run. When a general correlation for the adjustable parameters was obtained and included in the model, the model predictions reproduced satisfactorily most of the experimental data in both qualitative and quantitative fashions. Possible causes for the discrepancies found in some cases were discussed and recommendations for model improvement were suggested.

Termiskt expanderbara mikrosfärer är ihåliga polymera partiklar i vilka en flyktig drivgas har kapslats in. När mikrosfärerna upphettas förgasas drivgasen, vilket ökar trycket i mikrosfärerna så att de expanderar och deras volym ökar avsevärt. Denna unika egenskap gör att expanderade mikrosfärer har en låg densitet och är lämpliga för applikationer där låg vikt är väsentligt, och för att förändra ytstrukturer, så som i till exempel konstläder och textiler. Syftet med denna studie har varit att utveckla ett stabilt system för suspensionspolymerisation för att ge en liten mikrosfär (~20 μm efter expansion) som expanderar vid relativt höga temperaturer. Detta har uppnåtts genom att undersöka effekterna av förändringar i stabiliseringssystemet. Komponenterna som varierades var mängden silika (LX), kondensationsoligomeren mellan adipinsyra och dietanolamin (KO), olika formuleringar och mängd av dilauryl peroxid, samt mängden m(III)nitrat. Ytterligare tester gjordes runt effekten av tvärbindning, tillsats av monomeren metyl metakrylat (MMA), samt tillsats av salt (NaCl). Ett stabilt system för polymerisation i 1L-skala med en homogen dispersion uppnåddes med en av dilauryl peroxide formuleringarna tillsammans med en större mängde LX och KO. Studien visar även att kvoten mellan LX och KO har en signifikant effekt på systemets stabilitet och att mängden av både LX och KO påverkar partikelstorleken. / Thermally expandable microspheres are hollow polymeric particles in which a blowing agent has been encapsulated. Upon heating the blowing agent will vaporize, causing the internal pressure to increase, thereby expanding the microspheres. This unique expandable property reduces the density of the microspheres tremendously and makes them excellent for many applications, as for example as light weight fillers and to alter surface textures, such as in artificial leather and textiles. The purpose of this study has been to develop a viable system for the suspension polymerization of a small microsphere (~20 μm when expanded) expanding at fairly high temperatures. This has been accomplished by investigating the effect of changes in the stabilization system. Components of the stabilization system that have been varied were the amounts of silica (LX), condensation oligomer from adipic acid and diethanol amine (KO), and m(III)nitrate, as well as different formulations and amounts of the initiator dilauryl peroxide. Additional tests were performed concerning the effect of the crosslinking, adding the monomer methyl methacrylate (MMA), and the addition of salt (NaCl). A system for polymerization in 1L-scale was accomplished where it was found that one of the dilauryl peroxide formulations together with a higher amount of LX and KO provided a stable system giving homogeneous dispersions in which the microspheres have the desired expansion properties. Also, the ratio between LX and KO had a significant effect on the stability of the system and the amount of both LX and KO affects the particle size.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Multi-vesiculated particles (MVP) are synthetic insoluble polymeric particles containing a multitude of vesicles (micro-voids). The particles are generally produced and used as a suspension in an aqueous fluid and are therefore readily incorporated in latex paints as opacifiers. The coarse or suede MVP have a large volume-mean diameter (VMD) generally in the range of 35-60μm, the large VMD makes them suitable for textured effect paints. The general principle behind the MVP technology is as the particles dry, the vesicles drain of liquid and fill with air. The large refractive index difference between the polymer shell and air result in the scattering of incident light which give the MVP