Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / The synthesis of complex architectures, namely block copolymers with tailored enduse properties, is currently an important research area in academia and industry. The challenge is finding a versatile polymerization technique capable of controlling the molecular properties of the formed copolymers, which in turn determines their macroscopic properties. Reversible addition-fragmentation chain transfer (RAFT)- mediated living polymerization is a robust technique capable of producing controlled polymer products. With the great advances in living polymerization techniques and the environmental awareness of society there is an increasing demand to produce these polymer products via the RAFT living technique in heterogeneous media. Conventional emulsion and miniemulsion polymerization present various problems when used to produce polymers mediated by the RAFT process. There is an inherent need to find cost effective and flexible operating conditions to conduct RAFT polymerization in heterogeneous media with the ability to produce well-defined block copolymers. In this study the use of three novel trithiocarbonate RAFT agents to produce welldefined AB-type, ABA-type and star block copolymers via the RAFT process was investigated. Optimal operating conditions for the production of living block copolymers in homogenous and heterogeneous media were determined. The main focus was on the development of the RAFT process in heterogeneous media to efficiently produce block copolymer latex products. The RAFT-mediated miniemulsion polymerization system stabilized with non-ionic surfactants was thoroughly investigated. The ability of the ab initio and in situ RAFT-mediated emulsion polymerization systems to produce controlled latexes was demonstrated. Controlled block copolymer products were successfully synthesized in homogenous and heterogeneous media via the RAFT process when the optimum reaction conditions were chosen.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / Synthesis of two surfmers (cationic and anionic) was carried out and the surfmers were used to stabilize particles in miniemulsion polymerization. Surfmers were used to eliminate adverse effects associated with free surfactant in the final product e.g. films and coatings. The Reversible Addition Fragmentation chain Transfer (RAFT) polymerization process was used in miniemulsion polymerization reactions to control the molecular weight distribution. RAFT offers a number of advantages that include its compatibility with a wide range of monomers and solvents. Moreover block copolymer synthesis is possible via chain extension. A comparative study between classical surfactants and surfmers was conducted in regard to reaction rates and molar mass distribution. The rates of reactions of surfmer stabilized RAFT miniemulsion polymerization of Styrene and MMA were similar (in most cases) to classical surfactant stabilized RAFT miniemulsion polymerization reactions. The final particle sizes were also similar for polystyrene latexes stabilized by surfmers and classical surfactants. However PMMA latexes stabilized by surfmers had larger particle sizes compared to latexes stabilized by classical surfactants. The surfmers were also oligomerized in homogeneous media using the RAFT process and their Mn values were estimated using UV-VIS spectroscopy. The oligosurfmers were then used as emulsifiers in RAFT miniemulsion polymerization. The rates of reaction were slower than rates obtain when the surfmers (monomer or oligosurfmers) were used directly as emulsifiers in RAFT miniemulsion polymerization of styrene and MMA. The final latex particle sizes obtained with oligosurfmers were also larger than that of latex stabilized by their parent monomers. The RAFT process was successfully applied in miniemulsion polymerization in both classical surfactant and surfmer stabilized miniemulsions. The molecular weight increased with conversion showing that the molecular weights of the polymers were controlled.

Thesis (PhD (Chemistry and Polymer Science))--Stellenbosch University, 2008. / The synthesis of glycopolymers with various comonomers as prepared via the RAFT process is investigated. The macro-RAFT agent poly(3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose) (PMAlpGlc) was prepared by polymerization of the glycomonomer with cumyl phenyl dithioacetate as the chain transfer agent. Chain extension with styrene or methyl acrylate or acrylic acid afforded novel diblock copolymers, (PMAlGlc-b-poly[styrene] or PMAGlc-b-poly[methyl acrylate] or PMAlGlc-b-poly[acrylic acid]), with predetermined molecular weights and narrow molecular weight distributions. The poly(acrylic acid) based glycopolymer was used to modify the surface of CaCO3, forming what will be referred to as a ‘sugar-coated CaCO3’ particle. This surface modifying effect was evaluated in depth; a schematic study of the effect of reaction temperature, pH, reaction time and glycopolymer concentration on CaCO3 crystallization was carried out. The analytical techniques Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM) were used to verify that these ‘sugar-coated CaCO3’ particles have an increased adherence to cellulose compared to ‘non sugar-coated’ particles. A series of polymer configurations comprising various ratios of glycomoiety to poly(acrylic acid) was prepared. The effect of this polymer series on CaCO3 crystallization was evaluated and the ideal polymer configuration and its optimum synthesis conditions (i.e. reaction pH, temperature, time and polymer concentration) that gave maximum adherence of the ‘sugar-coated CaCO3’ particle onto cellulose were identified. The ability of these poly(acrylic acid) based glycopolymers to increase the interaction between CaCO3 and cellulose was then evaluated. This was done by simply mixing all three substrates, i.e. glycopolymer, cellulose and CaCO3 together. Analysis by TGA, SEM and Thin Layer Chromatography (TLC) revealed both the ideal polymer configuration that favoured increased adherence of the CaCO3 to cellulose and the optimum reaction conditions required for application and testing. In addition to studying the interaction between cellulose and CaCO3, the amphiphilic nature of the glycopolymers was determined. Transmission Electron Microscopy (TEM) confirmed that coreshell particles were prepared and that these particles are solvent exchangeable (in the case of styrene and methyl acrylate glyco-blocks) or pH exchangeable (in the case of acrylic acid glyco-blocks).

