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1
Ma, Yinghua. "Living cationic polymerization of styrene monomers." Thesis, Aston University, 2000. http://publications.aston.ac.uk/9636/.
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This thesis describes an experimental investigation of synthesis of polystyrene under various polymerization conditions such as solvent polarity, temperature, initial concentrations of initiator, catalyst, monomer and added salts or co-catalyst, which was achieved using the living cationic polymerization technology in conjunction with gel permeation chromatography (GPC) and NMR spectroscopy. Polymerizations of styrene were conducted using 1-phenyl ethylchloride (1-PEC) as an initiator and tin tetrachloride (SnCI4) as a catalyst in the presence of tetra-n-Butylammonium chloride (nBu4NCI). Effects of solvent polarity varied by mixing dichloromethane (DCM) and less polar cyclohexane (C.hex), temperature, initial concentrations of SnC14, 1-PEC and nBu4NCI on the polymerizations were examined, and the conditions under which a living polymerization can be obtained were optimised as: [styrene]o ~ 0.75 - 2 M; [1-PEC]o ~ 0.005 - 0.05 M; [SnCI4Jo ~ 0.05 - 0.4 M; [nBu4NCIJo ~ 0.001 - 0.1 M; DCM/C.hex ~ 50/0 - 20/30 v/v; T ~ 0 to -45°C. Kinetic studies of styrene polymerization using the Omnifit sampling method showed that the number average molecular weight (Mn) of the polymers obtained increased in direct proportion to monomer conversion and agreed well with the theoretical Mn expected from the concentration ratios of monomer to initiator. The linearities of both the 1n([MJoI[M]) vs. time plot and the Mn vs. monomer conversion plot, and the narrow molecular weight distribution (MWD) measured using GPC demonstrated the livingness of the polymerizations, indicating the absence of irreversible termination and transfer within the lifetimes of the polymerizations. The proposed 'two species' propagation mechanism was found to apply for the styrene polymerization with 1-PEC/SnCI4 in the presence of nBu4NCl. The further kinetic experiments showed that living styrene polymerizations were achieved using the 1-PEC/SnCI4 initiating system in mixtures of DCM/C.hex 30/20 v/v at -15°C in the presence of various bromide salts, tetra-n-butylammonium bromide, tetra-n-pentylammonium bromide, tetra-n-heptylammonium bromide, and tetra-n-octylammonium bromide, respectively. The types of the bromide salts were found to have no significant effect on monomer conversion, Mn, polydispersity and initiation efficiency. Living polymerizations of styrene were also achieved using titanium tetrachloride (TiCI4) as a catalyst and 1-PEC as an initiator in the presence of a small amount of 2,6-di-tert-butylpyridine or pyridine instead of nBu4NCl. GPC analysis showed that the polymers obtained had narrow polydispersities (P.D. < 1.3), and the linearities of both the In([MJo/[MJ) vs. time plot and the Mn vs. monomer conversion plot demonstrated that the polymerizations are living, when the ratio of DCM and C.hex was less than 40 : 10 and the reaction temperature was not lower than -15°C. The reaction orders relative to TiCl4 and 1-PEC were estimated from the investigations into the rate of polymerization to be 2.56 and 1.0 respectively. lH and 13C NMR analysis of the resultant polystyrene would suggest the end-functionality of the product polymers is chlorine for all living polymerizations.
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Bahrin, Nurfariza. "Renewable monomers for bio-styrene formation using phenolic acid decarboxylase." Thesis, University of Warwick, 2017. http://wrap.warwick.ac.uk/100542/.
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Lignocellulose is an abundant natural polymer on earth that contains renewable resource of aromatic compound, the lignin. Many industrially valuable chemicals can be developed from lignin and this can reduce the dependency on petrochemicals. Wheat straw contains ferulic acid as one of its building blocks, which can be accumulated as a major metabolite from growth with Rhodococcus jostii RHA1, a known lignin degrading bacteria in minimal media. Using the enzyme phenolic acid decarboxylase (PAD) in engineered E.coli, ferulic acid was converted into 4-vinylguaiacol (3-methoxy-4-hydroxystyrene). The substituted monostyrene was then enzymatically polymerised by laccase to form a polymer that showed an adhesive property. This enzymatically generated polymer can potentially provide an alternative to synthetic process, besides providing renewable option to generate environmental friendly material in ambient conditions.
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Tichagwa, Lilian M. "Synthesis of acrylate-based polymeric and polymerisable surfactants and their application in the emulsion polymerisation of styrene." Thesis, Stellenbosch : University of Stellenbosch, 2006. http://hdl.handle.net/10019.1/1185.
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Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2006.<br>The study described in this dissertation examines the synthesis of mainly acrylate-based surfactants and their subsequent use as emulsifiers/stabilisers in the emulsion polymerisation of styrene. Some acrylamide-based surfactants were also studied, for comparison purposes only. Two major types of surfactants, polymerisable (surfactant monomers or surfmers) and polymeric, were synthesised, characterised and used in emulsion polymerisation reactions. The prepared polymerisable surfactants, 12-acryloyloxydodecanoic acid (12-ADA) and 11-acrylamidoundecanoic acid (11-AAUA), and their sodium salts, had reactive acryloyl functionalities.
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Clark, Darren Cameron. "Dual monomer grafting of styrene and maleic anhydride onto polyethylene, effect of polyethylene microstructure." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0020/NQ54405.pdf.
