Macromolecular engineering is one of the most powerful tools to control the molecular parameters, including architecture of polymers, and to improve their performances or to impart them new properties. This contribution aims at reporting on a novel strategy for the macromolecular engineering of poly-ε-caprolactone (PCL) which is based on the use of functional ε-caprolactone, the α-chloro-ε-caprolactone (αClεCL). Indeed, αClεCL is a precursor of polymers and copolymers with εCL that bear pendant activated chlorides well suited to grafting from reaction. These (co)polyesters have been used as macroinitiators for the Atom Transfer Radical Polymerization (ATRP) of methyl methacrylate leading to the corresponding graft copolymer. They have also been involved in an Atom Transfer Radical Addition (ATRA) reaction with a series of olefins bearing different functional groups (hydroxyl, carboxylic acid and epoxy group) in order to functionalize the polyester backbone without deleterious degradation. ATRA of PEO chains with an unsaturation end groups has also been carried out in order to prepare PCL-g-PEO of different compositions to be used as stabilizers of polyester nanoparticles. Combination of ring-opening polymerization of ε-caprolactone and the copper-catalyzed Huisgens [3+2] cycloaddition is a novel strategy for going a step further in the macromolecular engineering of poly-ε-caprolactone (PCL). This click reaction is very well-suited to the chemical modification of aliphatic polyesters because, its implementation under very mild conditions prevents chain degradation from occurring. Indeed, alkynes were cycloadded onto azide containing PCL at low temperature (35°C) in an organic solvent (DMF or THF). Originally, α-chloro-ε-caprolactone and ε-caprolactone were randomly copolymerized in toluene at room temperature followed by reaction of the activated chlorides with sodium azide. In order to make a wide range of functional aliphatic polyesters available, poly(α-azide-ε-caprolactone-co-ε-caprolactone) copolyesters were reacted with a series of alkynes substituted by a functional group, e.g., hydroxyl, acrylate and quaternary ammonium salts, This strategy turned out to be efficient to synthesize for instance hydrophilic, photo-cross-linkable and hydrosoluble PCL. Moreover, a variety of graft copolymers were prepared by both the grafting from and the grafting onto techniques. Indeed, an ATRP initiator was attached onto PCL followed by polymerization of vinyl monomers, whereas alkyne endcapped PEO was cycloadded onto azide-containing PCL with formation of amphiphilic PCL-g-PEO copolymers. Last but not least, the click chemistry was very instrumental in imparting an antimicrobial activity to PCL or for the preparation of new functionalized caprolactones.

No description available.

Ces travaux de thèse portent sur la valorisation de la biomasse oléagineuse, via la polymérisation de synthons, issus d’huiles végétales, en polymères hyper-ramifiés. Ces recherches ont conduit à la synthèse et à la purification d’un nouveau monomère biosourcé, le 10,11-epoxy undecan-1-ol (EUnd), dont la polymérisation par ouverture de cycle (ROMBP) a permis de générer des polyéthers hyper-ramifiés biosourcés. Les conditions de polymérisations ont été étudiées en laboratoire dans le but d’optimiser les rendements de synthèse mais aussi afin de contrôler la structure chimique, ainsi que leurs propriétés. La copolymérisation de l’EUnd avec le glycidol a permis d’atteindre de nouvelles propriétés, notamment en termes de solubilité. Une seconde partie fut consacrée à la fonctionnalisation de polyesters hyper-ramifiés biosourcés, développés au LCPO lors du projet HyPerBioPol. L’objectif étant de contrôler la solubilisation des composés dans différents milieux, polaires et apolaires, afin de créer des polymères pouvant être utilisés comme agents de réticulation. / The aim of this thesis is to valorize oilseed biomass through the polymerization of building block, stemming from vegetable oils, into hyperbranched polymers. This research involves the synthesis and purification of a new bio-based monomer, coined as 10,11- epoxyundecanol (EUnd), which ring-opening multibranching polymerization (ROMBP) has generated bio-based hyperbranched polyethers (hbPEUnd). Conditions of polymerization have been studied in order to maximize yields of reaction and control both the chemical structure and the properties of hbPEUnd. Copolymerization of EUnd with glycidol has also been implemented, yielding hyperbranched copolyethers with varied properties (e.g. solubility). The second part of this work has been dedicated to the functionalization of bio-based hyperbranched polyesters, developed in the frame of a former project. Appropriate derivatizations have provided these modified polyesters with solubility in polar solvents and made them employable as curing agents.

