Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Novel poly(methacrylic acid)-graft-poly(dimethylsiloxane) copolymers were synthesised by conventional free radical reactions using a poly(dimethylsiloxane) macromonomer. The polymers were electrospun to investigate how the fibre morphology can be modified by manipulating the electrospinning solution parameters, and to determine the possibility of using the polymers as new materials for the production of polymer nanofibre hydrogels. The electrospinning solution parameters were varied by electrospinning the highly amphiphilic copolymers in solvents with variable solvent qualities. Scanning Electron Microscopy (SEM) and Field Emission Scanning Electron Microscopy (FE–SEM) was used to investigate the fibre morphology. Internal morphology was studied using a freeze fracture technique prior to FE-SEM imaging. It is revealed that the polymers in this study does not form any fine structure or pores even when self-assembled structures are present in the solution. Attempts were made to visualise any self-assembled structures of films produced from dilute solutions using TEM. Further studies included investigating the fibres properties, primarily with regards to their rate and extent of moisture and water uptake. The fibres showed hydrogel behaviour and the PDMS content were found to have an impact on the hydrogel stability. Post electrospinning crosslinking of the nanofibres was also explored. / AFRIKAANSE OPSOMMING: Unieke ent-kopolimere wat bestaan uit poli(metielakrielsuur) (PMAS) en poli(dimetielsiloksaan) (PDMS) is gesintetiseer deur middel van 'n “ent-deur” vryeradikaalkopolimerisasie. 'n PDMS makromonomeer is vir hierdie doel gebruik. Die polimere is geëlektrospin om vesels te vorm. Die doel was om die invloed van verkillende strukture in oplossing op die veselmorfologie te bepaal. Die moontlikheid om hierdie nanovesels as gels te gebruik is ook ondersoek. Die amfifiliese kopolimere is geëlektrospin uit die oplossing waarin dit wisselende oplosbaarheid toon. Skandeer elektron mikroskopie (SEM) is gebruik om die morfologie te ondersoek. Die interne morfologie van die vesels is ondersoek deur die vesels te vries en in die gevriesde toestand te breek. Die studie het getoon dat geen strukture op, of binne, die vesels vorm nie, selfs al moes daar assosiasie tussen segmente van die polimere gewees het. Hierdie tipe assosiasies sou strukture in die oplossing tot gevolg gehad het. 'n Poging is aangewend om die strukture in oplossing te visualiseer deur transmissie elektron mikroskopie (TEM) van dun films te ondersoek. Films is vanaf verdunde oplossings gevorm. Ander studies het ingesluit om die eienskappe van die vesels te ondersoek, met die fokus op hoeveel en hoe vinnig die vesels waterdamp en water kon absorbeer. Die vesels het soos 'n gel reageer. Hierdie gedrag is beïnvloed deur die hoeveelheid PDMS wat 'n definitiewe invloed op die stabiliteit van die gel gehad het. Kruisverbindings van die vesels, nadat dit geëlektrospin is, is ook ondersoek.

<p>In this study, attempts were made to diversify the application of potato starch based biopolymer as foam-grade materials. To improve foamability, which is largely dependent on melt strength, it is possible to modify hydrolyzed starch based biopolymers by bulk modification with bi- and multi- functional epoxy chain extenders. The modification work was carried out using a twin screw extruder (TSE) and an internal batch mixer (Haake Mixer) with four different chain extenders. The modified blends were characterized by Parallel Plate Rheometry, DSC, Intrinsic Viscosity and SEM techniques. Finally, foamability of the modified blends was examined by using supercritical CO₂ as a physical blowing agent in a high-pressure batch vessel. Variables such as saturation pressure, saturation time and saturation temperature were adjusted to determine their influence on the cell morphology of the foamed parts.</p> <p>The multi-functional epoxy chain extenders effectively increased the bulk melt viscosity and reduced the crystalline content of both hydrolyzed starch based biopolymers. The intrinsic viscosity measurements were quantified the chain extension reaction, which primarily occurred in the PLA/AAC or PLA phase in both biopolymers and the starch phase made no contribution towards increased bulk melt viscosity. The multi-functional Joncryl^® ADR 4370S was the most effective chain extender for improving the stability of foams by yielding smaller cell size and higher cell density in comparison with the original biopolymer during the batch foaming process at 10 MPa saturation pressure and 30 min saturation time. The use of other chain extenders proved to be mostly ineffectual in producing uniform cellular structure in their corresponding modified biopolymer at those same processing conditions.</p> / Master of Applied Science (MASc)

