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A series of modified poly(arylene ether sulfone)s (PAES) incorporating hexafluoroisopropylidene units and co-monomers, bisphenol A (BA), 4,4′-dihydroxyterphenyl (DHTP) and triptycene-1,4-hydroquinone (TPDH), were synthesized using a polyetherification synthetic method. These thermoplastic PAES were copolymerized with the elastomer, polydimethylsiloxane (PDMS) to form segmented block copolymers. The segmented block copolymers with diverse PAES structures were studied and investigated for their thermal, tensile, and morphological properties. These multiphase segmented block copolymer materials have the potential to impart useful combinations of optical transparency, thermal stability, and enhanced tensile properties, and enhanced environmentally resistant properties for various high impact, high performance applications. In Chapter 2, hexafluoroisopropylidene bisphenol PAES (BAF PAES) segmented block copolymers containing various volume fraction of PDMS were synthesized. Analysis of the segmented block copolymer films by atomic force microscopy (AFM) and small angle x-ray scattering (SAXS) show the materials are microphase separated. Further analysis of the BAF PAES segmented block copolymers by transmission electron microscopy (TEM) show an increased morphological order with decreasing PDMS content, with lamellar morphologies formed at higher or near equal PAES and PDMS volume fractions. Comparatively, the morphological properties of the BAF PAES segmented block copolymers are considerably different from the isopropylidene bisphenol PAES (BA PAES) segmented block copolymer of similar PDMS volume percents. In this document, segmented block copolymers prepared from BA PAES incorporating 4,4′-dihydroxyterphenyl (DHTP) and triptycene-1,4-hydroquinone (TPDH) co-monomers were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). Films of these materials, prepared from THF solution, were tested for thermal and tensile properties. These materials provide higher thermal stabilities over the BA PAES segmented block copolymers with thermal degradation ranging 380–435 °C under nitrogen at 5%-wt. loss. Similarly, the PAES incorporating co-monomers gave higher Tg (200 °C) than the BA PAES (183 °C) synthesized in our labs. Previously synthesized BA PAES segmented block copolymers showed plastic to elastomeric tensile properties upon increasing addition of PDMS content. These new segmented block copolymers, incorporating co-monomers, provided comparable results with the reported BA PAES segmented block copolymers analogues. The last research topic discussed in this dissertation covers the preparation of blends from 5% of segmented block copolymer and 95% of Udel®, donated by Solvay Advanced Polymers. The preparation of blends from the segmented block copolymers containing random copolymers led to materials with higher moduli than Udel® as observed by dynamic mechanical analysis (DMA). Tensile measurements performed by Instron also show the blends have high moduli, though no changes in the tensile elongation comparable to Udel®. / Ph. D.

Magnetic nanoparticles coated with polymers hold great promise as materials for applications in biotechnology. In this body of work, magnetic fluids for the treatment of retinal detachment are examined closely in three regimes; motion of ferrofluid droplets in aqueous media, size analysis of the polymer-iron oxide nanoparticles, and calculation of interparticle potentials as a means for predicting fluid stability. The macromolecular ferrofluids investigated herein are comprised of magnetite nanoparticles coated with tricarboxylate-functional polydimethylsiloxane (PDMS) oligomers. The nanoparticles were formed by reacting stoichiometric concentrations of iron chloride salts with base. After the magnetite particles were prepared, the functional PDMS oligomers were adsorbed onto the nanoparticle surfaces. The motion of ferrofluid droplets in aqueous media was studied using both theoretical modeling and experimental verification. Droplets (~1-2 mm in diameter) of ferrofluid were moved through a viscous aqueous medium by an external magnet of measured field and field gradient. Theoretical calculations were made to approximate the forces on the droplet. Using the force calculations, the times required for the droplet to travel across particular distances were estimated. These estimated times were within close approximation of experimental values. Characterization of the sizes of the nanoparticles was particularly important, since the size of the magnetite core affects the magnetic properties of the system, as well as the long-term stability of the nanoparticles against flocculation. Transmission electron microscopy (TEM) was used to measure the sizes and size distributions of the magnetite cores. Image analyses were conducted on the TEM micrographs to measure the sizes of approximately 6000 particles per sample. Distributions of the diameters of the magnetite cores were determined from this data. A method for calculating the total particle size, including the magnetite core and the adsorbed polymer, in organic dispersions was established. These estimated values were compared to measurements of the entire complex utilizing dynamic light scattering (DLS). Better agreement was found for narrow particle size distributions as opposed to broader distributions. The stability against flocculation of the complexes over time in organic media were examined via modified Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations. DLVO theory allows for predicting the total particle-particle interaction potentials, which include steric and electrostatic repulsions as well as van der Waals and magnetic attractions. The interparticle potentials can be determined as a function of separation of the particle surfaces. At a constant molecular weight of the polymer dispersion stabilizer, these calculations indicated that dispersions of smaller PDMS-magnetite particles should be more stable than those containing larger particles. The rheological characteristics of neat magnetite-PDMS complexes (i.e, no solvent or carrier fluid were present) were measured over time in the absence of an applied magnetic field to probe the expected properties upon storage. The viscosity of a neat ferrofluid increased over the course of a month, indicating that some aggregation occurred. However, this effect could be removed by shearing the fluids at a high rate. This suggests that the particles do not irreversibly flocculate under these conditions. / Ph. D.

