Orientador: Liliane Maria Ferrareso Lona / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-24T00:08:56Z (GMT). No. of bitstreams: 1 Vieira_RonierikPioli_M.pdf: 2090320 bytes, checksum: 2a9ff9a429c08577f877080fe8c48d01 (MD5) Previous issue date: 2013 / Resumo: O processo de polimerização radicalar via transferência de átomo (ATRP) consiste numa das técnicas de polimerização radicalar controlada para a síntese de materiais com estruturas macromoleculares específicas. Através desta técnica, podem-se sintetizar homopolímeros monodispersos (baixos índices de polidispersidade), polímeros com funcionalidades terminais ou numa determinada posição da cadeia, o que permite produzir diversos copolímeros (em bloco, gradiente, aleatório etc), possibilitando agregar aos materiais propriedades requisitadas na indústria automobilística e aeroespacial, cosméticos, tintas e adesivos, além de possibilitar a produção de materiais para a liberação controlada de drogas e outras aplicações biomédicas. Apesar de todo este potencial relacionado à ATRP, a maioria das pesquisas encarrega-se de desenvolver novos materiais em escala laboratorial, deixando de lado a condução do processo em escalas comerciais. Neste contexto, o presente trabalho encarrega-se de desenvolver uma modelagem cinética do processo ATRP, juntamente com uma análise dos resultados da simulação para proporcionar aos leitores uma compreensão geral do processo, além de uma ferramenta matemática para futuros trabalhos de otimização e Scale up. A modelagem matemática foi desenvolvida utilizando balanços materiais, para prever perfis de concentração no reator, e o método dos momentos, para prever as massas molares e polidispersidades dos polímeros formados. Os modelos foram resolvidos numericamente em um programa computacional desenvolvido em linguagem Fortran e validados através de dados de literatura utilizando gráficos de dispersão. Por fim, uma análise paramétrica foi realizada com o intuito de estudar o comportamento do processo sob situações práticas, como por exemplo, alterações na constante de equilíbrio do processo (Keq), influência das razões iniciais de catalisador e iniciador sobre as propriedades finais, influência das terminações e transferências de cadeia, além da influência da temperatura de operação do reator / Abstract: Atom transfer radical polymerization (ATRP) is one of controlled radical polymerization techniques for the synthesis of materials with specific macromolecular structures. Using this technique, one can synthesize monodisperse homopolymer (low polydispersity index), end groups polymers or polymers with functionality in a particular position in the chain, which allows to produce different copolymers (block, gradient, random, etc.), allowing aggregate materials properties required in automotive and aerospace industry, cosmetics, paints and adhesives, and enable the production of materials for the controlled delivery of drugs and other biomedical applications. Despite this potential related to ATRP, most research is responsible for developing new materials on the laboratory scale, leaving aside the conduct of proceedings at commercial scales. In this context, this paper undertakes to develop a kinetic modeling of the ATRP process, together with an analysis of the simulation results to give readers a general understanding of the process, as well as a mathematical tool for future work on optimization and Scale up. A mathematical model was developed using material balances to predict concentration profiles in the reactor, and the method of moments to predict the molecular weight and polydispersities of the polymers formed. The models were solved numerically on a computer program developed in Fortran and validated through literature data using scatter plots. Finally, the parametric analysis was performed in order to study the behavior of chemical species in practical situations, such as changes in the process equilibrium constant (Keq), the influence of the initial ratio of catalyst and initiator on the final properties, influence terminations and chain transfers, beyond the influence of the operating temperature of the reactor / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Liliane Maria Ferrareso Lona / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T21:14:25Z (GMT). No. of bitstreams: 1 Manzato_FranciniGoncalves_M.pdf: 1285915 bytes, checksum: 839277a475811cdc2ed9b03dc34df2fc (MD5) Previous issue date: 2012 / Resumo: O conceito de polimerização via radical livre controlada (do inglês Living Free Radical Polymerization - LFRP) tem atraído interesse significativo devido às suas vantagens como um processo de radicais livres, cujas condições de reação não são tão rigorosas quanto às da polimerização iônica, usualmente utilizada para a produção de polímeros com baixa polidispersidade, e para a produção de polímeros com arquiteturas moleculares complexas e pré-definidas. No presente trabalho, estes princípios foram aplicados na investigação experimental da polimerização de estireno mediado por nitróxidos (NMRP), em solução de xileno em reator tanque agitado em batelada, com o objetivo de estudar a viabilidade do aumento de escala da produção de polímeros