<p>In this thesis work, two new CO₂-responsive monomers have been synthesized. These amidine-containing monomers were prepared in a simple and effective one-step reaction, giving a very high yield (98.5 %) of product. Furthermore, there was no complicated further purification required to obtain the highly pure product. The CO₂ switchability, conductivity and partitioning of the monomers were measured. It was confirmed that the monomers could be protonated CO₂ in the present of trace amount of water and reversibly switched back and forth to their natural forms by N₂ at room temperature.</p> <p>The polymers having different molecular weights were prepared from one monomer via conventional free radical polymerization method. The polymers also showed the reversible switchability property with CO₂ and N₂ stimuli. This was confirmed by the results of conductivity and partitioning tests. Temperature showed a major influence on the conductivity of the monomer and polymers. The effect of molecular weight on the polymer switchability of was further investigated through conductivity tests and potentiometric titration. The conductivity decreased with the increased molecular weight. The apparent equilibrium constant (pK_a)decreased with the degree of protonation (δ) suggesting that the basicity of the polymers is strongly depended on the value of δ.</p> / Master of Applied Science (MASc)

<p>Cellulose is the most abundant biopolymer on earth, derived from a variety of living species. An attractive source to obtain cellulose is from agriculture wastes, for instance, potato peel. Potato is one of the most important crops for human consumption, but in recent years its consumption in raw form has decreased, especially in developed countries. Many potatoes are processed into value-added products to meet the demand of fast food industries. So far the main use of the potato peel is sold for animal feed at very low prices. In addition, there are significant quantities of rotten potatoes generated during the years of heavy rain fall, which represent a substantial financial loss to the farmers unless an alternative industrial use can be found for the biomass. Therefore, extracting cellulose from potato peel and processing them into a higher valuable product is not only an environment-friendly solution to the disposal issues but also creates a non-food based economy for potatoes.</p> <p>Cellulose nanocrystals (CN) are a promising material and have been widely studied over the past two decades. This material is interesting as nanofiller due to its nanoscale dimensions, high specific area, and highly rigid crystalline structure. In comparison to mineral or metal nanofillers that are industrially available, cellulose nanocrystals are prepared from renewable feedstocks, feature low density, are relatively low cost, and remain biodegradable.</p> <p>This study investigated the effectiveness of cellulose nanocrystal derived from potato peel waste to improve the mechanical and barrier properties of a polymer. The nanocrystals were chemically derived from the cellulosic material in potato peel waste by alkali treatment and subsequently acid hydrolysis with sulfuric acid. Infrared spectroscopy indicated sufficient removal of lignin and hemicellulose from the raw potato peel biomass whereas X-ray diffraction confirmed that the prepared nanocrystals maintained their original crystalline lattice structure as the extracted cellulose, with a crystallinity of 85%. TEM images showed that the average fiber length of the nanocrystals was 410 nm with a diameter of 10 nm (aspect ratio of 41). Cellulose nanocrystal-filled polyvinyl alcohol (PVA) and thermoplastic starch (TPS) were prepared by solution casting method to maintain uniform dispersion of the 1-2% (w/w) fibers. An increase of 19% and 38% (starch composite) and 32% and 54% (PVA composite) in Young’s modulus was observed for the 1% and 2% CN-reinforced composites, respectively. Water vapor transmission rate measurements showed a reduction of water permeability for the PVA nanocomposite, whereas no effect was observed for starch nanocomposite.</p> / Master of Applied Science (MASc)