Two novel classes of siloxane containing, organic-inorganic block copolymers were prepared using different synthetic approaches. The first copolymers were alternating poly(arylene ether phosphine oxide)-poly(dimethylsiloxane) systems, prepared via oligomeric silylamine-hydroxyl reactions. Secondly, segmented nylon 6,6-poly(dimethylsiloxane) block copolymers were synthesized via a non-aqueous adaptation of the "nylon 6,6 salt" hydrolytic polyamidization, using bis(aminopropyl) dimethylsiloxane oligomer as a co-reactant. Three series of "perfectly" alternating block copolymers were produced from well characterized hydroxyl-terminated poly(arylene ether phosphine oxide) and dimethylamine-terminated poly(dimethylsiloxane) oligomers, in order to investigate both block length and chemical composition effects. Copolymerization in chlorobenzene resulted in high molecular weight materials capable of forming optically clear, nanophase separated films, which displayed unusual morphologies and good mechanical strength. Thermal gravimetric analysis showed high thermo-oxidative stability and increasing char yield with increasing siloxane content. Additional thermal and mechanical investigations provided evidence of selective phase mixing, particularly at shorter block lengths. Surface analysis showed an enrichment of the siloxane blocks at the air-polymer interface in comparison to the bulk state. This behavior increased in proportion to the length of the parent siloxane oligomers. Evaluation of selected optical properties, e.g., refractive indices, revealed linear trends resulting in values of compositionally weighted averages. Conversely, a series of nylon 6,6-siloxane copolymers were produced from the polycondensation of preformed propylamine-terminated poly(dimethylsiloxane)s, solid nylon 6,6 salt and a corresponding amount of adipic acid to afford siloxane-amide semi-crystalline copolymers with siloxane content ranging from 10 to ~45 wt%. The characterization of high molecular weight and covalent siloxane-amide linkages was hindered by insolubility. For example, crystallinity of the nylon 6,6 precluded the use of common solution techniques, while the susceptibility of the siloxane blocks towards ionic redistribution prevented the use of strongly acidic solvents. However, development of a novel analytical technique using solid state 13C NMR and liquid-solid extraction provided evidence for the presence of covalent bonding between the dissimilar oligomer chains. Thermal gravimetric analysis of resultant copolymers revealed an increase in char yield with increasing siloxane content, a preliminary indicator of increased fire resistance, which was supported by subsequent qualitative Bunsen burner observations. Differential scanning calorimetry showed retention of the polyamide crystalline melt with levels of siloxane incorporation of up to 45 weight %. In conclusion, two novel classes of polydimethylsiloxane containing block copolymers have been successfully synthesized, despite the complications created as a result of the polar/non-polar interactions developed between a semi-inorganic polydimethylsiloxane and the hydrocarbon based polyarylene ethers and nylon 6,6. / Ph. D.

For over a century, Langmuir films have served as excellent two-dimensional model systems for studying the conformation and ordering of amphiphilic molecules at the air/water (A/W) interface. With the equipment of Wilhelmy plate technique, Brewster angle microscopy (BAM), and surface light scattering (SLS), the interfacial phase and rheological behavior of Langmuir films can be investigated. In this dissertation, these techniques are employed to examine Langmuir films of polyhedral oligomeric silsesquioxane (POSS), polymer blends, and magnetic nanoparticles (MNPs). In a first time, SLS is employed to study POSS molecules. The interfacial rheological properties of trisilanolisobutyl-POSS (TiBuP) indicate that TiBuP forms a viscoelastic Langmuir film that is almost perfectly elastic in the monolayer state with a maximum dynamic dilational elasticity of around 50 mNâ m-1 prior to film collapse. This result suggests that TiBuP can serve as model nanofiller with polymers. As an interesting next step, blends of TiBuP and polydimethylsiloxane (PDMS) with different compositions are examined via surface pressure (surface pressureâ surface area occupied per molecule (A) isotherms and SLS. The results show that TiBuP, with its attendant water, serves as a plasticizer and lowers the dilational modulus of the films at low surface pressure. As surface pressure increases, composition dependent behavior occurs. Around the collapse pressure of PDMS, the TiBuP component is able to form networks at the A/W interface as PDMS collapse into the upper layer. Blends of non-amphiphilic octaisobutyl-POSS (OiBuP) and PDMS are also studied as an interesting comparison to TiBuP/PDMS blends. In these blends, OiBuP serves as a filler and reinforces the blends prior to the collapse of PDMS by forming "bridge" structure on top of PDMS monolayer. However, OiBuP is non-amphiphilic and fails to anchor PDMS chains to the A/W interface. Hence, OiBuP/PDMS blends exhibit negligible dilational viscoelasticity after the collapse of PDMS. Furthermore, the phase behavior of PDMS blended with a trisilanol-POSS derivative containing different substituents, trisilanolcyclopentyl-POSS (TCpP), is also investigated via the Wilhelmy plate technique and BAM. These TCpP/PDMS blends exhibit dramatically different phase behavior and morphological features from previously studied POSS/PDMS blends, showing that the organic substituents on trisilanol-POSS have considerable impact on the phase behavior of POSS/PDMS blends. The interfacial rheological behavior of tricarboxylic acid terminated PDMS (PDMS-Stabilizer) and PDMS stabilized MNPs are investigated and compared with "regular" PDMS containing non-polar end groups. The tricarboxylic acid end group of the PDMS-Stabilizer leads to a different collapse mechanism. The PDMS stabilized MNPs exhibit viscoelastic behavior that is similar to PDMS showing all the tricarboxylic acid end groups are bound to the magnetite cores. Studying the interfacial behavior of different Langmuir films at the A/W interface provides us insight into the impact of molecule-molecule and molecule-subphase interactions on film morphology and rheology. These results are able to serve as important guides for designing surface films with preferred morphological and mechanical properties. / Ph. D.

Langmuir-monolayer formation at the air/water interface (A/W) can be achieved by spreading amphiphilic molecules on a liquid subphase and compressing them into an ordered arrangement. The use of the Langmuir-Blodgett technique (LB) to prepare ultra thin films on solid surfaces from monolayers at A/W has considerable utility for studying surface interactions. In particular, the phase behavior of polyhedral oligomeric silsesquioxanes (POSS) was examined using a combination of LB and Brewster angle microscopy (BAM).Polymer fillers have been shown to reduce the cost and often improve the properties of high performance polymer composites. The utility of POSS as a potential nanofiller in blends with polymers such as poly(dimethylsiloxane) (PDMS) and poly(vinylacetate) (PVAc) was explored using surface pressure-area per monomer isotherms (P-A) and BAM. Substantial morphological differences are seen between polymer blends with heptasubstituted trisilanol-POSS and fully condensed octasubstituted-POSS due to differences in subphase affinity.Several poly(1-alkene-alt-maleic anhydride) (PXcMA) polymers were studied at both the gas/liquid interface as Langmuir films and at the gas/solid interface as Langmuir-Blodgett thin films on silicon substrates. A 0.01 M HCl solution (pH~2) was used during film deposition to ensure the carboxylic acids were fully protonated. The PXcMA polymers included X=1-hexene, 1-octene, 1-decene, and 1-octadecene (represented as PHcMA, POcMA, PDcMA, and PODcMA respectively). The P-A isotherms of these polymers were consistent with those obtained previously.1Tensiometry was used to determine the critical micelle concentrations (c.m.c.) of variable molar mass poly(dimethylsiloxane-b-(3-cyanopropyl)methylsiloxane-b-dimethylsiloxane) (PDMS-PCPMS-PDMS) triblock copolymers and a poly(dimethylsiloxane-b-2-ethyl-2-oxazoline) diblock copolymer. Dynamic light scattering (DLS) corroborated interfacial tension results. The polymers exhibited well-defined temperature-independent c.m.c.'s. These measurements ensured that the synthesis of cobalt nanoparticles for biocompatible magnetic fluids occurred above the c.m.c. / Master of Science

No / The aim of the present work is to evaluate the similarity between PDMS membranes and human skin in vitro in permeation study by linear free energy relationship (LFER) analyses. The values of the permeability coefficient log Kp (cm/s) under reliable experimental conditions were collected from the literature for a set of 94 compounds including both neutral and ionic species, which cover a broad range of structural diversity. The values of log Kp (cm/s) have been correlated with Abraham descriptors to yield an equation with R2 = 0.952 and SD = 0.38 log units. The established LFER model for log Kp (cm/s) across PDMS membranes showed no close analogy with that through human skin in vitro. A further critical analysis of the coefficients of the LFER models confirmed that the PDMS permeation system is a very poor model for human skin permeation.

No / Originally developed as a heat exchange fluid, Volasil 245 (decamethylcyclopentasiloxane) has been found to dissolve 10 times more ozone than water does. This article proposes and investigates the extraction of wastewater contaminants to ozone-loaded Volasil 245 as a means of providing rapid treatment. In a series of bench-scale tests, the effectiveness of ozone-loaded Volasil 245 contact was compared with that of conventional gas contact. Tests were conducted with respect to a range of organic compounds: namely, phenol, 2-chlorophenol, 2,3-dichlorophenol, 1,3-dichlorobenzene, o-nitrotoluene, and nitrobenzene. Contact with the ozone-loaded solvent was suggested to be the more rapid technique, reducing aqueous concentrations by at least 85% within 30 s. In the case of 2-chlorophenol, Volasil 245 contact was shown to require just ~0.5 min to achieve a residual aqueous fraction of 5%, as opposed to ~4.5 min of gas contact. However, water/solvent interfacial mass transfer resistance was suggested to limit the degree of aqueous decontamination ultimately achieved.

La synthèse de particules polyuréthane par organo-catalyse dans le dioxyde de carbone supercritique a été étudiée. Des réactions modèles ont été préalablement conduites et suivies par spectroscopie infrarouge in situ dans le CO2 supercritique afin d'identifier les catalyseurs organiques de réaction d'uréthanisation les plus efficients. Une série de polymères siliconés CO2-phile, porteurs de la fonction organo-catalytique en bout de chaîne (organo-catasurfs), a ensuite été préparée et testée dans le CO2 supercritique pour la polymérisation en dispersion de polyuréthane. / The organocatalysed synthesis of polyurethane particles in supercritical carbon dioxide has been studied. Model reactions were first carried out in supercritical CO2 and monitored by in situ infrared spectroscopy in order to indentify the most efficient catalysts for the urethanisation reaction. A series of CO2-philic silicone polymers, end-functionalised with the organocatalytic group (organocatasurfs), were then synthesised and tested in supercritical CO2 for the dispersion polymerisation of polyurethane.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Hybrid graft copolymers of polystyrene (PSty) and polydimethylsiloxane macromonomers (PDMS) were synthesised. PSty-g-PDMS was synthesised employing the grafting through technique via a conventionally free radical polymerization (FRP) using a polydimethylsiloxane macromonomer. In this series the amount of PDMS incorporated into the copolymer was varied by varying the macromonomer to styrene ratios as well as the length of the PDMS side chain. This allows for the study of the effect that the macromonomer content and the branching length has on the efficiency of the grafting process. A second series of PDMS-g-PSty was also synthesized where the PDMS forms the backbone and the PSty the grafts. Two synthetic techniques were employed for the formation of these polymers. Firstly, the grafting onto approach was used where functional polystyrene prepolymers with either an allyl or vinyl end-groups were synthesised anionically (living anionic polymerization) prior to the coupling of a functional prepolymer using a hydrosilylation reaction with a Karstedt platinum catalyst. This technique was successful and gave insight to the effect of the polystyrene prepolymer graft length has on the grafting efficiency as well as the functional groups needed on the PDMS backbone. Furthermore, the effect of the viscosity (of the PDMS macromonomer) plays on the grafting efficiency was also elucidated. Lastly, the grafting from approach was employed for the formation of PDMS-g-PSty. ATRP, atom transfer radical polymerization, of styrene using a bromoisobutyrate functional PDMS macroinitiator was used for the synthesis of these copolymers. This was accomplished by reacting commercial silane functional PDMS molecules via a hydrosilylation reaction (using a Karstedt catalyst) with allyl-2- bromo-2-methyl-propionate to give a PDMS macroinitiator with bromoisobutyrate functional groups. This will allow for the initiation and growth of polystyrene branches from the PDMS backbone (employing ATRP with a suitable catalyst and ligand). The formation of the endproduct, PDMS-g-PSty, via this route proved to be extremely difficult and largely unsuccessful. Liquid chromatography (LC) at the critical point (LCCC) of polystyrene was used to separate the graft material from homo-polymers which might have formed as well as from the PDMS macromonomer. This technique allows for a very fast chromatographic analysis of the grafting reaction. Under the critical conditions of PSty it was found that the graft copolymer eluted at a lower retention time than the unreacted macromonomer and PSty homopolymer. Two-dimensional chromatography, where LCCC (1st dimension) was coupled to size exclusion chromatography (2nd dimension), was used for the evaluation of the CCD and MMD (molecular mass distribution) of the graft material. LC was furthermore coupled off-line to FTIR and TEM using an LC interface. LCFTIR gave insight to the microstructure of the material, whilst LC-TEM gave insight to the morphological nanostructure of the material. / AFRIKAANSE OPSOMMING: Hibried ent-kopolimere is gesintetiseer uit polistireen (PSty) en polidimetielsiloksaan (PDMS). PSty-g-PDMS is gesintetiseer deur gebruik te maak van die ent-deur tegniek via ‘n konvensionele vrye radikaal polimerisasie proses (VRP). In die reeks is die hoeveelheid PDMS wat geïnkorporeer is, gevarieer deur die hoeveelheid PDMS tot PSty verhouding te verander asook die lengte van die PDMS sytak. Gevolglik het dit toegelaat vir die studie van die effek wat die makromonomeer inhoud, sowel as die taklengte het op die effektiwiteit van die ent-proses. ‘n Tweede reeks is ook gesintetiseer, waar die PDMS die ruggraat vorm van die ko-polimeer, en die stireen die takke vorm van die ko-polimeer. Dus is PDMS-g-PSty gesintetiseer. Twee sintetiese tegnieke is benut vir die vorming van die kopolimere. In die eerste geval is daar van die ent-op tegniek gebruik gemaak waar funksionele polistireen prepolimere met ‘n alliel of ‘n silaan end-groep gesintetiseer is deur gebruik te maak van ‘n anioniese lewendige polimerisasie voor die koppeling van die PDMS makromonomere deur ‘n hidrosililasie proses met ‘n Karstedt platinum katalisator. Die tegniek was suksesvol en het in diepte insig gegee van die effek wat die molekulêre lengte van die polistireen prepolimeer het op die effektiwiteit van die ent-proses, sowel as die minimum hoeveelheid funksionele groepe wat teenwoordig moet wees op die PDMS ruggraat. Verder is die effek wat die viskositeit (van die PDMS makromonomeer) op die ent-proses het, bekend gemaak. Laastens is daar ook van die ent-vanaf tegniek gebruik gemaak vir die vorming van PDMS-g-PSty. AORP, atoom oordrag radikale polimerisasie, van stireen, deur gebruik te maak van ‘n bromoisobutiraat funksionele PDMS makro-inisieerder, is gebruik vir die sintese van die kopolimere. Die makro-inisieerders is bekom deur gebruik te maak van kommersiële silaan funksionele PDMS, en dit is gereageer deur middel van ‘n hidrosililasie proses met alliel-2-bromo- 2-metiel-propionaat. Dit het PDMS makroinisieerders tot gevolg gehad met bromoisobutiraat funksionele groepe. Gevolglik kon stireen takke vanaf die PDMS ruggraat gegroei word deur gebruik te maak van AORP met ‘n geskikte katalisator en ligand. Die vorming van die end-produk, PDMS-g-PSty, deur middel van hierdie roete was onsuksesvol. Vloeistof chromatografie by die kritiese punt van polistireen was gebruik om die ent-produk te skei van die homo-polimere en PDMS makromonomeer. Gevolglik kon die chemiese samestelling van die ent-produk geëvalueer word. Twee-dimensionele chromatografie, waar vloeistof chromatografie by die kritiese punt van polistireen in die eerste vlak gekoppel was aan grootte uitsluitings chromatografie in die tweede vlak, was benut om die chemiese komposisie sowel as die molekul re massa verdeling van die entproduk te verkry. Verder was vloeistof chromatografie indirek aan Fourier-oordrag infrarooi en transmissie elektron mikroskopie (TEM) gekoppel. Eergenoemde het insig gegee tot die mikrostruktuur van die materiaal, terwyl laasgenoemde insig gegee het tot die morfologiese nanostruktuur van die materiaal.