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Levy, Florence. "Fonctionnalisation d'un latex de polystyrène par un monomère chloré : le bis 2 chloroéthyl-itaconate." Lyon 1, 1987. http://www.theses.fr/1987LYO10538.
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Fonctionnalisation superficielle du polystyrene par bis 2-chloro ethyl-itaconate. Determination des constantes cinetiques et physicochimiques. Etude de la copolymerisation avec le styrene et l'acrylate de butyle
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Srichan, Sansanee. "Synthesis of sequence-controlled polymers by copolymerization of para-substituted styrenic derivatives and N-substituted maleimides." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF005/document.
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Dans ce travail, les copolymérisations radicalaires contrôlées de monomères donneurs (dérivés du styrène) et accepteurs (maleimides N-substitués) ont été effectuées afin de préparer des polymères à séquences contrôlées. Ces macromolécules ont été préparées par polymérisation radicalaire contrôlée par la voie des nitroxides en utilisant le SG1 comme agent de contrôle. Des polymères ayant des microstructures bien définies ont été obtenus par le contrôle du temps de l’addition d’une petite quantité de monomère accepteur au cours de la polymérisation d’un large excès de monomère de type donneur. Dans cette thèse, des nouveaux dérivés styréniques para-substitués ont été sélectionnés afin de préparer une variété de polymères fonctionnels à séquences contrôlées. Par exemple, des polyélectrolytes à base de poly(4-hydroxystyrène)s et poly(vinyl benzyle amine)s ont été obtenus par polymérisation de dérivés protégés du styrène (4-tert-butoxystyrène, 4-acetoxystyrène et N-(p-vinyl benzyl)phthalimide) avec une quantité non-stœchiométrique de maleimides N-substitués. Par ailleurs, des polymères PEGylés biocompatibles et solubles dans l’eau ont également été étudiés. Des polymères à séquences contrôlées portant des fonctions alcynes protégées sur chaque unité de styrène ont été dans un premier temps synthétisés. La suppression de ces groupes protecteurs a permis le greffage du α-méthoxy-ω-azido-PEG sur les fonctions alcynes libres en employant la chimie click de type CuAAC. Finalement, des polymères semi-cristallins à séquences contrôlées ont été élaborés en utilisant le styrène d’octadécyle comme monomère donneur. Les propriétés thermiques de ces polymères ont été étudiées afin d’évaluer l’influence de la microstructure sur le comportement de leur cristallisation<br>In this work, controlled radical copolymerizations of donor (styrenic derivatives) and acceptor monomers (N-substituted maleimides, MIs) have been investigated in order to synthesize sequence-controlled polymers. These macromolecules were prepared by nitroxide mediated polymerization using the nitroxide SG1 as a control agent. Polymers with defined microstructures were obtained by time-controlled addition of small amounts of acceptor monomers during the polymerization of a large excess of donor monomer. In this thesis, new styrenic derivatives have been studied in order to design sequence-controlled polymers with functional backbones. For example, sequence-controlled polyelectrolytes based on poly(4-hydroxystyrene)s and poly(vinyl benzyl amine)s were obtained through the polymerization of protected styrenic derivatives (i.e. 4-tert-butoxystyrene, 4-acetoxystyrene and N-(p-vinyl benzyl)phthalimide) with non-stoichiometric quantities of N-substituted maleimides. Furthermore, the preparation of PEGylated biocompatible water-soluble polymers was also investigated. Sequence-controlled polymers bearing protected alkyne functional groups on each styrene units were first synthesized followed by the removal of their protecting groups allowing the grafting of α-methoxy-ω-azido-PEG on free alkyne moieties via CuAAC mediated click reaction. Finally, sequence-controlled semi-crystalline polymers were synthesized using octadecylstyrene as a donor monomer. The thermal properties of these polymers were studied to evaluate the influence of polymer microstructure on crystallization behavior
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Applin, Samantha. "Surfactant Free Emulsion Polymerization of Poly(Styrene-Co-Methyl Methacrylate): Correlation of Microsphere Characteristics with Monomer Reactivity and Water Solubility." W&M ScholarWorks, 2017. https://scholarworks.wm.edu/etd/1530192354.
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Polymeric microspheres have been used in a broad range of applications from chromatographic separation techniques to analysis of air flow over aerodynamic surfaces. The preparation of microspheres from many polymer families has consequently been extensively studied using a variety of synthetic approaches. Although there are a myriad of polymeric microsphere synthesis methods, free-radical initiated emulsion polymerization is one of the most common techniques. In this work, poly(styrene-co-methyl methacrylate) microspheres were synthesized via surfactant-free emulsion polymerization. The effects of the co-monomer composition and addition time on particle size distribution, particle formation, and particle morphology were investigated. Particles were characterized using dynamic light scattering and scanning electron microscopy to gain further insight into particle size and size distributions. Reaction kinetics were analyzed through consideration of characterization results. A particle formation mechanism for poly(styrene-co-methyl methacrylate) microspheres was proposed based on characterization results and known reaction kinetics.
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Drockenmuller, Eric. "Synthèse de nouveaux nitroxydes et alcoxyamines fonctionnalisés. Application à la polymérisation radicalaire vivante/contrôlée de monomères vinyliques." Université Louis Pasteur (Strasbourg) (1971-2008), 2002. http://www.theses.fr/2002STR13071.