<p>Low molecular weight functionalized polyolefins are mainly used as additives in adhesive formulations, compatibilizing agents and aqueous dispersions. However, the low viscosity and functionality they offer has never been explored to generate high molecular weight products that offer improved processing routes for polyolefins as well as wider applications.</p> <p>The aim of this thesis work was to investigate the preparation and characterization of thermoset material by reactions between a highly functionalized, low viscosity maleic anhydride grafted polyethylene and diamines. Reactions were performed both in solution and in the melt state to generate the target thermoset materials. Products from these reactions were extensively explored using different techniques to understand the reaction kinetics and mechanism. Thermosets generated were also characterized for the degree of crosslinking, thermal, mechanical and thermomechnical properties.</p> <p>Reactions in solution showed that the degree of reaction could be easily controlled by manipulating the concentration of reactants in the reaction mixture. Mixing torque data from the melt blender generated during reactions in the melt phase suggested that reaction between anhydride and amine moieties in these systems happen at much slower rate than widely reported for conventional high molecular weight polymeric systems. Unlike a single or two closely merged peaks in mixing torque associated with melting of polymer and chain extension and crosslinking due to reaction between anhydride and amine functionality widely reported, two separate peaks were observed in this study. A combination of FTIR and insoluble fraction data generated suggested that the first peak observed in mixing torque represents a combination of melting and partial reaction between anhydride and amine functionality. Whereas, the second peak in the mixing torque represents the initiation of crosslinking. The slower kinetics observed in the current investigation was found not to be a consequence of immiscibility of polyether diamine and polyethylene or the relatively higher molecular weight of diamines utilized in some reactions since using a low molecular weight aliphatic diamine, hexamethylenediamine, produced similar trends. FTIR and gel content (insoluble fraction) data generated on the prepolymers by processing them at high temperatures, suggested residual anhydride presence in products which could not be assessed using FTIR. This observation renders the popular monitoring of anhydride peak in such systems to assess the degree of reaction highly questionable. Cured thermosets from the prepolymers produced showed gel fractions of the same scale as in traditional crosslinked products. DSC heat scans on the thermosets showed separate crystal populations for polyethylene in cured and uncured fraction. Dynamic mechanical analysis result showed the thermosets withstood temperature up to 200 °C without failure and a crosslink plateau could be observed following the melting transition. Tensile properties of the thermosets were observed to be promising and composition dependent.</p> <p>These thermosets are expected to extend the polyolefins applications in areas like sealant, adhesive and coatings. The low viscosities of starting materials could also lead to new processing routes for polyolefins.</p> / Doctor of Philosophy (PhD)

<p>Maleation is a common means of modification for many commodity polymers and is used to several ends. In this study, various waxes were functionalized with maleic anhydride through several maleation processes, with the end goal of obtaining a cost effective processes to make emulsifiers to be used in emulsions that impart water-resistance to building products, such as gypsum wallboards. Research was done in collaboration with an industrial partner, in order to replace commercially available emulsifiers currently being used in their processes with a less costly product that could easily be made on-site based on their consumption requirements, through a solvent-free approach. Reactions involving both the free-radical initiated maleation of paraffin waxes and thermal addition of maleic anhydride to alpha-olefins were examined extensively. It was found that emulsions with properties matching or exceeding those of control emulsion formulations were obtainable using experimental emulsifiers made through both maleation methods. When used in gypsum wallboards, emulsifiers made through thermal maleation showed levels of water-repellency that matched or exceeded those of control formulations at lower loading levels, while emulsifiers made through free-radical maleation were subject to performance issues.</p> / Master of Applied Science (MASc)

<p>In this study new value-added products were developed from four commercially available refined waxes for use as commercial emulsifiers via the technique of maleation. This research was performed in collaboration with an industrial partner with the hope of developing a wax emulsifier product that could replace commercially used wax emulsifiers in engineered wood product emulsions at a cost reduction by beginning with the design of a cost effective process that could be incorporated into an existing factory production line. Through the investigation and subsequent optimization of this process, a highly maleated product was achieved using 6 different quick and simple approaches. A standardized experimental design was applied to the parameters of the experiment: reaction time, peroxide, starting wax, maleic anhydride concentration, and temperature to observe and understand the individual effects of each on the resultant final product. Three organic peroxide initiators were evaluated; di-<em>tert</em>-butyl peroxide, di-<em>tert</em>-butyl peroxybenzoate and benzoyl peroxide, as well as a thermally initiated approach. The resultant waxes were then identified by their acid number and drop melt point; and from this, the overall efficiency of the combined parameter levels was calculated as a function the initial maleic anhydride amount versus that of the final. The maleated wax emulsifiers were incorporated into emulsions and applied to engineered wood products. Emulsifiers made via the thermally initiated approach showed statistically significant improvements in the desired properties, water absorbance and thickness swell, of the engineered wood products as compared to a commercial control formulation.</p> / Master of Science (MSc)