L’objectif de ces travaux de thèse a été de développer des polyesters issus de ressources oléagineuses pour les utiliser comme additifs pour moduler la viscosité d’huiles lubrifiantes. Pour ce faire, l’approche par polycondensation de monomères de type hydroxy-acide a été privilégiée. Dans un premier temps, le poly(ricinoléate de méthyle) et son homologue saturé, le poly(12-hydroxystéarate de méthyle), ont été synthétisés dans une large gamme de masses molaires et leur utilisation comme épaississant d’huiles lubrifiantes a été démontrée. Dans un second temps, des polyesters dérivés du poly(ricinoléate de méthyle) et présentant des architectures de polymère en peigne ont été synthétisés par addition thiol-ène et polycondensation. Une étude de l’impact de l’architecture de ces polyesters sur leur comportement en solution a permis de prouver que les structures en peigne étaient les plus adaptées pour des applications visant, à la fois, un épaississement et une diminution du point d’écoulement de l’huile lubrifiante. Par la suite, des copoly(9-alkyl 12-hydroxystéarate)s en peigne possédant différentes chaînes pendantes ont été synthétisés afin de contrôler leur solubilité dans une huile minérale, la Yubase 4+, et ont permis de réduire la diminution de viscosité de cette huile avec la température. Finalement, l’étude dans le dodécane de deux copoly(9-alkyl 12-hydroxystéarate)s en peigne a révélé un phénomène d’agrégation des chaînes polymères lesquelles se désagrègent avec l’augmentation de la température, ce qui est en accord avec un des mécanismes d’action des additifs modulant la viscosité des huiles lubrifiantes décrit dans la littérature. / The aim of this thesis was to promote the use of polyesters from oleaginous resources as viscosity control additives for lubricants. The hydroxyl-acid type monomers were polymerized through polycondensation route. First, poly(methyl ricinoleate) and its homologous poly(methyl-12-hydroxystearate) were synthesized in a large range of molecular weights and their use as thickeners of lubricant oils was demonstrated. Secondly, comb polyesters derived from poly(methyl ricinoleate) were designed via thiol-ene addition and polycondensation process. The effect of the polyester architecture on their behavior in solution was investigated and revealed that comb polymers are the most suitable for applications that required a thickening efficiency and a pour point depressant effect. Then, comb (co)poly(9-alkyl 12-hydroxystearate)s with various pendant alkyl chains were designed in order to control their solubility in a mineral oil, the Yubase 4+, and to limit the oil viscosity decrease of these oils with temperature. Finally, the behavior in dodecane of two comb (co)poly(9-alkyl 12-hydroxystearate)s revealed that the polymer chains tend to aggregate at low temperature and to disaggregate with the temperature increase. This phenomenon is in accordance with one of the oil Viscosity Index Improver behaviors, described in literature.

Ces travaux de thèse traitent de la valorisation des huiles végétales comme plateforme pour la synthèse de polyesters d’architecture hyper-ramifiée. Pour ce faire, l’approche par polycondensation de monomères de type ABn (n ≥ 2) a été privilégiée. Des précurseurs plurifonctionnels portant des fonctions ester (A) et alcool (B) ont ainsi été préparés par modification chimique d’huiles végétales et/ou d’esters méthyliques d’acide gras. Plusieurs méthodologies de synthèse simple, sûres et efficaces ont été mises en place afin de garantir une réalité industrielle à ce projet. Deux plateformes de monomères de type ABn ont été obtenues par (1) hydrolyse acide d’huiles végétales époxydées et (2) en faisant appel à des réactions d’addition de thiol-ène et de métathèse. Le développement de procédés de polycondensation en masse, a alors permis l’accès à de nouveaux polyesters hyper-ramifiés. La densité de ramifications ainsi que les propriétés thermo-mécaniques de ces matériaux ont été modulées par le choix adapté de la structure chimique des précurseurs ‘gras’ utilisés. Enfin, un travail exploratoire a été conduit concernant la post-fonctionnalisation du coeur comme de la périphérie de ces polyesters hyper-ramifiés dans le but de moduler leurs propriétés et ainsi d’étendre la portée de leurs applications, des plastiques de commodité aux matériaux avancés. / The aim of this thesis was to use vegetable oils as a platform for the design of more sustainable polyesters of hyperbranched architecture. For that purpose, the approach by polycondensation of ABn-type monomers (n ≥ 2) was favored. Plant oils and/or fatty acid methyl esters were chemically modified to synthesize multifunctional precursors featuring ester (A) and alcohol moieties (B). Simple, safe and efficient chemical transformations were considered to provide industrial perspectives to this work. Two main platforms of ABn-type monomers were developed by (1) acid hydrolysis of epoxidized vegetables oils and (2) thiol-ene/metathesis coupling reactions. The subsequent polycondensation of these oily-derived monomers, performed in bulk, gave access to novel renewable hyperbranched polyesters. The branching density as well as the thermo-mechanical properties of these materials were adjusted by designing and selecting the chemical structure of the fatty acid-based monomers. Finally, an exploratory work was carried out regarding the post-functionalization of both the core and the periphery of these hyperbranched polyesters with the aim at tuning their properties and thus opening the scope of their applications, from commodity plastics to advanced materials.