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Les travaux effectués au cours de cette thèse concernent la polymérisation radicalaire vivante/contrôlée de monomères vinyliques par les nitroxydes. Le principe de ce type de polymérisation repose sur l'établissement d'un équilibre entre espèces dormantes (ou alcoxyamines) et espèces actives (radicaux alkyle et nitroxyle). Afin d'abaisser la température de ce procédé et de l'étendre à d'autres monomères, nous avons modifié la réactivité du nitroxyde en introduisant divers substituants de polarité et d'encombrement stérique variables. Ainsi, une nouvelle classe de nitroxydes (b-sulfinyl nitroxydes), comportant une fonction polaire sulfoxyde sur le carbone situé en b, a été synthétisée. Ces radicaux ont été caractérisés par spectroscopie RPE (stabilité thermique, couplages aN et aH, constante de vitesse de dissociation kd). A partir de ces résultats, un de ces radicaux (NO_XI) a été engagé dans la polymérisation de monomères vinyliques. Il permet le contrôle de la polymérisation du styrène (Vp >> Vth) ainsi que celui des acrylates d'éthyle et de n-butyle à 90 ʿC. De plus, il a été montré que l'orientation de la fonction sulfoxyde, induite par la stéréochimie du nitroxyde, a une forte influence sur les caractéristiques du radical et sur les comportements cinétiques observés. Divers analogues structuraux de NO_XI ont ensuite été synthétisés, en remplaçant la fonction sulfoxyde par des groupements de polarité variable. L'un de ces radicaux (NO_XI_pentyl) permet un parfait contrôle de la polymérisation du styrène à 60 ʿC et une vitesse de polymérisation nettement supérieure à celle de la polymérisation thermique. La comparaison de l'ensemble des comportements cinétiques observés aux évolutions théoriques, a permis de déterminer les ordres de grandeurs des constante cinétiques impliquées dans ces systèmes (K et kc). Les résultats obtenus montrent que la valeur de kc dépend essentiellement de l'encombrement stérique des substituants portés par la fonction nitroxyle<br>This thesis focuses on the living/controlled radical polymerization of vinyl monomers mediated by nitroxides. The principle of this process is based on the establishment of an equilibrium between dormant species (or alkoxyamines) and active species (alkyl and nitroxyl radicals). In order to decrease the temperature of this process and to extend it to other monomers, we modified the nitroxide reactivity by introduction of substituents with different polarity and steric hindrance. A new class of nitroxides (b-sulfinyl nitroxides), bearing a polar sulfoxide function on the b-carbon atom, was then synthesized. These radicals have been characterized by ESR spectroscopy (thermal stability, coupling constants aN and aH, rate constant of dissociation kd). From these results, one of these radicals (NO_XI) has been engaged in the polymerization of vinyl monomers. It affords the control of the styrene (Vp >> Vth), ethyl and n-butyl acrylates polymerizations at 90 ʿC. Moreover, it has been shown that the orientation of the sulfoxide function, induced by the nitroxide stereochemistry, has a strong effect on the radical properties and on the polymerization kinetics. Various structural analogues of NO_XI were then synthesized, replacing the sulfoxide function by substituents of variable polarity. One of these radicals (NO_XI_pentyl) allows a perfect control of the styrene polymerization at 60 ʿC and a rate of polymerization clearly higher than the thermal polymerization one. The comparison of all polymerization kinetics with theoretical evolutions, allowed the determination of the orders of magnitude of the kinetic constants involved in the process (K and kc). These results show that the kc value depends mainly on the steric hindrance of the substituents carried by the nitroxide function
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Malek, Fouad. "Synthèse de nouveaux monomères à chaînes latérales pyrazole et bipyrazole et leurs polymérisations." Montpellier 2, 1992. http://www.theses.fr/1992MON20140.
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Ce travail concerne la synthese et la caracterisation des polymeres et copolymeres obtenus par polymerisation de nouveaux monomeres styreniques, vinyliques, maleimiques et methacryliques porteurs des cycles pyridine, pyrazole et bipyrazole. Une discussion sur la copolymerisation de ces monomeres avec d'autres monomeres conduisant a des systemes accepteur-donneur est presentee. En plus, des comparaisons entre la structure et les proprietes, notamment thermiques, sont abordees. Enfin deux applications ont ete etudiees: la premiere concerne les resines acetylantes selectives, la seconde l'obtention de membranes specifiques a la separation des metaux
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Ramirez, Marquez Walter. "Relations procédé de synthèse microstructure-morphologie-propriétés des copolymères acrylate de méthyle-styrène." Lyon 1, 1987. http://www.theses.fr/1987LYO19025.
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Copolymerisation en emulsion. Par le procede en reacteur ferme, l'existence d'azoetropes plus nombreux qu'en solution ou en masse confirme que les taux de reactivite sont des grandeurs cinetiques apparentes. Synthese de copolymeres a composition et a structuration controlees, par des procedes semicontinu, batch corrige et core-shell
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Guillaume, Jean-Luc. "Synthèse de colloïdes modèles par polymérisation en émulsion de styrène et d'acrylate de n-butyle : leur utilisation dans des études de rhéologie et de formation de film." Lyon 1, 1985. http://www.theses.fr/1985LYO10042.