<p>The controlled synthesis of functional low molecular weight polyethylene and polyethylene mimics is important in tuning polymer properties and is of great industrial interests. Living polymerization is a method that allows for precise control in polymer structure. Although high molecular weight polymers with controlled structures can be efficiently produced via living polymerization, the production of low molecular weight polymers faces the challenges of the use of large amounts of expensive catalyst and the broadening of polydispersity.</p> <p>The synthesis of well-defined functional low molecular weight polyethylene and polyethylene mimics is studied. Promising polymerization systems, including living ring opening metathesis polymerization (ROMP), living coordination polymerization, coordinative chain transfer polymerization (CCTP), and living C1 polymerization, are identified and are analyzed based on product properties, efficiency, cost, and safety.</p> <p>Within the identified systems, living ROMP is selected for study due to the industrial relevance of ROMP polymers, the availability of raw materials, and the ease of reaction setup. The efficiency of ROMP is challenged by polydispersity broadening resulting from slow initiation and poor reactor volume efficiency due to its implementation as a solution polymerization process. The challenges are addressed by the use of excess phosphine and the realization of ROMP as a bulk polymerization process.</p> <p>Experimental results demonstrate that bulk ROMP with and without phosphines yield product with similar or enhanced molecular weight distribution control as solution ROMP. Kinetic studies confirm living polymerization behaviour of bulk ROMP. A mathematical model is developed for the first time using method of moments to describe the kinetics and development of molecular weight distribution of ROMP. The model is a useful tool in preliminary research and commercialization of ROMP. The success of bulk ROMP and the development of a representative model yield ROMP as a promising method for the production of low molecular weight polymers with controlled architecture.</p> / Master of Applied Science (MASc)

<p>Intermeshing counter-rotating twin screw extruders (ICRTSE) are used extensively in the polymer processing industry for pelletizing, devolatilization and extrusion of various plastic products. ICRTSE have better positive displacement ability and are more suitable for shear sensitive materials compared to other types of twin screw extruders.</p> <p>The objectives of this thesis are to understand the flow mechanism and the effects of screw geometries and processing conditions in the ICRTSE. First, a simple flow model based on a volume of the conveying element of ICRTSE was used to calculate flow rate. Since ICRTSE do not give complete positive displacement, the various leakage flows were identified and taken into account in the simple flow model. Although the simple flow model provided reasonable results in terms of flow rate, computer simulations were found necessary due to the limitations of simple flow model. Second, a 3D computer simulation of ICRTSE was developed for various screw geometries and processing conditions. Both Newtonian and non-Newtonian fluids were examined.</p> <p>It was shown the simple model based on geometrical parameters for pumping behaviour give reasonable prediction of flow rate. It was found that determination of negative pressure should be taken into account in numerical simulations. The pumping efficiency is influenced positively by the ratio of flight width-to-channel width but it is affected negatively by the screw pitch length. It is negligibly changed with screw speed. Finally, the dominant flow is shear flow in ICRTSE and therefore, dispersive mixing capacity is very limited due to a lack of elongational effects.</p> / Master of Applied Science (MASc)

<p>N-chloramide containing and primary amine-containing microgels were prepared by post-modification of thermosensitive microgels in alkaline bleach. The objective of this project was to develop simple strategies for preparation of functionalized microgels.</p> <p>N-chlorination of linear poly(N-isopropylacrylamide) (PNIPAM) in bleach at high pH resulted in a novel N-chloramide containing copolymer: poly(NIPAM-co-NIPAMCl). The chlorinated PNIPAM showed controlled phase transition temperature and oxidative ability. The N-chlorination of linear PNIPAM inspired the preparation of N-chloramide containing PNIPAM microgels in a similar way. The phase transition temperature of the resulted chlorinated microgels, which corresponds to the extent of N-chlorination, was affected by the reaction temperature and salt concentration. The reaction between the chlorinated microgels and glutathione is proposed as diffusion controlled.</p> <p>The N-chlorination of poly(N-isopropylmethacrylamide) (PNIPMAM) microgels in bleach was restricted, in comparison with PNIPAM microgels. The active chlorine content of chlorinated PNIPMAM microgels was about one-tenth of that of chlorinated PNIPAM microgels under the same N-chlorination condition. It is proposed that the high stability of PNIPMAM in bleach is a result of the electron-donating effect of methyl groups on PNIPMAM backbone. Hence, core-shell microgels with PNIPAM cores and poly(NIPAM-co-NIPMAM) shells showed improved colloidal stability after N-chlorination because the shell was less chlorinated and served as a steric stabilizer.</p> <p>Finally, primary amine-containing microgels were prepared via Hofmann rearrangement of copolymers of methacrylamide, which decomposed to give amines, and NIPMAM, which did not react. The method was further extended to give amphoteric microgels by including acrylic acid in the starting microgels. Although other approaches to aminated and amphoteric microgels have been developed, this approach is particularly attractive because of the ease of the reaction and the ability to control the microgel isoelectric points.</p> / Doctor of Philosophy (PhD)