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Unsaturated polyesters resins (UPRs) of maleic anhydride (MA), phthalic anhydride (PA) and propylene glycol (PG) were synthesized using the fusion polycondensation process for use in Multi-vesiculated Particles (MVPs). The UPRs were synthesized using different MA:PA mole ratios and process parameters, including heating rates, agitation speed, exotherm rate and maximum processing temperature. Design of Experiments (DoE) software (Design Expert 7) was employed to find the optimum experimental space, i.e. least amount of experiments, but covering all the factors. The variations in the formulation and process parameters had a significant effect on the molecular structure and physical properties of the UPRs. The molecular structure and physical properties of the UPRs was successfully determined using various techniques including viscometry, acid-base titration, Proton Nuclear Magnetic Resonance (1H NMR) spectroscopy, Size-Exclusion Chromatography (SEC), Fourier Transform Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). Furthermore, the carboxyl and hydroxyl end-group concentrations of the UPRs were determined by derivatization of the groups with trichloroacetyl isocyanate (TAI) and analysis by 1H NMR. As a second part of the study, the effect of the above-mentioned monomer ratio and process factors of the UPRs, on the properties of the MVPs (produced from the UPRs), was investigated. Results showed that these factors had a significant effect on the particle size and degree of vesiculation of the MVPs. The degree of vesiculation of the MVPs was determined by Scanning Electron Microscopy (SEM). Attempts were also made to determine the relative hardness of the MVPs by AFM and microhardness testing to determine a relationship with UPRs properties (e.g. molecular weight, degree of unsaturation and chain branching). These techniques were however found to be unsuitable due to the physical nature of the MVPs. / AFRIKAANSE OPSOMMING: Onversadigde poliësters (OPs) van maleïensuuranhidried (MA), fataalsuuranhidried (PA) en propileen glikol (PD) is berei deur die fusie polikondensasie-proses vir gebruik in multi-vesikulerende partikels (MVPs). Die OPs is berei deur gebruik te maak van verskillende MA:PA molverhoudings en reaksie faktore wat verhittingstempo‟s, roerspoed, eksoterm tempo en maksimum reaksie temperatuur, insluit. As gevolg van die groot hoeveelheid faktore is eksperimentontwerp sagteware (Design Expert 7) gebruik om die aantal eksperimente te verminder, maar ook waardevolle afleidings van die data te maak. Die verskille in die formulasie en reaksie faktore het „n merkwaardige effek op die molekulêre struktuur en fisiese eienskappe van die OPs gehad. Hierdie eienskappe is bepaal m.b.v. verskeie tegnieke, naamlik viskometrie, suur-basis titrasie, Proton Kern-Magnetiese Resonansie (1H KMR) spektroskopie, Grootte-Uitsluitings-Chromatografie (SEC), Fourier Transform Infrarooi (FTIR) spektroskopie en Differensiële Skandeerings Kalorimetrie (DSC). Die hidroksiel en karboksielgroep konsentrasies van die OPs is bepaal deur hul reaksie met trichloroasetiel-isosianaat (TAI) gevolg deur 1H KMR analise. In die tweede deel van hierdie studie is die invloed van bogenoemde faktore op die eienskappe van die MVPs ondersoek. Die resultate het getoon dat hierdie faktore „n merkwaardige effek op die partikel grootte en graad van “vesiculation” van die MVPs gehad het. Die graad van “vesiculation” van die MVPs is bepaal met behulp van Skandeer Elektron Mikroskopie (SEM). Pogings is ook gemaak om die relatiewe hardheid van die MVPs te bepaal deur middel van AFM en Mikro-hardheid toetsing. Dit is gedoen om die verhouding van die OPs eienskappe (molekulêre gewig, graad van onversadigheid en sy-kettings) vas te stel. Hierdie tegnieke is egter ongeskik bevind as gevolg van die inherente fisiese aard van die OPs.