their white opaque appearance making them suitable as an opacifier for the partial replacement of TiO2 in coating systems. Whilst the coarse MVP have been successfully commercialized, insufficient understanding of the influence of the MVP system parameters on the final MVP product characteristics coupled with the MVP’s sensitivity towards the unsaturated polyester resin (UPR) resulted in a product with significant quality variation. On the other hand these uncertainties provided the opportunity to model and optimise the MVP system through developing a better understanding of the influence of the MVP system parameters on the MVP product characteristics, developing a model to mathematically describe these relationships and to optimise the MVP system to achieve the product specifications whilst simultaneously minimising the variation observed in the product characteristics. The primary MVP characteristics for this study were the particle size distribution (quantified by the volume-mean diameter (VMD)) and the reactor buildup.1 The approach taken was to analyse the system determining all possible system factors that may affect it, and then to reduce the total number of system factors by selecting those which have a significant influence on the characteristics of interest. A model was then developed to mathematically describe the relationship between these significant factors and the characteristics of interest. This was done utilising a set of statistical methods known as design of experiments (DoE). A screening DoE was conducted on the identified system factors reducing them to a subset of factors which had a significant effect on the VMD & buildup. The UPR was characterised by its acid value and viscosity and in combination with the identified significant factors a response surface model (RSM) was developed for the chosen design space, mathematically describing their relationship with the MVP characteristics. Utilising a DoE method known as robust parameter design (specifically propagation of error) an optimised MVP system was numerically determined which brought the MVP product within specification and simultaneously reduced the MVP’s sensitivity to the UPR. The validation of the response surface model indicated that the average error in the VMD prediction was 2.16μm (5.16%) which compared well to the 1.96μm standard deviation of replication batches. The high Pred-R2 value of 0.839 and the low validation error indicates that the model is well suited for predicting the VMD characteristic of the MVP system. The application of propagation of error to the model during optimisation resulted in a MVP process and formulation which brought the VMD response from the standard’s average of 44.56μm to the optimised system’s average of 47.84μm which was significantly closer to the desired optimal of 47.5μm. The most notable value added to the system by the propagation of error technique was the reduction in the variation around the mean of the VMD, due to the UPR, by over 30%1 from the standard to optimised MVP system. In addition to the statistical model, dimensional analysis, (specifically Buckingham-Π method) was applied to the MVP system to develop a semi-empirical dimensionless model for the VMD. The model parameters were regressed from the experimental data obtained from the DoE and the model was compared to several models sited in literature. The dimensionless model was not ideal for predicting the VMD as indicated by the R2 value of 0.59 and the high average error of 21.25%. However it described the VMD better than any of the models cited in literature, many of which had negative R2 values and were therefore not suitable for modelling the MVP system. / AFRIKAANSE OPSOMMING: Sintetiese polimeer partikels wat veeltallige lugblasies huisves en omhul, staan beter bekend as MVP (verkort vanaf die Engelse benaming, "multi-vesiculated particles"). Tipies word hierdie partikels berei en gestabiliseer in 'n waterige suspensie wat dit mengbaar maak met konvensionele emulsie sisteme en dit dus in staat stel om te funksioneer as 'n dekmiddel in verf. Deur die volume gemiddelde deursnee (VGD) te manipuleer tot tussen 35 en 60μm, word die growwe partikels geskik vir gebruik in tekstuur verwe, soos byvoorbeeld afwerkings met 'n handskoenleer (suède) tipe tekstuur. Die dekvermoë van MVP ontstaan soos die partikels droog en die water in die polimeer partikel vervang word met lug. As gevolg van die groot verskil in brekingsindeks tussen die polimeer huls en die lugblasies, word lig verstrooi in alle rigtings wat daartoe lei dat die partikels wit vertoon. Dus kan die produk gebruik word om anorganiese pigmente soos TiO2 gedeeltelik te vervang in verf. Alhoewel growwe MVP al suksesvol gekommersialiseer is, bestaan daar nog net 'n beperkte kennis oor die invloed van sisteem veranderlikes op die karakteristieke eienskappe van die finale produk. Dit volg onder andere uit waarnemings dat die kwaliteit van die growwe MVP baie maklik beïnvloed word deur onbekende variasies in die reaktiewe poliëster hars wat gebruik word om die partikels te maak. Dit het egter die geleentheid geskep om die veranderlikes deeglik te modeleer en te optimiseer om sodoende 'n beter begrip te kry van hoe eienskappe geaffekteer word. 'n Wetenskaplike model is opgestel om verwantskappe te illustreer en om die sisteem te optimiseer sodat daar aan produk spesifikasies voldoen word, terwyl produk variasies minimaal bly. Die oorheersende doel in hierdie studie was om te fokus op partikelgrootte en verspreiding (bepaal met behulp van die VGD) as primêre karakteristieke eienskap, asook die graad van aanpaksel op die reaktorwand gedurende produksie. Vanuit eerste beginsel is alle moontlike veranderlikes geanaliseer, waarna die hoeveelheid verminder is na slegs dié wat die karakteristieke eienskap die meeste beïnvloed. Deur gebruik te maak van eksperimentele ontwerp is die wetenskaplike model ontwikkel wat die effek van hierdie eienskappe statisties omsluit. 'n Afskerms eksperimentele ontwerp is uitgevoer om onbeduidende veranderlikes te elimineer van dié wat meer betekenisvol is. Die hars is gekaraktiseer met 'n getal wat gebruik word om die aantal suur groepe per molekuul aan te dui, asook die hars se viskositeit. Hierdie twee eienskappe, tesame met ander belangrike eienskappe is gebruik om 'n karakteristieke oppervlakte model te ontwikkel wat hul invloed op die VGD van die partikels en reaktor aanpakking beskryf. Deur gebruik te maak van 'n robuuste ontwerp, beter beskryf as 'n fout verspreidingsmodel, is die MVP sisteem numeries geoptimiseer. Dit het tot gevolg dat die MVP binne spesifikasie bly en die VGD se sensitiwiteit vir variasie in die hars verminder het. Geldigheidstoetse op die oppervlakte model het aangetoon dat die gemiddelde fout in VGD 2.16μm (5.16%) was. Dit is stem goed ooreen met die 1.96μm standaard afwyking tussen herhaalde lopies. Hoë Pred-R2 waardes (0.839) en lae geldigheidsfout waardes het getoon dat die voorgestelde model die VGD eienskappe uiters goed beskryf. Toepassing van die fout verspreidingsmodel gedurende optimisering het tot gevolg dat die VGD vanaf die standaard gemiddelde van 44.56μm verskuif het na die geoptimiseerde gemiddelde van 47.84μm. Dit is aansienlik nader aan die verlangde optimum waarde van 47.5μm. Die grootste waarde wat toegevoeg is na afloop van hierdie studie, is dat die afwyking rondom die gemiddelde VGD, toegeskryf aan die eienskappe van die hars, verminder het met oor die 30%1 (vanaf die standaard tot die optimiseerde sisteem). Verdere dimensionele analise van die sisteem deur spesifiek gebruik te maak van die Buckingham-Π metode het gelei tot die ontwikkeling van 'n semi-empiriese dimensielose VGD model. Regressie op eksperimentele data verkry uit die eksperimentele ontwerp is vergelyk met verskeie modelle beskryf in ander literatuur bronne. Hierdie dimensionele model was nie ideaal om die VGD te beskryf nie, aangesien die R2 waarde 0.59 was en die gemiddelde fout van 21.25% relatief hoog was. Nietemin, hierdie model beskryf die VGD beter as enige ander model voorgestel in die literatuur. In talle gevalle is negatiewe R2 waardes verkry, wat hierdie literatuur modelle geheel en al ongeskik maak vir toepassing in die MVP sisteem.