controlados via processo NMRP. A polimerização controlada via processo NMRP é geralmente estudada considerando sistema em massa (bulk). Poucas pesquisas existem na literatura considerando o processo NMRP em solução, uma alternativa para aumentar o controle da temperatura e da agitação do sistema. Neste trabalho, com o objetivo de produzir polímeros com distribuições de massas molares estreitas, com polidispersidades (PDI) próximas da unidade a uma elevada velocidade de conversão, foi utilizada uma combinação de dois tipos de iniciadores: o TBEC (tert-butilperóxido-2-etilhexil carbonato), que possui uma constante de decomposição baixa, e o BPO (peróxido de benzoíla), com constante de decomposição maior. A conversão do polímero foi determinada através de análise gravimétrica, e a caracterização do polímero foi feita através da análise das massas molares médias e das distribuições de massa molar pela técnica de Cromatografia de Permeação em Gel (GPC). Observou-se a possibilidade de produzir polímeros controlados, a uma velocidade de reação razoável, a partir do processo NMRP em solução / Abstract: The concept of Living Free Radical Polymerization (LFRP) has attracted considerable interest due to its advantages like its reaction conditions which are not as strict as in the ionic polymerization, usually, used for the production of polymers with low polydispersity. The LFPR also allows the production of polymers with complex and predefined molecular architectures. In this work, these principles were applied in an experimental investigation of living free radical polymerization mediated by nitroxide (NMPR) in xylene solution using a batch reactor, with the purpose of study the viability of scaling up the production of polymers controlled via NMRP process. Generally, NMRP technique is studied in bulk polymerization systems and a few works have been performed in solution which is an alternative to improve the temperature and stirring control of the system. The main objective of this work was to produce polymer with narrow molecular weight distribution and polydispersity around 1 at high conversion speed through solution polymerization. A combination of two types of initiators was used: tert-butylperoxy 2-ethylhexyl carbonate (TBEC) and benzoyl peroxide (BPO), which have low and high decomposition rates respectively. The polymer conversion was determined by gravimetry, and the polymer average molecular weights and molecular weight distributions were obtained by gel permeation chromatography (GPC). The experimental results show that is possible to produce polymers controlled at a reasonable rate of reaction from the NMRP process in solution / Mestrado / Desenvolvimento de Processos Químicos / Mestra em Engenharia Química

Piezotech, une start-up rachetée en 2010 par le leader français de la chimie, Arkema, développe et commercialise des copolymères fluorés électroactifs (EAPs). Ces copolymères présentent un grand intérêt pour des applications dans l’électronique imprimée, les capteurs, les actionneurs, les muscles artificiels, et le stockage de l’énergie. Les copolymères à base de fluorure de vinylidène (VDF) et de trifluoroéthylène (TrFE) possèdent les meilleures propriétés piézoélectriques et ferroélectriques (FE) parmi les polymères existants. L’introduction d’un termonomère, tel que le 1,1-chlorotrifluoroéthylène (CFE) ou le chlorotrifluoroéthylène (CTFE), modifie la conformation de la chaine polymère et change le comportement du matériau en relaxeur ferroélectrique (RFE). Le travail de thèse s’inscrit dans la recherche de nouveaux EAPs fluorés et la compréhension des relations structure-propriétés de ces matériaux. Après l’étude de la cinétique de copolymérisation avec le VDF et le TrFE de différents termonomères porteurs de groupements CF3, les terpolymérisations ont été examinées. Dans une première partie, le trans-1,3,3,3-tetrafluoropropène (1234ze), un termonomer qui n’homopolymérise pas, a été étudié. Des terpolymères de composition homogène ont été synthétisés. Ensuite, le 3,3,3-trifluoropropène (TFP) et le 2,3,3,3-tetrafluoropropène (1234yf) ont été terpolymérisés avec le VDF et le TrFE. Bien que les terpolymérisations batch amènent à une forte dérive de composition, un procédé de polymérisation en suspension en semi-continu a permis d’obtenir une meilleure homogénéité. Les propriétés thermiques et électroactives de tous les terpolymères ont été caractérisées. Dans une dernière partie, l’introduction d'une faible quantité d’un monomère fonctionnel (2-(trifluorométhyl) acide acrylique, MAF), dans les chaines du copolymère poly(VDF-co-TrFE), a permis une amélioration des propriétés d’adhésion sur le verre et le métal sans altérer les propriétés électroactives. L’étude des terpolymérisations avec le VDF, le TrFE et un termonomère porteur d’un groupement CF3 a contribué l’amélioration de la compréhension des relations structure-propriété dans les EAPs fluorés. En particulier, il a été montré que la réduction de la taille des cristaux n’est pas une condition suffisante pour obtenir un caractère RFE. / Piezotech, a start-up acquired in 2010 by the French leader in Chemistry, Arkema, develops and commercializes fluorinated electroactive