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Complex polymers are defined by their distributive properties with respect to molecular weight, chemical composition, functionality and molecular topology. As a result, polymer properties are very frequently determined not only by one of these entities but by the correlation of two or more distributions. Aliphatic polyesters are industrially implemented in high performance coatings, paints and varnishes. However, it is typically difficult to correlate the resulting properties with the synthesis parameters as these polymers vary in reactivity and application properties. Copolyester synthesis by direct polyesterification is often assumed to produce randomized products due to the mechanisms involved in stepwise polymerization. The formation of cyclic products by intramolecular reactions of hydroxyl (OH) and carboxylic (COOH) functional groups, sidereactions such as transesterification, alcoholysis, and ester-ester interchange allow even further randomization, enabling a highly complex system. Therefore, in addition to molecular weight distribution, polyesters exhibit chemical composition, functionality type as well as branching distributions, classifying them as complex polymeric systems. The different methods of polymer chromatography in combination with sophisticated spectrometry techniques are useful tools for enabling the full description of the molecular heterogeneity of these complex polyesters. The present study entails method development of different modes of chromatography and mass spectrometry along with their combination, to facilitate the analysis of the various distributions of two model polyester systems, phthalic and maleic anhydride, respectively, in combination with propylene glycol. Gradient HPLC analysis enabled an oligomeric separation based on chemical composition of the respective anhydride/propylene glycol samples. Its off-line coupling to MALDITOF MS and ESI-QTOF MS revealed the presence of several distributions of varying endgroup functionality type and molecular weight distributions at different intervals throughout the polymerization. In addition, online gradient HPLC x size exclusion chromatography (2D-LC) was conducted to obtain the dual chemical composition-molecular weight (CCD-MWD) distribution. The combination of the different coupling techniques provided the opportunity to a more in-depth analysis of the structure-property relationships. / AFRIKAANSE OPSOMMING: Komplekse polimere word gedefinieer deur hul verdelings eienskappe ten opsigte van molekulêre massa, chemiese samestelling, funksionaliteit en molekulêre topologie. Gevolglik, word hul eienskappe dikwels bepaal deur nie net een van hierdie entiteite nie, maar ‘n korrelasie van twee of meer verdelings. Alifatiese poliësters word industrieel geϊmplimenteer in hoë werkverrigting bestrykings, verwe en politoere, dog is dit tipies moeilik om die uiteinde eienskappe met die verwante sintese parameters te korrelleer, aangesien die polimere varieer in reaktiviteit en toepassingseienskappe. Ko-poliëster sintese vanaf direkte poliësterivering word dikwels aanvaar om willekeurige produkte op te lewer as gevolg van die meganismes wat betrokke is tydens trapgroei polimerisasie. Die produsering van sikliese produkte weens intra-molekulêre reaksies van hidroksiel(OH) en karboksiel (COOH) verwante funksionele groepe, newereaksies soos transverestering, alkoholise en ester-ester verwisseling, het verdere ewekansigmaking tot gevolg wat ‘n hoog gekomplekseerde sisteem tot gevolg het. Benewens die molekulere massa verdeling, vertoon poliësters dus chemiese samestelling, funksionaliteit tipe so wel as vertakkings verdeling wat hul as komplekse polimeer sisteme klassifiseer. Die verskillende metodes van polimeer chromatografie in kombinasie met gesofistikeerde spektrometriese tegnieke dien as nuttige bronne vir die volledige beskrywing wat betref die molekulêre heterogeniteit van komplekse poliesters. Die huidige studie stel metode ontwikkeling van verskillende modus van chromatografie, massa spektrometrie sowel as hul aaneenvoeging bekend, om die die verskillende verdelings van twee model poliester sisteme, ftaal- en maleϊensuuranhidried onderskeidelik in kombinasie met propileenglikol, suksesvol te analiseer. Gradiënt hoë-druk vloeistof chromatografie (HPLC) analise het ‘n oligomeriese skeiding, gebaseer op die chemiese samestelling van die verskeie anhidried /propileenglikol monsters, opgelewer. Die nie-gekoppelde skakeling met matriks-assisteerdelaser/ desorpsie-ionisasie tyd-van-vlug (MALDI-TOF) en elektron-sproei-ionisasie kwadrupool-tyd-van-vlug (ESI-QTOF) massa spektrometrie het die teenwoordigheid van verskeie verdelings van varieërende endgroep funksionaliteit tipe en molekulêre verdelings by verskillende intervalle tydens die polimerisasie aan die lig gebring. Gekoppelde skakeling van gradient HPLC en grootte uitsluitings chromatografie is ook uitgevoer om die tweedelige chemiese samestelling-molekulere massa verdeling te bepaal. Aaneenvoeging van die verskeie skakelings tegnieke het die geleentheid gebied om ‘n deeglike studie van die struktuureienskappe verhoudinge suksesvol uit te voer.

Ternary blends comprising Polysulphones [Polyethersulphone (PES) and Polysulphone (PSO)], the Polyhydroxyether of bisphenol-A (Phenoxy), and Polyesters [Poly( ethylene terephthlate) (PET) and Poly(butylene terephthlate) (PBT)] have been studied particularly with the aim in mind of elucidating the factors determining their miscibility and morphology. Binary and ternary combinations, including equivalent systems based on a butylene terephthlate-tetramethylene oxide block copolymer (PBT-TMO), were prepared from solution and by mixing in the melt state using both an internal mixer and a twin screw extruder. Scanning electron microscopy was employed to examme the morphology of these blends. A co-continuous, (interpenetrating), dual-phase morphology was displayed by both the PSO/PBT and PSO/PBT-TMO (70/30) combinations. The compatibility was further increased by the addition of Phenoxy, which was evidenced by the formation of a very fine dispersion of the two phases for both PSO/Phenoxy/PBT and PSO/Phenoxy/PBT-TMO blends, in the weight ratio of (60/15/25). A lower level of compatibility was displayed by the equivalent blends based on PES and PET, as a matrix/dispersed particle type of morpholgy was usually observed. Differential thermal analysis and dynamic mechanical analysis measurements were also employed to ascertain the level of miscibility in these systems. A single composition dependent glass transition temperature was displayed by the binary PBT/Phenoxy and PBT-TMO/Phenoxy melt blends, and the binary PES/Phenoxy and _PSO/Phenoxy solution blends. The remaining blends displayed two separate glass transition temperatures that were often broader and closer together than those of the homopolymers. This effect was more significant for blends containing the Phenoxy compatibiliser, confirming that these systems are semi-miscible. Solvent resistance measurements were made on 500μm thick extruded sheets by measuring the time to failure at stress levels corresponding to 30% and 50% of the tensile strength. The blends displaying a matrix/dispersed particle type of morphology revealed poor solvent resistance and mechanical properties. The blends displaying a cocontinuous interpenetrating dual-phase morphology on the other hand displayed a much higher solvent resistance and enhanced mechanical properties.

The theoretical part of this diploma work is focused on the polymeric nanoparticles, their properties and advantages connected with them. There are introduced also particular types of organic and inorganic nanoparticles and methods of their preparation. The great attention was directed on biodegradable polymers in particular to poly lactic-co-glycolic acid, which was used in experimental part as carrier for base of terbinafine branched to tripentaerythritol. PLGA is the most suitable copolymer for practice because of good explored its physical, chemical and biological properties, methods of preparation and factors affecting degradation. The aim of this work was to find suitable emulsifier with suitable concentration for preparation of nanoparticles containing the base of terbinafine, suitable solvent for terpolymer and optimal concentration of emulsion to reach the highest yield of terbinafine without any exceptional loss. How it was mentioned, as carrier was used terpolymer of poly lactic-co-glycolic acid with tripentaerythritol. As technique of preparation of nanoparticles was used emulsification by evaporating of organic solvent (solvent evaporation method). During the experimental work we found out some of conclusions, it goes to reduce of polydispersity with increasing concentration of...

CHARLES UNIVERSITY IN PRAGUE Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical technology Name of the student: Anna Hánová Title of diploma thesis: Rheological properties of White Soft Paraffin Consultant: PharmDr. Eva Šnejdrová, Ph.D. This diploma thesis deals with the evaluation of consistency and rheological properties of the Soft Paraffin after viscosity modification by either Liquid or Solid Paraffin. The theoretical part focuses the characteristics and application of the hydrocarbon excipients, their use in pharmacy and comparison with other substances, rheological properties of semisolids and their consistency. Consistency by penetrometry according the Czech Pharmacopoeia 2009 and rheological properties using Kinexus rheometer were measured. Consistency of Soft Paraffin was significantly influenced with 5 % of Liquid Paraffin and 10 % of Solid Paraffin. The result of consistency assessment is significantly influenced by the method of the samples preparation. Rheograms and viscosity curves was constructed. Plastic systems were described in detail by the parameters of power law model and yield stress value. The addition of 5 % of Liquid Paraffin to the Soft White Paraffin caused the decrease of the coefficient of consistency and the flow index. A further addition of Liquid...