No description available.

<p>Liquid chromatography is an important separation technique for a vast number of analytes. This thesis mainly focuses on the development of stationary phases for liquid chromatography based on zwitterionic sulfobetaine polymers.</p><p>In the thesis, various ways to prepare zwitterionic polymers in an aqueous environment using reversible addition fragmentation chain transfer (RAFT) polymerization are described. Both telomers, i.e. short soluble polymer chains containing a functional terminal group, as well as graft polymers on various supports have been synthesized. The RAFT polymerization technique provides an increased degree of control of the final polymers, which may aid in the preparation of more specifically tailored separation materials.</p><p>Sulfobetaine polymers carry both a positive and a negative charge within a single entity, which results in interesting solution properties as well as highly biocompatible features. These unique features make them especially suited for separation of highly polar and/or charged compounds. An example of the successful separation of short peptides using a stationary phase synthesized with the RAFT technique is given.</p><p>The unusual properties of sulfobetaine-type polymers are believed to be associated with the structure of water close to the polymer. A study of water structure in some silica based stationary phase grafted with zwitterionic sulfobetaine polymers was conducted. The impact of water structure on retention characteristics was investigated.</p>

The Reversible Addition Fragmentation Chain Transfer (RAFT) process using the new RAFT agent benzyldithiophenyl acetate is shown to be a powerful polymerization tool to synthesize novel well-defined amphiphilic diblock copolymers composed of the constant hydrophobic block poly(butyl acrylate) and of 6 different hydrophilic blocks with various polarities, namely a series of non-ionic, non-ionic comb-like, anionic and cationic hydrophilic blocks. The controlled character of the polymerizations was supported by the linear increase of the molar masses with conversion, monomodal molar mass distributions with low polydispersities and high degrees of end-group functionalization. <br><br> The new macro-surfactants form micelles in water, whose size and geometry strongly depend on their composition, according to dynamic and static light scattering measurements. The micellization is shown to be thermodynamically favored, due to the high incompatibility of the blocks as indicated by thermal analysis of the block copolymers in bulk. The thermodynamic state in solution is found to be in the strong or super strong segregation limit. Nevertheless, due to the low glass transition temperature of the core-forming block, unimer exchange occurs between the micelles. Despite the dynamic character of the polymeric micellar systems, the aggregation behavior is strongly dependent on the history of the sample, i.e., on the preparation conditions. The aqueous micelles exhibit high stability upon temperature cycles, except for an irreversibly precipitating block copolymer containing a hydrophilic block exhibiting a lower critical solution temperature (LCST). Their exceptional stability upon dilution indicates very low critical micelle concentrations (CMC) (below 4∙10^-4 g∙L^-1). All non-ionic copolymers with sufficiently long solvophobic blocks aggregated into direct micelles in DMSO, too. Additionally, a new low-toxic highly hydrophilic sulfoxide block enables the formation of inverse micelles in organic solvents. <br><br> The high potential of the new polymeric surfactants for many applications is demonstrated, in comparison to reference surfactants. The diblock copolymers are weakly surface-active, as indicated by the graduate decrease of the surface tension of their aqueous solutions with increasing concentration. No CMC could be detected. Their surface properties at the air/water interface confer anti-foaming properties. The macro-surfactants synthesized are surface-active at the interface between two liquid phases, too, since they are able to stabilize emulsions. The polymeric micelles are shown to exhibit a high ability to solubilize hydrophobic substances in water. / Amphiphile sind Moleküle, die aus einem hydrophilen und einem hydrophoben Molekülteil aufgebaut sind. Beispiele für Amphiphile sind Tenside, deren makromolekulares