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Hidalgo, Manuel. "Synthèse et caractérisation physicochimique et thermomécanique des matériaux filmogènes issus de latex à base styrène-acrylate de butyle fonctionnalisés." Lyon 1, 1992. http://www.theses.fr/1992LYO10015.
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On a etudie les aspects lies a la synthese chimique par polymerisation en emulsion de latex a base d'acrylate de butyle, d'une part et de copolymeres styrene-acrylate de butyle, d'autre part, fonctionnalises par des monomeres reticulants, ainsi que les aspects lies aux proprietes thermomecaniques des films obtenus a partir de ces latex. Les resultats ont ete regroupes en quatre parties, a savoir: i) etude des systemes a base de styrene-acrylate de butyle non fonctionnalises, utilises comme systemes de reference; ii) etude des systemes a base de styrene-acrylate de butyle fonctionnalises par un monomere carboxylique, l'acide methacrylique; iii) etude des systemes a base d'acrylate de butyle fonctionnalises par des monomers reticulables derives de l'acrylamide et du methacrylamide; iv) etude des systemes a base de styrene-acrylate de butyle fonctionnalises par les memes monomeres utilises dans l'etude precedente. On a conduit chacune de ces etudes en suivant des approches chimiques et physiques liees respectivement a la synthese des latex (microstructure des macromolecules et structuration des particules) et aux proprietes des films en relation avec la morphologie. La complementarite des renseignements obtenus en suivant cette demarche a pu etre demontree et des bases pour l'etablissement de modeles theoriques quantitatifs ont ete jetees
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Bonardi, Christian. "Copolymérisation en émulsion styrène-acrylate de butyle en présence d'un monomère réticulable (n-méthylolacrylamide) : relation procédé de synthèse-structure-propriétés." Lyon 1, 1987. http://www.theses.fr/1987LYO10543.
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Synthese de copolymeres styrene/acrylate de butyle filmables et reticulables par un traitement thermique. Determination de la morphologie des particules de latex et de la repartition du monomere fonctionel. Etude des proprietes mecaniques
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Bonardi, Christian. "Copolymérisation en émulsion styrène-acrylate de butyle en présence d'un monomère réticulable (N-méthylolacrylamide) relation procédé de synthèse-structure-propriétés /." Grenoble 2 : ANRT, 1987. http://catalogue.bnf.fr/ark:/12148/cb376030979.
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Quinebeche, Sébastien. "Suivi cinétique des polymérisations et copolymérisations anioniques de monomères éthyléniques par spectroscopie IR et UV-visible in situ." Bordeaux 1, 2007. http://www.theses.fr/2007BOR13359.
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Les travaux présentés dans ce texte concernent la mise au point d'une nouvelle technique de suivi cinétique des polymérisations et copolymérisations anioniques du styrène (S), de l'isoprène (l), du 1,1-diphényléthythylène (DPE) et du méthacrylate de méthyle (MMA), au moyen du couplage des spectroscopies IR et UV-visible in situ. L'objectif de l'étude est de mieux comprendre l'influence de certains paramètres expérimentaux sur les différentes étapes qui interviennent dans la préparation des copolymères triblocs poly(styrène-b-butadiène-b-méthacrylate de méthyle) (SBM) dans les solvants non polaires. Pour des raisons d'opportunité expérimentale, l'isoprène a été pris comme modèle du butadiène. La technique de suivi des polymérisations utilise des sondes lesquelles, plongées dans le milieu réactionnel, permettent de mesurer simultanément et en temps réel les concentrations en monomères et en espèces activesau cours de la polymérisation. Bien qu'elle ne fasse pas appel aux techniques sous haut vide qui permettent l'accès aux conditions de grande pureté du milieu réactionnel, notre méthode a cependant permis des mesures rapides, précises et reproductibles des constantes de vitesse des différentes homo- et copolymérisations étudiées. Les résultats de l'étude cinétique ont ainsi pu être utilisés pour une meilleure connaissance du comportement réactionnel de ces systèmes. Ainsi, par exemple, il a été montré que, lors de la copolymérisation à blocs du styrène et de l'isoprène amorcée par le n-butyllithium, la nature du solvant aromatique influence seulement la cinétique d'homopolymérisation du styrène (Kss toluène > Kss éthylbenzène). Il a aussi été montré que l'ajout du 2-méthoxyéthanolate de lithium lors de l'étape d'addition du DPE sur le S-b-Ili accélère non seulement la réaction d'addition du DPE mais améliore également l'efficacité de l'amorçage de la polymérisation du MMA, ce qui est essentiel pour la qualité des produits obtenus. Ce ligand, initialement utilisé pour contrôler la polymérisation du MMA, joue donc un rôle triple dans la préparation des SBM.
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Filho, Aluisio Pinelli. "Modelagem matemática e estudo experimental da copolimerização de estireno e butadieno em emulsão." Universidade de São Paulo, 2006. http://www.teses.usp.br/teses/disponiveis/3/3137/tde-17112006-123329/.