L’embolisation thérapeutique est devenu le traitement de choix pour l’hémorragie, les malformations artériovéneuses ou certains types de cancer. Parmi différents agents d’embolisation,les microsphères non dégradables (Embozene®, Bead BlockTM,…) sont les plus utilisées. Leur forme bien sphérique et leur taille calibrée permettent un meilleur ciblage dans les vaisseaux et une bonne qualité de l’occlusion. Dans certains cas cliniques, l’embolisation temporaire, envisageable avec l’utilisation des microsphères résorbables peut être bénéfique pour les patients. Le but du travail réalisé au cours de cette thèse a été le développement de microsphères résorbables satisfaisant les différents critères pour être employées comme matériaux d’embolisation (taille calibrée,biocompatibles, élastique pour être injectée au travers des cathéters mais suffisamment rigide pour résister à la pression sanguine). Dans cet objectif, nous avons développé une méthode de synthèse de microsphères constituées d’hydrogels hydrolysables par polymérisation en suspension. Une large gamme de microsphères ont été synthétisées en modulant la nature du réticulant et/ou la composition des milieux de polymérisation. Les expériences in vitro ont démontré que les microsphères obtenues sont satisfaisantes pour permettre leur injection au travers des cathéters. La dégradation rapide des ponts de réticulation a été confirmée à travers la diminution du module élastique G’ et du pH du surnageant, accompagnée d’une augmentation du taux de gonflement.Malgré une dégradation partielle des microsphères (due à une réaction secondaire formant des liaisons de réticulation non dégradables), le temps de l’hydrolyse a répondu parfaitement au cahier de charges (entre 7 et 49 jours). Des études complémentaires pour optimiser la réaction de polymérisation vont permettre le développement de microsphères totalement dégradables. / Therapeutic embolization is nowadays a first line treatment for haemorrhage, arteriovenous malformation or tumors. Among different embolization agents, non degradable microspheres(Embozene®, Bead BlockTM,…) are the most employed thanks to their well calibrated spherical shape which allows good occlusion. In some cases including treatment of uterine fibroids or chemo-sensitive tumors, it may be interesting to achieve a temporary embolization to avoid definitive destruction of the tissue. Temporary embolization would be possible using biodegradable microspheres. The aim of our work was to develop degradable microspheres having all requiredcharacteristics to be used as embolization material (well calibrated in size, biocompatible, rigide enough to resist blood pressure but elastic enough to remain intact during injection through catheter). To this purpose, we have developed hydrolysable hydrogel based microspheres by suspension polymerization. A wide range of microspheres was synthesized by varying the type of crosslinker and composition of the polymerization medium. In vitro test showed that the microspheres have suitable characteristics to pass through catheter. Degradation studies revealed a rapid diminution of G’ modulus and the pH of the supernatants, accompanied by an increase of swelling ratio due to the hydrolysis of the crosslinkings. Although microspheres were not totally degradable as expected (since a side reaction had created non degradable crosslinking during the polymerisation), characterisations showed promising results that the degradation did occur within a suitable time scale requirements for temporal embolization.

<p>An intrinsic mathematical model for simulation of fixed bed chromatography was demonstrated and compared to more simplified models. The former model was shown to describe variations in the physical, kinetic, and operating parameters better than the latter ones. This resulted in a more reliable prediction of the chromatography process as well as a better understanding of the underlying mechanisms responsible for the separation. A procedure based on frontal liquid chromatography and a detailed mathematical model was developed to determine effective diffusion coefficients of proteins in chromatographic gels. The procedure was applied to lysozyme, bovine serum albumin, and immunoglobulin γ in Sepharose™ CL-4B. The effective diffusion coefficients were comparable to those determined by other methods.</p><p>Molecularly imprinted polymers (MIPs) are traditionally prepared as irregular particles by grinding monoliths. In this thesis, a suspension polymerization providing spherical MIP beads is presented. Droplets of pre-polymerization solution were formed in mineral oil with no need of stabilizers by vigorous stirring. The droplets were transformed into solid spherical beads by free-radical polymerization. The method is fast and the performance of the beads comparable to that of irregular particles. Optimizing a MIP formulation requires a large number of experiments since the possible combinations of the components are huge. To facilitate the optimization, chemometrics was applied. The amounts of monomer, cross-linker, and porogen were chosen as the factors in the model. Multivariate data analysis indicated the influence of the factors on the binding and an optimized MIP composition was identified. The combined use of the suspension polymerization method to produce spherical beads with the application of chemometrics was shown in this thesis to drastically reduce the number of experiments and the time needed to design and optimize a new MIP.</p>

An intrinsic mathematical model for simulation of fixed bed chromatography was demonstrated and compared to more simplified models. The former model was shown to describe variations in the physical, kinetic, and operating parameters better than the latter ones. This resulted in a more reliable prediction of the chromatography process as well as a better understanding of the underlying mechanisms responsible for the separation. A procedure based on frontal liquid chromatography and a detailed mathematical model was developed to determine effective diffusion coefficients of proteins in chromatographic gels. The procedure was applied to lysozyme, bovine serum albumin, and immunoglobulin γ in Sepharose™ CL-4B. The effective diffusion coefficients were comparable to those determined by other methods. Molecularly imprinted polymers (MIPs) are traditionally prepared as irregular particles by grinding monoliths. In this thesis, a suspension polymerization providing spherical MIP beads is presented. Droplets of pre-polymerization solution were formed in mineral oil with no need of stabilizers by vigorous stirring. The droplets were transformed into solid spherical beads by free-radical polymerization. The method is fast and the performance of the beads comparable to that of irregular particles. Optimizing a MIP formulation requires a large number of experiments since the possible combinations of the components are huge. To facilitate the optimization, chemometrics was applied. The amounts of monomer, cross-linker, and porogen were chosen as the factors in the model. Multivariate data analysis indicated the influence of the factors on the binding and an optimized MIP composition was identified. The combined use of the suspension polymerization method to produce spherical beads with the application of chemometrics was shown in this thesis to drastically reduce the number of experiments and the time needed to design and optimize a new MIP.

Made available in DSpace on 2014-06-11T19:22:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-29Bitstream added on 2014-06-13T20:10:04Z : No. of bitstreams: 1 basso_gg_me_sjrp_parcial.pdf: 127718 bytes, checksum: 3bfde1c4f9ff597bf78cc0fd338d9fe8 (MD5) Bitstreams deleted on 2015-08-28T16:08:53Z: basso_gg_me_sjrp_parcial.pdf,. Added 1 bitstream(s) on 2015-08-28T16:09:58Z : No. of bitstreams: 1 000670722.pdf: 6039395 bytes, checksum: a8326c9658e562fa0ebe828de242a31a (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Financiadora de Estudos e Projetos (FINEP) / Partículas poliméricas com tamanho e morfologia controlados e propriedades físico-químicas adequadas são amplamente utilizadas em aplicações médicas, como na embolização, uma técnica cirúrgica utilizada para tratar malformações arteriovenosas (MAVs), conter hemorragias, tratar localmente tumores hipervascularizados (THVs) e outras doenças vasculares. Este procedimento é realizado com materiais de diferentes formas e composições, sendo as partículas de poli(álcool vinílico) (PVA) freqüentemente utilizadas por apresentarem um alto grau de desempenho. Elas estão disponíveis no mercado nas morfologias esférica e não-esférica, sendo que as esféricas apresentam uma maior eficácia no tratamento. O presente trabalho objetivou desenvolver e aprimorar partículas esféricas de PVA e poli(acetato vinílico) (PVAc) para serem utilizadas em embolização. Suas sínteses foram realizadas em duas etapas: a polimerização em suspensão do monômero acetato vinílico (VAc) em PVAc e a saponificação do polímero PVAc em PVA, com variações na velocidade de agitação e na concentração da solução de hidróxido de sódio (NaOH), na etapa da saponificação. As partículas foram caracterizadas por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria diferencial de varredura (DSC) e ressonância magnética nuclear de 13 C - cross polarization / magic angle spinning (13 C RMN CP/MAS). Foram analisadas a distribuição de tamanhos, a dimensão fractal, a determinação da biocarga, que determinou os parâmetros de esterilização por radiação gama, e a citotoxicidade, pelo teste de “Reatividade Biológica in vitro”. Os resultados indicaram que a morfologia esférica foi obtida durante a primeira etapa da síntese e que essa morfologia não foi afetada pelo segundo processo. A velocidade de agitação e a concentração de NaOH influenciaram... / Polymeric particles with controlled size and morphology and appropriated physicochemical properties are widely used in medical applications, such as embolization, a surgical technique used to treat arteriovenous malformations (AVMs), stop bleedings, treat locally hypervascular tumors (HVTs) and other vascular diseases. This procedure is performed with materials of different shapes and compositions, and the poly(vinyl alcohol) (PVA) particles are often used for presenting a high degree of performance. They are commercially available in spherical and non-spherical morphologies, and the spherical particles have a greater efficacy in the treatment. This study aimed to develop and improve spherical PVA and poly(vinyl acetate) (PVAc) particles for use in embolization. Their syntheses were performed in two stages: the suspension polymerization of vinyl acetate (VAc) monomer in PVAc and the saponification of PVAc polymer in PVA, with variations in the stirring speed and the concentration of sodium hydroxide (NaOH) solution, at the saponification step. The particles were characterized by scanning electronic microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and 13 C nuclear magnetic resonance - cross polarization / magic angle spinning (13 C NMR CP/MAS). We analyzed the size distribution, the fractal dimension, the determining of the bioburden, which determined the parameters of sterilization by gamma irradiation, and the cytotoxicity, by the “Biological Reactivity in vitro”. The results indicated that the spherical morphology was obtained during the first stage of the synthesis and that this morphology was not affected by the second process. The stirring speed and the NaOH concentration influenced the size of the particles. The commercial particles have a fractal dimension greater than the synthesized particles... (Complete abstract click electronic access below)