copolymers (EAPs). These copolymers arouse a significant interest in printed electronics, printed memories, sensors, actuators, artificial muscles, and energy storage devices. Vinylidene fluoride (VDF) and trifluoroethylene (TrFE) -based copolymers are the polymers exhibiting the highest piezoelectric and ferroelectric (FE) properties. The introduction of a third slightly bulkier termonomer such as 1,1-chlorofluoroethylene (CFE) or chlorotrifluoroethylene (CTFE) was shown to modify the polymer chain conformation and change their electroactive behaviors into those of relaxor ferroelectric (RFE) materials. This PhD work aimed to discover new fluorinated EAPs and to better understand their structure-properties relationships. After the study of the kinetics of copolymerization of various CF3-bearing termonomers with VDF and TrFE; the terpolymerizations were investigated. First trans-1,3,3,3-tetrafluoropropene (1234ze), a non-homopolymerizable termonomer, was studied. Terpolymers with homogeneous compositions were synthesized. Then, 3,3,3-trifluoropropene (TFP) and 2,3,3,3-tetrafluoropropene (1234yf) were terpolymerized with VDF and TrFE. Although batch terpolymerizations resulted in terpolymers with strong compositional drift, the semi-continuous suspension process afforded better homogeneity. The thermal and electroactive properties of all the terpolymers were characterized. Finally, the introduction into poly(VDF-co-TrFE) copolymer chains of small amounts of a functional monomer (2-(trifluoromethyl)acrylic acid, MAF) allowed an increase of the adhesion properties onto glass and metal substrates without altering the electroactive properties. The study of the terpolymerizations of VDF, TrFE and a CF3-bearing termonomer contributed to a better understanding of the structure-properties relationships in fluorinated EAPs. Notably, the reduction of the crystal size was shown to be insufficient to afford RFE properties.

The commercial field of radical polymerized polymers, such as polyvinyl alcohol, is very broad partly because they are easy to polymerize and cheap. One aspect that could improve their commercial range is to enhance their degradation rate. As the environmental aspect of polymers grows bigger an enhancement of biological degradation is a great improvement. This thesis deals with the prospect of polymerizing polyvinyl alcohol with degradable linkages in the main chain. In order to achieve the aim the monomer 2-methylene-1,3-dioxepane is successfully synthesized and characterized. The synthesis is followed by copolymerization of 2-methylene-1,3-dioxepane with vinylacetate at the feed compositions; 30/70, 50/50, 70/30 mol% respectively. The copolymerization was successful and reached over 90% conversion at the reaction time 3-4 hours with the conditions 60°C and 5mol% 2,2-Azobis(2-methylpropionitrile) as initiator. The copolymerization is followed by hydrolysis with potassium hydroxide or Candida Rugosa Lipase. The results show that chain scission occurs when the polymer is hydrolyzed by potassium hydroxide but not by lipase. There is also a tendency toward hydrolysis of the chain with lipase.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23226号 / 工博第4870号 / 新制||工||1760(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大内 誠, 教授 秋吉 一成, 教授 田中 一生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18296号 / 工博第3888号 / 新制||工||1596(附属図書館) / 31154 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 中條 善樹, 教授 赤木 和夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18522号 / 工博第3914号 / 新制||工||1601(附属図書館) / 31408 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 辻井 敬亘, 教授 金谷 利治, 教授 山子 茂 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19894号 / 工博第4210号 / 新制||工||1651(附属図書館) / 32971 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 秋吉 一成, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<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)

<p> This thesis presents a study on silane based polymerization in two parts. </p> <p> In Part A, diphenylvinylsilane (1) underwent oligomerization with initiation by azo(bisisobutyronitrile) (AIBN) or benzoyl peroxide (BPO). The vinyl groups were preferentially consumed under either set of conditions. Several products were isolated; these included oligomers 3, an AIBN adduct 4, a dimer 5, and a trimer 6. The residual SiH moieties could be subsequently coupled hydrosilylatively with alkynes or vinylsilicones. The efficiency of the radical reactions was very low. 15% starting material was recovered even with 200 mol% of initiating radicals added to the reaction mixture. The relative radical reactivities of the two functional groups is discussed.</p> <p> In Part B, 1 was radically copolymerized with styrene and methyl methacrylate (MMA). From the results of infrared and 1H NMR it was determined that 1 participated in copolymerization via a vinyl type polymerization and not in the form of a hydrogen-transfer type polymerization. Residual SiH groups along the backbone of the polymer remained reactive. A vinylsilicone and 9-vinylanthracene were grafted onto the copolymer from MMA and 1 by hydrosilylation and radical methods, respectively.</p> / Thesis / Master of Science (MSc)