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Neste trabalho, estudos da copolimerização em emulsão de estireno e butadieno foram realizados em duas etapas. A primeira etapa consistiu na obtenção de um modelo matemático que representasse os processos em batelada e em semicontínuo através das principais variáveis do processo. Na segunda etapa, o efeito de diversas variáveis importantes ao processo foi avaliado, dentre elas: o tempo de adição dos reagentes, o tipo de alimentação empregado e a temperatura da reação. O modelo matemático se baseia em um trabalho previamente publicado que foi adaptado para simular o processo de copolimerização de estireno e butadieno em emulsão. Foram simulados processos em batelada e em semicontínuo. Em conjunto com os resultados experimentais, foi realizada a estimação de parâmetros não obtidos na literatura utilizando o método de Marquardt. As características do processo e as propriedades do polímero, tais como, conversão, diâmetro de partícula, taxa de polimerização e pressão interna do reator também foram obtidas, fornecendo condições para otimização e avaliação do processo de polimerização em batelada e em semicontínuo. Adicionalmente, também foi proposto um modelo de equilíbrio líquido-vapor dos monômeros. Os ensaios experimentais foram realizados em reator encamisado semicontínuo de mistura com 3 litros, nos quais foram utilizados persulfato de sódio como iniciador, lauril sulfato de sódio como emulsificante e tercdodecil mercaptana como agente de transferência de cadeia. Foram estudados os efeitos da temperatura, do tipo e do tempo de alimentação utilizada. A velocidade de polimerização, os diâmetros médios de partículas, o teor de monômero residual, o teor de insolúveis e o teor de resíduos foram avaliados. A cromatografia gasosa foi aplicada com sucesso em análises de látex e monômeros com finalidades diversas, destacando-se a obtenção de coeficientes de atividade necessários ao modelo de equilíbrio líquido-vapor, análise da concentração de monômeros ao longo da reação e análise da concentração de monômero residual.<br>In this work, studies of the styrene butadiene emulsion copolymerization had been performed in two stages. The first stage composed of a mathematical model that represented the batch and semi continuous process. In the second stage, the effects of diverse process variables were evaluated, among them: the time of addition of the reagents, feeding type and temperature reaction. The mathematical model was based on previously published work that it was adapted to simulate the styrene butadiene emulsion copolymerization process. Batch and semi continuous processes were simulated. In assembly with the experimental results, Marquardt method was applied to estimate some parameters that wasnt found in literature. The variable process and the properties of polymer, such as, conversion, particle diameter, rate of polymerization and pressure of the reactor had been also simulated to batch and semicontinous process. A liquid-vapor balance of monomers model was proposed. The experimental stage had been carried through in a semi continuous stirring jacket tank reactor with 3 liters. Sodium persulfate as initiating, sodium lauryl sulfate as surfactant and Tert dodecyl mercaptan as chain transference agent had been used. The effect of temperature, type and time feeding had been studied. Polymerization rate, particles diameter, residual monomer had been evaluated. The gaseous chromatography was successfully applied in analyses of latex with diverse purposes: activity coefficient estimation, adjustment of liquid-vapor model, analysis of residual monomer of the reaction and volatiles organic components concentration in final latex.
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Goussé, Cécile. "Applications de la réaction de Diels-Alder aux polymères furaniques." Grenoble INPG, 1997. http://www.theses.fr/1997INPG0007.
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Certains derives furaniques, obtenus a partir de la biomasse, se comportent comme d'excellents dienes vis a vis de la reaction de diels-alder. Dans cette perspective, l'application de cette reaction aux polymeres furaniques peut etre envisagee sous deux aspects. Le premier consiste en la modification de polymeres tels l'alcool polyvinylique ou le polystyrene par greffage de groupements pendants furaniques, qui seront ensuite mis en reaction avec des mono ou bismaleimides conduisant respectivement a des polyadduits ou des gels. Le second concerne la synthese et la polycondensation de monomeres possedant des extremites dieniques et/ou dienophile (aa + bb et ab). Cette these decrit l'elaboration et la caracterisation de divers materiaux bases sur l'application de ces differents concepts. La reversibilite de la reaction de diels-alder sur ce type de composes a egalement ete etudiee.
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CHYANG, SHEU JIH, and 許繼強. "Styrene Miniemulsion Polymerization ：Effect of Functional Monomers." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/07496673192438647699.
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碩士<br>國立臺灣科技大學<br>化學工程系<br>88<br>In MMA miniemulsions stabilized by SDS/DMA, both the Ostwald ripening and creaming rates decrease with increasing [DMA] upon aging at 35℃. On the other hand no appreciable Ostwald ripening and creaming were detected for the SMA containing MMA miniemulsions. In addition, MMA miniemulsion shows a larger Ostwald ripening rate than STY miniemulsion stabilized by SDS/DMA.
In STY miniemulsion polymerization stabilized by SDS/DMA（or SDS/SMA）, Rp increases with increasing [HEMA]. Nd and Nw also increase when [HEMA] increases. In addition, Mw increases with incresing [HEMA], but the Zeta potential of latex particles decreases with increasing [HEMA]. In STY miniemulsion polymerization stabilized by SDS/DMA（or SDS/SMA）, the addition of HEMA or HPMA increases both Rp and Pdye. This can attribute to the different of hydrophilicity between HEMA and HPMA. The Mw of emulsion polymer goes up but the ζ of latex particles decreases when HEMA or HPMA is used.
In STY miniemulsion polymerization stabilized by SDS/SMA, the ratio Np,f/Nm,i goes up with increaseing [C5OH]. In STY miniemulsion polymerization stabilized by SDS/DMA, Rp increases with increaseing [C5OH], whereas Np,f/Nm,i seems to be insensitive to changes in [pentanol].
In STY miniemulsion polymerization stabilized by SDS/DMA（or SDS/SMA）, both Rp and Xf decreases with increasing [AA]. Pdye and Nd increase but Nw decreases with increasing [AA]. Mw and PDI of the emulsion polymer also goes up with increasing [AA]. In STY miniemulsion polymerization stabilized by SDS/DMA（or SDS/SMA）, the addition of AA or MAA tends to decrease both the Rp and Xf . In addition, Pdye also increases when AA or MAA is added to the reaction system.
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Li, Donghong. "Copolymerization of styrene and butadiene monomers via miniemulsion /." Diss., 1998. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:9831807.
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Sanchez, John Lawrence. "Synthesis and characterization of divinyl monomers for styrene-based reaction injection molding." Thesis, 2003. http://wwwlib.umi.com/cr/utexas/fullcit?p3118071.
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Kuricová, Miroslava. "Molecular mechanisms involved in genotoxicity of industrially important monomers (styrene, 1,3-butadiene)." Doctoral thesis, 2009. http://www.nusl.cz/ntk/nusl-370561.
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1 ABSTRACT The evaluation of individual health risk in workers occupationally exposed to industrial xenobiotics requires the use of a large number of parameters reflecting external exposure, internal exposure, biological effects and individual susceptibility. Environmental, occupational and life style-related exposure to mutagenic agents may contribute to cancer risk in humans. To prevent the potentially hazardous effects of such agents it is important to understand their mechanisms of action. Styrene is one of the most important monomer for producing polymers and copolymers in plastics, latex paints and together with 1,3-butadiene (BD) in the manufacture of synthetic rubbers. In this thesis, a large set of parameters, including markers of external and internal exposure and biomarkers of biological effects and susceptibility have been studied in relation to the occupational exposure to both styrene and BD. First part of the present study was focused on evaluating the role of various biomarkers to assess genotoxic effects of above mentioned xenobiotics. Biomarkers reflecting styrene- and BD-induced genotoxicity and mutagenicity: O6 -styrene guanine DNA adducts, haemoglobin adducts, single-strand breaks (SSBs), SSB Endo III sites, chromosomal aberrations (CA), hypoxanthine-guanine phosphoribosyltransferase...
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Jayanthi, S. "Oxidative Copolymerization Of Vinylmonomers : Studies On The Microstructure And Reactivities Of The Copolyperoxides." Thesis, 1995. https://etd.iisc.ac.in/handle/2005/1840.
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Jayanthi, S. "Oxidative Copolymerization Of Vinylmonomers : Studies On The Microstructure And Reactivities Of The Copolyperoxides." Thesis, 1995. http://etd.iisc.ernet.in/handle/2005/1840.
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Wei, Jy-Jinn, and 魏進枝. "Fundamentally Thermal Hazard Analysis for Inhibited Styrene Monomer." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/02627565451554346482.
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碩士<br>國立雲林科技大學<br>環境與安全工程系碩士班<br>91<br>ABSTRACT
Inhibited Styrene Monomer (SM) is one of the important raw materials used in the petrochemical industry. Under ambient conditions, it demonstrates extremely weak exothermic behaviors.Compared with other calorimeters used for hazard analysis, such as Vent Sizing Package2, (VSP2) which cannot detect such weak exothermic phenomena, in this research, the exothermic polymerization is characterized by an isothermal microcalorimeter, Thermal Activity Monitor (TAM) and Differential Scanning Calorimeter (DSC). Thermograms showed that SM with 10 ppm inhibitor of 4-t-butylcatechol (TBC) in the temperature range above 120℃ follows n-th order reaction. However, from 50℃ to 85℃, it follows an autocatalytic reaction. In addition, reaction order, rate constant and activation energy are verified to be 0.5, 53.419 kJ/mol and 1.117×103 exp (-53,419/8.314×T), respectively. From the experimental the exothermal onset temperature is linearly proportion to the inhibitor concentration. Meanwhile the logarithm time reach maximum reaction rate is linearly proportion to the inhibitor concentration, as well. Finally, the acquired parameters can be provided to proactively the accidents at low temperature conditions during storage and transportation.
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Chin-Chuan, Chen, and 陳進傳. "Exothermic Decomposition of Styrene Monomer at Low Temperature Conditions." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/02473290762355739699.
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碩士<br>國立雲林科技大學<br>環境與安全工程系碩士班<br>90<br>Styrene Monomer (SM) has been widely used for polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), styrene-acryonitrile (SAN) in the petrochemical industry. In recent years, from 1994 to 2001, several serious accidents occurred in Taiwan due to human errors, its inherent instability, accidents or external fire.
Compared with other calorimrtries on thermal hazard analysis, such as differential scanning calorimetry (DSC), vent sizing package, (VSP) which can not detect such weak exothermic phenomena, in this research, the exothermic polymerization is characterized by an isothermal microcalorimeter, thermal activity monitor (TAM). Thermograms show that in the temperature range from 50℃ to 80℃, follows the autocatalytic reaction. In addition, the reaction order, activation energy and rate constant are verified be 0.5, 62.8 kJ/mol and 5.039×104 exp (-62,083/8.314×T), respectively. Finally, the practical suggestions can be provided to prevent the specific plant from accidents, especially at low temperature conditions during storage and transportation.
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"Determination of styrene monomer in food-contact polymers and foodstuffs by gas chromatography." Chinese University of Hong Kong, 1991. http://library.cuhk.edu.hk/record=b5886905.
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by Lung Man Tung.<br>Thesis (M.Phil.)--Chinese University of Hong Kong, 1991.<br>Includes bibliographical references.<br>ACKNOWLEDGMENT --- p.i<br>ABSTRACT --- p.ii<br>Chapter CHAPTER 1 --- GENERAL INTRODUCTION --- p.1<br>Chapter 1.1 --- Stationary phases and detectors --- p.2<br>Chapter 1.2 --- Internal standardization --- p.5<br>Chapter 1.3 --- Common pre-treatment technique --- p.6<br>Chapter 1.4 --- Pre-treatment techniques --- p.9<br>Chapter 1.5 --- Objectives of this work for the determination of styrene --- p.11<br>Chapter CHAPTER 2 --- EXPERIMENTAL --- p.13<br>Chapter 2.1 --- Instrumentation --- p.13<br>Chapter 2.2 --- Reagents and solutions --- p.16<br>Chapter 2.3 --- Preparation of stock solutions --- p.18<br>Chapter 2.4 --- Sample preparation --- p.19<br>Chapter 2.5 --- Extraction method for food samples --- p.20<br>Chapter 2.6 --- Procedure for the analytical finish --- p.22<br>Chapter 2.7 --- Assessment of the food matrix effect on the recovery of styrene --- p.23<br>Chapter 2.8 --- Confirmatory Procedures --- p.23<br>Chapter 2.9 --- Treatment of data --- p.24<br>Chapter CHAPTER 3 --- DEVELOPMENT OF METHOD --- p.26<br>Chapter 3.1 --- Development of GC method --- p.26<br>Chapter 3.2 --- Development of the extraction method --- p.29<br>Chapter CHAPTER 4 --- DETERMINATION OF RESIDUAL STYRENE IN POLYSTYRENE POLYMER --- p.50<br>Chapter 4.1 --- The proposed method --- p.50<br>Chapter 4.2 --- Identification of polymer and one cup for the ice-cream cone --- p.51<br>Chapter 4.3 --- Determination of residual styrene monomer in polystyrene container and cup --- p.52<br>Chapter CHAPTER 5 --- DETERMINATION OF STYRENE MONOMER MIGRATED INTO FOODSTUFFS --- p.58<br>Chapter 5.1 --- Methodolgy and scope --- p.58<br>Chapter 5.2 --- Determination of styrene migrated into ice-cream --- p.59<br>Chapter 5.3 --- Determination of styrene migrated into Yakult and Yogo --- p.60<br>Chapter 5.4 --- Determination of styrene migrated into foodstuff kept at elevated temperature in polystyrene containers --- p.60<br>Chapter 5.5 --- Conclusion --- p.74<br>REFERENCES --- p.76<br>APPENDIX --- p.80
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Hu, Wei-Chun, and 胡偉駿. "Ethylene-Derived Process Design and Integration:Case Studies of Ethylene Oxide and Styrene Monomer." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/69ft88.
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碩士<br>淡江大學<br>化學工程與材料工程學系碩士班<br>95<br>Since energy crisis, heat integration has become one of the important issues in the process systems engineering. Due to the price of energy is constantly rising, how to increase the efficient use of energy in the process has also become of great importance in the field of process design.
Ethylene oxide and styrene are both derived from the most basic and important building block of petrochemicals, i.e., ethylene. Ethylene oxide is a chemical used to make ethylene glycol, which is the primary ingredient in antifreeze. It is also used in the manufacture of ethylene-oxide derivatives (EOD), including both of the low molecular and high molecular polymers for use in many applications such as detergent additives. Styrene is the monomer used to make polystyrene, which has a multitude of uses, and has been an important intermediate chemical in the plastics industries and rubber industries. In terms of inherent safe designs, since ethylene oxide has a very wide range of explosion limits－3-80%, we have to pay attention to the design of reactors. It is also worth mentioning that the styrene product can spontaneously polymerize at higher temperature, it is necessary to maintain the product temperature below 125℃.
In this thesis, we have carried out two case studies: one is “ethylene oxide process”, and the other is “styrene monomer process”. Ethylene-oxide process belongs to an important category as oxidation in the chemical industries. Like most ethyl benzene/styrene facilities, there is significant heat integration between the two plants. The ethyl benzene reaction is exothermic, so steam is produced, and the styrene reaction is endothermic, so energy is used in the form of steam. Both of the two cases were simulated first by using AspenPlus. Then, heat- exchanger network designs were synthesized and analyzed by using SuperTarget. Significant utility savings were achieved for both of the two case studies. The hot utility savings is 34% and cold utility savings is 25%, as compared with the base-case design, for the ethylene-oxide process with a minimum approach temperature of 10℃. While the hot utility savings is 70% and cold utility savings is 63%, as compared with the base-case design, for the alkylation reaction (exothermic) of the styrene process with a minimum approach temperature of 10℃, the hot utility savings is 30% and cold utility savings is 3%, as compared with the base-case design, for the dehydrogenation reaction (endothermic) of the styrene process with the same minimum approach temperature. Finally, if we take appropriate cold/hot streams for heat integration from the whole styrene process, we found the hot utility savings is 65% but no cold utility savings with a minimum approach temperature of 10℃.
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謝如嘉. "Studies on the soapless emulsion copolymerization of styrene and the monomer of chelating functional group." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/41756080406117303282.
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碩士<br>國立成功大學<br>化學工程學系<br>88<br>Modify GMA, a new monomer with chelating functional group, which was synthesized by Glycidyl methacrylate（GMA） and Iminodiacetic acid（IDA）. M-GMA and styrene copolymer was prepared by soapless emulsion polymerization. The variables studied were the monomer concentration, initiator concentration, temperature, pH value and cosolvent. The reaction kinetics, which expressed as follow, were determined by measuring the pH value, conductivity, zeta potential, particle size and conversion.
R=k[kps]0.22[M-G]-2[styrene]1
The nucleation mechanism was characterized by FTIR, DSC and EA(element analysis). The nucleation mechanism suggested that polymerization took place in aqueous phase at first. After Poly(M-G) chain growth to a certain length, the radical transferred to styrene. Then the styrene in the aqueous phase continuously diffused into the particle. In the end, the particle was stabilized by Poly(M-G).
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Wang, Ching-Yi, and 王瀞儀. "Risk Management of Styrene Monomer Market for Plasticized Raw Materials - Application of Value-at-Risk." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/av6rd4.
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碩士<br>淡江大學<br>財務金融學系碩士在職專班<br>106<br>In this paper, the jump - diffusion model ARJI is used to investigate the abnormal beating state and the variability reaction caused by the styrene monomer market risk management. The jump frequency and jump size estimated by the model are confirmed, the styrene monomer market risk management, research findings The market risk application of styrene monomer further captures the fat tail, the optimization of time fluctuation and discontinuous jump behavior, and the instantaneous jump behavior fluctuation caused by the common information is 5.096% , which is caused by the jump process of styrene monomer return rate. The change accounted for 60.19% of the total change . It is possible to predict the risk of the risk under the 99% confidence level of the model outside the sample , indicating that the estimation of risk value and risk management have important information. Therefore, it is possible to extend the recommended intention of enterprise management decision-making: styrene monomer market risk, price hopping state, companies can refer to their volatility trend hopping frequency, and conduct risk-avoidance reference to ensure the lowest market risk, so as to avoid losses and avoid losses. When the existing inventory price is higher than the market risk, the inventory should be quickly degraded. Otherwise, when the inventory price is lower than the market risk, the destocking should be slowed down, and the new inventory should be increased or decreased according to the inventory; Raw material cost is estimated to be positive or negative, and its management and sales model are adjusted to facilitate sustainable business operations; enterprise managers can set minimum and maximum values that can withstand market risk, when they exceed their settings. When the value is involved in the management, let its work target be assigned to the implementer, in order to fully authorize the work.
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Chang, Yih-Her, and 張義和. "Sulfonated Tetracarboxylic Polyester (SMTAPE) Emulsifier：Synthesis, Surfactant Characteristics, and Studies on The Emulsion Polymerization of Butyl Methacrylate/Styrene Monomer." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/02331666243821373135.
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博士<br>國立清華大學<br>化學工程學系<br>87<br>A novel polymeric emulsifier， SSIPM modified tetracarboxylic acid terminated polyester (SMTAPE)was prepared by end-capping sulfopolyester polyol with TMA in this study. The surface characteristics of SMTAPE， the optimum hydrophobic length of SMTAPE for the emulsion polymerization of PBMA， the nucleation mechanism and the surface area occupied by a SMTAPE molecule on a polymer latex particle at room temperatuve were studied by analyzing the surfactant characteristics， the reaction kinetic and the stability of the latices， the consumption of SMTAPE emulsifier during emulsion polymerization and the adsorption behavior of SMTAPE on polystyrene latices.
The SMTAPE emulsifier is surface active， lowering the surface tension of water by about 15 mN/m at the cmc.
Experimental results also indicate that SMTAPE emulsifiers with a shorter average hydrophobic length stabilize the PBMA latex by the depletion mechanism. Although possessing good mechanical stability， using those emulsifiers have a higher coagulum during the synthesis stage. However， the SMTAPE emulsifiers with a longer average hydrophobic length anchor strongly on the PBMA latex particles and stabilize them by an electrotatic force with a negligible amount of steric stabilization. Although possessing better synthesis stability， using these emulsifiers have a poor mechanical stability. Results presented herein also confirm that the SMTAPE emulsifiers with optimum hydrophobic length can anchor latex particles and show steric stabilization mechanism with good synthesis and mechanical stability.
Futhermore， according to the experimental results， formation of the subsequent PBMA latex is attributed to a coagulation process of particle precursors， micellar particles as well as existing PBMA latex particles.
The effect of the stirring speed and the amount of emulsifier on the kinetics and particle size distribution were studied to obtain more quantitative evidence for the nucleation mechanism in this system. The experimental results from the kinetic studies and the emulsifier consumption clearly showed that a continuous nucleation mechanism with no Smith-Ewart interval II present were the characteristics of this system. this was attributed to the high concentration of SMTAPE emulsifier in the polymerization， which led to a large surface area and vast number of ~10nm micelles which served as the major locus of particle nucleation and the nucleation period lasted well into the reaction until the disappearance of the micelles or the disappearance of monomer droplets. A broad particle size distribution was oberved thoughout the reaction.
The surface area occupied by a SMTAPE molecule on a PS latex particle at 25℃ was found to be 187 at saturation. The conformation of SMATAPE emulsifier molecule adsorbed on a PS latex particle is thought to be a hydrophobic segment “trains” anchored to the polymer surface.