Resumo: Partículas poliméricas com tamanho e morfologia controlados e propriedades físico-químicas adequadas são amplamente utilizadas em aplicações médicas, como na embolização, uma técnica cirúrgica utilizada para tratar malformações arteriovenosas (MAVs), conter hemorragias, tratar localmente tumores hipervascularizados (THVs) e outras doenças vasculares. Este procedimento é realizado com materiais de diferentes formas e composições, sendo as partículas de poli(álcool vinílico) (PVA) freqüentemente utilizadas por apresentarem um alto grau de desempenho. Elas estão disponíveis no mercado nas morfologias esférica e não-esférica, sendo que as esféricas apresentam uma maior eficácia no tratamento. O presente trabalho objetivou desenvolver e aprimorar partículas esféricas de PVA e poli(acetato vinílico) (PVAc) para serem utilizadas em embolização. Suas sínteses foram realizadas em duas etapas: a polimerização em suspensão do monômero acetato vinílico (VAc) em PVAc e a saponificação do polímero PVAc em PVA, com variações na velocidade de agitação e na concentração da solução de hidróxido de sódio (NaOH), na etapa da saponificação. As partículas foram caracterizadas por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria diferencial de varredura (DSC) e ressonância magnética nuclear de 13 C - cross polarization / magic angle spinning (13 C RMN CP/MAS). Foram analisadas a distribuição de tamanhos, a dimensão fractal, a determinação da biocarga, que determinou os parâmetros de esterilização por radiação gama, e a citotoxicidade, pelo teste de "Reatividade Biológica in vitro". Os resultados indicaram que a morfologia esférica foi obtida durante a primeira etapa da síntese e que essa morfologia não foi afetada pelo segundo processo. A velocidade de agitação e a concentração de NaOH influenciaram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Polymeric particles with controlled size and morphology and appropriated physicochemical properties are widely used in medical applications, such as embolization, a surgical technique used to treat arteriovenous malformations (AVMs), stop bleedings, treat locally hypervascular tumors (HVTs) and other vascular diseases. This procedure is performed with materials of different shapes and compositions, and the poly(vinyl alcohol) (PVA) particles are often used for presenting a high degree of performance. They are commercially available in spherical and non-spherical morphologies, and the spherical particles have a greater efficacy in the treatment. This study aimed to develop and improve spherical PVA and poly(vinyl acetate) (PVAc) particles for use in embolization. Their syntheses were performed in two stages: the suspension polymerization of vinyl acetate (VAc) monomer in PVAc and the saponification of PVAc polymer in PVA, with variations in the stirring speed and the concentration of sodium hydroxide (NaOH) solution, at the saponification step. The particles were characterized by scanning electronic microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and 13 C nuclear magnetic resonance - cross polarization / magic angle spinning (13 C NMR CP/MAS). We analyzed the size distribution, the fractal dimension, the determining of the bioburden, which determined the parameters of sterilization by gamma irradiation, and the cytotoxicity, by the "Biological Reactivity in vitro". The results indicated that the spherical morphology was obtained during the first stage of the synthesis and that this morphology was not affected by the second process. The stirring speed and the NaOH concentration influenced the size of the particles. The commercial particles have a fractal dimension greater than the synthesized particles... (Complete abstract click electronic access below) / Orientador: José Geraldo Nery / Coorientador: Ana Paula Marques de Lima Oliveira / Banca: Rosa Sayoko Kawasaki Oyama / Banca: Moacir Fernandes de Godoy / Mestre

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, copolímeros à base de acrilonitrila e divinilbenzeno foram sintetizados, utilizando a técnica de polimerização em suspensão, na presença de três agentes porogênicos diferentes (álcool isoamílico, metil-etil-cetona e tolueno). Esses copolímeros foram caracterizados por meio da determinação da densidade aparente, do volume e diâmetro de poros, por microscopia ótica e microscopia eletrônica de varredura e foram avaliados quanto à capacidade de inchamento em heptano e tolueno. O principal intuito dessa pesquisa foi correlacionar a formação da estrutura porosa desses materiais com os principais parâmetros de síntese (grau de diluição dos monômeros, poder solvatante do diluente e teor do agente de reticulação). Desses parâmetros, o que mais influenciou na formação da estrutura porosa desses materiais foi o poder solvatante do diluente. A teoria dos parâmetros de solubilidade de Hansen e Hildebrand foi utilizada com o intuito de fazer uma previsão das características porosas dos copolímeros à base de acrilonitrila e divinilbenzeno sintetizados na presença de três diluentes diferentes. Dentre esses diluentes, o álcool isoamílico foi o pior solvente para os copolímeros de AN-DVB, em todos os teores de agente de reticulação e em todas as diluições utilizadas. O tolueno foi o melhor solvente para os copolímeros que contêm altos teores de agente de reticulação. Estas observações estão de acordo com as previsões dos parâmetros de solubilidade de Hansen e Hildebrand. A metil-etil-cetona foi o melhor solvente para os copolímeros que contêm teores intermediários de agente de reticulação. Esta observação só está condizente com o parâmetro de solubilidade de Hansen. / In this work, acrylonitrile-divinylbenzene copolymers were synthesized using the technique of suspension polymerization in the presence of three different solvents (isoamyl alcohol, methyl-ethyl-ketone and toluene). These copolymers were characterized by apparent density, pore volume and pore diameter, optical and scanning electron microscopy, and were evaluated for their ability to swell in heptane and toluene. The principal aim of this research was to correlate the porous structure formation of these materials, with the main synthesis parameters (degree of dilution, solvating power of the diluent and crosslinking degree). Among these parameters, the most important on the formation of the materials porous structure was the solvating power of the diluent. The theory of solubility parameters of Hansen and Hildebrand was used in order to make a prediction of the porous characteristics of acrylonitrile-divinylbenzene copolymers synthesized in the presence of three different diluents. Among these solvents, the isoamyl alcohol was the worst solvent for acrylonitrile-divinylbenzene copolymers, at all levels of crosslinking degree and at all dilutions used. Toluene was the best solvent for the copolymers containing high levels crosslinking degree. These observations are consistent with the predictions of the solubility parameters of Hansen and Hildebrand. The methyl-ethyl-ketone was the best solvent for the copolymers containing intermediate crosslinking degree. This observation is only consistent with the Hansen solubility parameters. In this work, acrylonitrile-divinylbenzene copolymers were synthesized using the technique of suspension polymerization in the presence of three different solvents (isoamyl alcohol, methyl-ethyl-ketone and toluene). These copolymers were characterized by apparent density, pore volume and pore diameter, optical and scanning electron microscopy, and were evaluated for their ability to swell in heptane and toluene. The principal aim of this research was to correlate the porous structure formation of these materials, with the main synthesis parameters (degree of dilution, solvating power of the diluent and crosslinking degree). Among these parameters, the most important on the formation of the materials porous structure was the solvating power of the diluent. The theory of solubility parameters of Hansen and Hildebrand was used in order to make a prediction of the porous characteristics of acrylonitrile-divinylbenzene copolymers synthesized in the presence of three different diluents. Among these solvents, the isoamyl alcohol was the worst solvent for acrylonitrile-divinylbenzene copolymers, at all levels of crosslinking degree and at all dilutions used. Toluene was the best solvent for the copolymers containing high levels crosslinking degree. These observations are consistent with the predictions of the solubility parameters of Hansen and Hildebrand. The methyl-ethyl-ketone was the best solvent for the copolymers containing intermediate crosslinking degree. This observation is only consistent with the Hansen solubility parameters.