Pendant amphiphile Block-Copolymere sind, die häufig auch als Makro-Tenside bezeichnet sind. Ihre Lösungseigenschaften in einem selektiven Lösungsmittel, i.e., ein für einen Block gutes und für den anderen schlechtes Lösungsmittel, sind analog zu denen von Tensiden. Die Unverträglichkeit der Polymersegmente führt zu einer von hydrophoben Wechselwirkungen getriebenen Mikrophasenseparation, d.h. zur Selbstorganisation der amphiphilen Makromoleküle zu Mizellen unterschiedlichster Form, während die kovalente Bindung zwischen den Blöcken eine Makrophasenseparation verhindert. Aufgrund ihres besonderen strukturellen Aufbaus adsorbieren Makro-Tenside an Grenzflächen, was zahlreiche Anwendungen, z.B. zur (elektro)sterischen Stabilisierung von Emulsionen und Dispersionen findet. <br><br> Die vorliegende Arbeit demonstriert, dass die neuen kontrollierten radikalischen Polymerisationen wie die RAFT-Methode („Reversible Addition Fragmentation Chain Transfer“) für die Synthese von neuen wohldefinierten amphiphilen Diblock-Copolymerstrukturen sehr gut geeignet sind. Eine Reihe von neuen amphiphilen Diblock-Copolymeren wurde mittels RAFT synthetisiert, mit einem konstanten hydrophoben Block und verschiedenen hydrophilen Blöcken unterschiedlichster Polaritäten. Die engen Molmassenverteilungen und der lineare Aufstieg der Molmassen mit dem Umsatz belegen den kontrollierten Charakter der Polymerisation. <br><br> Die thermodynamisch favorisierte Selbstorganisation der synthetisierten Blockcopolymere in Wasser führt zur Bildung von Mizellen, deren Eigenschaften aber von der Präparationsmethode stark abhängig sind. Korrelationen zwischen den Mizelleigenschaften und der Blockcopolymerstruktur zeigen, dass die Mizellgröße vor allem von der Länge des hydrophoben Blocks kontrolliert wird, wohindagegen die Natur des hydrophilen Blocks der entscheidende Faktor für die Mizellgeometrie ist. Die gebildeten Mizellen sind besonders stabil gegenüber Verdünnung und Temperaturzyklen, was ein großer Vorteil für eventuelle Anwendungen ist. Wegen der niedrigen Glasübergangstemperatur des hydrophoben Blocks findet ein Austausch von Makromolekülen zwischen den Mizellen statt, d.h. es handelt sich um dynamische Mizellsysteme. <br><br> Das Potential der neuen Makrotenside für Anwendungen wurde untersucht. Die Polymermizellen zeigen eine hohe Kapazität wasserunlösliche Substanzen in Wasser zu solubilisieren. Die Blockcopolymere sind grenzflächenaktiv, d.h. sie adsorbieren an Wasser / Luft oder Wasser / Öl Grenzflächen. Entsprechend sind die Blockcopolymere in der Lage, Emulsionen zu stabilisieren oder als Antischaumsubstanzen zu wirken.

No description available.

Liquid chromatography is an important separation technique for a vast number of analytes. This thesis mainly focuses on the development of stationary phases for liquid chromatography based on zwitterionic sulfobetaine polymers. In the thesis, various ways to prepare zwitterionic polymers in an aqueous environment using reversible addition fragmentation chain transfer (RAFT) polymerization are described. Both telomers, i.e. short soluble polymer chains containing a functional terminal group, as well as graft polymers on various supports have been synthesized. The RAFT polymerization technique provides an increased degree of control of the final polymers, which may aid in the preparation of more specifically tailored separation materials. Sulfobetaine polymers carry both a positive and a negative charge within a single entity, which results in interesting solution properties as well as highly biocompatible features. These unique features make them especially suited for separation of highly polar and/or charged compounds. An example of the successful separation of short peptides using a stationary phase synthesized with the RAFT technique is given. The unusual properties of sulfobetaine-type polymers are believed to be associated with the structure of water close to the polymer. A study of water structure in some silica based stationary phase grafted with zwitterionic sulfobetaine polymers was conducted. The impact of water structure on retention characteristics was investigated.

No description available.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23222号 / 工博第4866号 / 新制||工||1759(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 秋吉 一成, 教授 大内 誠, 准教授 松岡 秀樹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM