Yes / Polymer self-assembly in solution is a simple strategy for the preparation of elegant yet complex nanomaterials. However, exhaustive synthesis of the copolymer synthons is often required to access specific assemblies. In this work we show that the blending of just two diblock copolymers with identical block lengths but varying hydrophobic monomer incorporations can be used to access a range of assemblies of intermediate hydrophobic composition. Indeed, the nanostructures produced from blending are identical to those formed with the directly synthesized copolymer of the same composition. This new approach presents researchers with a more efficient and accessible methodology to access precision self-assembled nanostructures, and we highlight its potential by applying it to a demonstrator catalytically active system. / European Science Foundation (ESF), Engineering and Physical Sciences Research Council (EPSRC), United States. Air Force. Office of Scientific Research (AFOSR)

It’s becoming more and more difficult to make smaller, denser, and faster computer chips. There’s an increasing demand to design new materials to be applied in current lithographic process to get higher patterning performance. In this work, the aqueous developable single molecule resists were introduced, synthesized and patterned. A new group of epoxide other than glycidyl ether, cyclohexene oxide was introduced to functionalize a molecular core and 15 nm resolution was obtained. The directed self-assembly (DSA) of block copolymers as an alternative lithographic technique has received growing interest in the last several years for performing higher levels of pitch subdivision. A 3-step simplified process for DSA by using a photodefinable substrate was introduced by using a functionalized polyphenol with an energy switchable group and a crosslinkable group. Two high χ block copolymers PS-b-PAA and PS-b-PHEMA were successfully designed and synthesized via ATRP with controlled Mw and PDI. The size of the same PS-b-PAA polymer was tunable by varying the thermal annealing time. PS-b-PHEMA shows to be a suitable block polymer for the industry-friendly thermal annealing process. A self-complementary hydrogen-bonding urea group as a center group was used to facilitate the self-assembly of polymers. “Click” chemistry is promising for synthesis of PS-Urea-Urea-PMMA.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / Hybrid A-B type block copolymers of polydimethylsiloxane (PDMS) and polystyrene (PS) were synthesised. Three different synthetic routes, which allowed control over polymer structure, were chosen to synthesise these block copolymers. The first technique, coupling of functional prepolymers, involved using anionic polymerisation to produce PDMS and PS functional prepolymers of controlled structure. These prepolymers were functionalised with either silane or allyl functionality and then coupled using a hydrosilylation reaction with Karstetds platinum catalyst. This technique was the least efficient in block synthesis due to the incompatibility of the disparate prepolymers. The second technique under study, sequential anionic polymerisation, gave excellent block copolymer formation with good control over the chain architecture. The final technique employed atom transfer radical polymerisation (ATRP) of styrene using a bromoisobutyrate functionalised PDMS macroinitiator. Silane functional PDMS molecules underwent a hydrosilylation reaction with allyl-2-bromo-2-methyl-propionate to produce the bromoisobutyrate functionalised polymer in excellent yields. Subsequent ATRP with styrene allowed the successful synthesis of block copolymers of controlled structure. Chromatographic systems that allowed liquid chromatography at the critical conditions (LC-CC) of PS and gradient elution chromatography (GEC) of the products were developed. GEC was used successfully in the monitoring of the presence and removal of PDMS homopolymer present in the block copolymer products. LCCC at the critical point of PS allowed successful chromatographic separation of PS homopolymer from the block material, as well as, the molecular weight distribution of the block material according to the segmental length of the PDMS component. LC-CC coupled to FT-IR using a LC-transform device allowed successful characterisation of the block copolymer chemical composition. Corona treatment was used to modify the surface structure of the block copolymer films. Optical microscopy and slow positron beam studies highlighted the formation of a thin silica like layer on the surface of the films after corona. The positron studies enabled determination of the silica like layer’s thickness. Contact angle studies provided the first evidence of hydrophobic loss and recovery for these PDMS containing hybrid polymer materials after corona treatment. A novel offline coupling technique was developed between LC-CC separation and transmission electron microscopy (TEM) analysis. This allowed easy sample preparation without the difficult bulk extraction procedures needed to remove homo-PS contaminants from the block copolymer. This technique also provided morphological information as a function of PDMS segmental length.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Graft and block copolymers were synthesized using multifunctional and monofunctional macroinitiators to produce the copolymers. The process involved hydroboration of commercially available unsaturated rubbers and chain-end unsaturated macromonomers with 9-borabicyclo [3.3.1] nonane (9-BBN). The resulting secondary alkyl 9-BBN moieties in the starting materials were subsequently exposed to oxygen in the presence of free radical polymerizable monomers to facilitate the formation of graft and block copolymers. This research was initiated by first studying the hydroboration of a model compound, 2-hexene, in order to determine the optimal conditions for the graft reactions. The model compound was subsequently used as a macroinitiator to initiate the polymerization of methylmethacrylate (MMA). The same borane chemistry was extended to the synthesis of polystyrene (PS) block copolymers. Chain-end unsaturated PS macromonomers, synthesized by anionic polymerization, were effectively hydroborated and then polymerized to produce PS-b-PMMA block copolymers. The synthesis of polyolefin graft copolymers was subsequently achieved by hydroboration. Several commercial rubbers with different levels of unsaturated segments were efficiently grafted with vinyl monomers MMA and styrene (St) following the “graft from” approach. The grafted reactions were carried out under various reaction conditions to determine the effect of the following factors: concentration of oxygen, amount of borane and monomer concentration. By controlling these factors, different graft densities were achieved with high graft efficiencies. All reactions produced mixed products including unreacted (non-functional) macroinitiator, homopolymer, graft copolymer and in case of the highly unsaturated polymer a crosslinked gel. Finally, the chemical compositions as well as the molar mass distribution of the graft copolymers were fully characterized by different chromatographic techniques. 1H-NMR and FTIR were also used to confirm the structure of these copolymers. Gradient HPLC was developed and extensively used to characterize the graft copolymers.

Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2005. / This study involves the synthesis and characterisation of PEG-based amphiphilic block copolymers for the hydrophilization of polysulphone ultrafiltration membranes. PEG based macro RAFT agents were synthesized and characterised. PEG-b-PS block copolymers were synthesized via the RAFT assisted controlled free radical polymerisation utilizing the synthesized PEG macro RAFT agents. The resulting polymerisation products were then analyzed by two-dimensional chromatography at the “critical conditions” for PS. In the second phase of this study PEG-b-PSU block copolymers were synthesized via the polycondensation of bis (4-chlorophenyl) sulphone, Bisphenol A, and PEG. The resulting products were characterised by NMR spectrometry. PEG-b-PS films and modified PSU membranes (modified by the addition of PEG-b-PSU block copolymer to the membrane casting solution) were prepared and analyzed. Surface analyses included static contact angle, AFM force-distance analysis, and FTIR-PAS analysis. Results showed the successful synthesis of both PEG-b-PS and PEG-b-PSU amphiphilic block copolymers. Surface analysis proved the successful hydrophilization of the surface of the modified PSU membranes.

This dissertation presents solid-state NMR studies that probe the dynamic and conformational properties of polymers adsorbed on solid surfaces in the dry state. The systems studied include a series of ethylene based random copolymers where the binding group is modified, and two diblock copolymer systems where the blocks have different intrinsic mobilities and surface interactions. The thesis begins by looking at the structures formed by the adsorption of poly (ethylene-co-acrylic acid) (PEA), poly (ethylene- co-vinyl alcohol) (EVOH), poly (ethylene-co-vinyl acetate) (EVA), and polyethylene (PE) on metal oxide powders (zirconia and alumina). NMR spectroscopy, FTIR-PAS, and TGA were used to characterize the surface behaviour of the systems with comparisons made between the bulk and adsorbed copolymers. 13C CPMAS, 1H and T 1 relaxation measurements were all recorded with the aim of correlating the microscopic structure of the surface with changes in NMR data. The chain conformation of adsorbed ethylene copolymers was found to strongly depend on the binding strength of the polar sticker groups with the substrates. / The chain dynamics of adsorbed diblock copolymers in the dry state are reported for the first time. Poly (styrene)-b-poly ( t-butyl acrylate) (PS-PtButA) and poly (styrene)-b-poly (acrylic acid) (PS-PAA) were selected to vary both the block size and the binding strength. Once again the primary surface characterization methods are NMR spectroscopy, FTIR-PAS, and TGA. 13C CPMAS, 1H, T1, and T1rho relaxation measurements were all recorded with the aim of correlating the surface structures with changes in NMR data. For the most part, the observed trends in the chain mobilities of the anchor (PAA) and buoy (PS) blocks with block size can be correlated with the predicted mushroom, intermediate and extended brush structures which collapse upon removal of the solvent. However, the chain mobility of the PS buoys decreases with increasing anchor block size. Although the chain mobility of the PS buoys are moderately enhanced relative to the bulk state, the mobility is sufficiently restricted to comfirm the picture of a thin glassy layer with adhesive properties similar to the surface of bulk polystyrene. / The diblock copolymers poly (2-vinylpyridine), poly (isoprene)- b-poly (2--vinylpyridine), (PI-P2VP) and poly (isoprene)- b-poly (4-vinylpyridine) (PI-P4VP) were selected to complement the PS-PAA system as both systems have been studied by surface force microscopy. The large contrast in chain mobilities of the PI and PVP blocks allowed spectral editing through variation of the 13C cross polarization parameters. The trends in mobility with block size differ from that of PS-PAA in that the segmental mobility of the buoys increases with anchor block size as expected. The chain mobility of the collapsed PI brushes is significantly enhanced as compared to the bulk state, again supporting the interpretation of surface microscopy studies which require an entropically unfavorable flattened, yet rubbery, surface structure.

No description available.

No description available.

The structure-property relationships for various segmented copolymers were investigated. A number of mechanical and thermal characteristics were determined. The morphology was characterized by SAXS with respect to size and dispersion of domains; degree of phase separation and the domain interfacial thickness. a. Novel segmented copolymers were synthesized using amino terminated polydimethylsiloxane oligomers as the soft component and various hard component. lt was found that the performance of these copolymers was affected by the varying the hard segment linkages, hard segment content, soft segment MW, stiffness of the siloxane backbone, and amount of chain extender. Two-phase nature of these copolymers was verified by dynamic mechanical, thermal, and SAXS studies. The phase separation was found to occur in these copolymers with as little as 6% HS. These materials displayed behavior similar to the segmented polyurethanes and were found to be superior to the unfilled silicone elastomers. The final materials were used as reasonable models for investigating various methods for determining the interfacial layer thickness between the hard and soft phase. Specifically, due to the fact that there is no hard segment length distribution as is the usual case for segmented urethanes, these materials have some degree of model characteristics. Utilizing Porod's law, and appropriate analysis, both positive and negative deviations were found in the systematic series of copolymers with the degree of positive and negative character dependent upon composition. Negative deviations were accounted for in terms of a finite interfacial thickness which turned out to be relatively small as anticipated, while the positive deviations arose due to isolated hard segments that reside within the soft segment matrix, concentration fluctuations. ln calculating the interfacial thickness, several methods were applied and in general, close agreement was obtained. Finally, correlation function analysis in conjunction with determination of the coherent Porod lengths, etc. were determined and discussed accordingly. b. The structure-property behavior of novel 'water extended' segmented polyurethane-urea copolymers was also investigated. These copolymers were synthesized by utilizing the dehydration characteristics of tertiary alcohols at sufficiently high temperature in weak acidic medium. Mechanical, thermal, dynamic mechanical, and x-ray experiments were carried out to characterize the morphology and properties of these segmented copolymers of systematically varying hard segment content, soft segment MW, block length, and hard segment type. lt was observed that these properties depended primarily on the degree of order in the hard domains and the order could be improved by increasing either the HS content at constant soft segment MW or soft segment molecular weight at the same HS content. The results obtained for these materials were compared with those from conventional polyurethanes to investigate the effect of intermolecular hydrogen bonding on molecular arrangement. c. The final series of segmented copolymers studied were based on polysulfone and polydimethylsiloxane, synthesized by solution polymerization. lt is shown that by varying the length of the segments for each phase and their relative content, it is possible to alter the mechanical and thermal characteristics. The mechanical response was also influenced according to which phase is predominantly continuous. In addition to dynamic mechanical and SAXS measurements, the evidence of the two-phase structure was obtained by TEM. / Ph. D. / incomplete_metadata

Dissertation (MSc)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: Polymers prepared via radical techniques are very common in our every day environment. The technique is however limited by a lack of control over the polymerization and an inability to produce block copolymers. Block copolymers have a significant number of potential applications in advanced materials and as a result are a field in which significant research is being conducted. Reversible Addition-Fragmentation chain transfer (RAFT) is a living free radical process that overcomes the disadvantages inherent in the traditional process. In this study the mediation behaviour of two inherently different RAFT agents was investigated by the “living” free radical polymerization of model monomers via the RAFT process in homogeneous and aqueous dispersed media with the focus on differentiating between the two types of agents. To ensure that the agents were comparable a new RAFT agent had to be prepared which has not previously been documented. The efficiency of the RAFT agents was compared in terms of rate effects, the predictability of the molecular weights of the polymers, the polydispersities of the polymers and their ability to allow block copolymer formation via sequential addition of monomers. Block copolymerizations were conducted by the addition of new monomer to the already existing RAFT end-capped chains. Monomer addition was done via three different approaches; namely shot addition, feed addition and pre-swelling (in the case of emulsions). Chromatographic analysis was conducted on the resulting block copolymers via liquid chromatography at critical conditions (LCCC), and its online coupling with size-exclusion chromatography (SEC) to obtain two-dimensional information on the differences in heterogeneity of their molecular distributions. Other analyses included dynamic light scattering analysis (DLS) and transmission electron microscopy (TEM). The detailed analysis enabled the understanding of the different products that are produced via the two different classes of RAFT agent. Potential causes for the differences are discussed and possible areas for future research are highlighted. The work presented here is the most detailed investigation of this class of polymerization to date and will provide new insight for researchers working in this vibrant and important research field. / AFRIKAANSE OPSOMMING: Polimere gesintetiseer deur die gebruik van radikaal tegnieke is algemeen in ons daaglikse omgewing. Die tegniek is egter beperk deur die gebrek aan beheer oor die polimerisasie en die onvermoë om blokkopolimere te sintetiseer. Blokkopolimere beskik oor ‘n aansienlike hoeveelheid potensiele aanwendinge in gevorderde materiale en is gevolglik ‘n belangrike navorsingsgebied. Omkeerbare addisie fragmentasie ketting oordrag (OAFO) is ‘n lewende vrye radikaal proses wat die inherente nadele van die tradisionele proses oorkom. In die betrokke studie is die mediasie gedrag van twee verskillende OAFO agente bestudeer deur die lewende vrye radikaal polimerisasie van model monomere deur die OAFO proses in homogene en waterig dispersie media met die fokus op differensiering tussen die twee tipes agente. Om te verseker dat die twee agente vergelykbaar is, is ‘n nuwe OAFO agent voorberei wat tot op hede nog nie gedokumenteer is nie. Die effektiwiteit van die OAFO agente is vergelyk in terme van tempo effekte, die voorspelbaarheid van die molekulêre massa van die polimere, die polidispersiteit van die polimere en die moontlikheid om blokkopolimerisasie deur kronologiese byvoeging van monomere te fasiliteer. Blokkopolimerisasie is uitgevoer deur die byvoeging van nuwe monomeer tot die alreeds bestaande OAFO eind-groep kettings. Monomeer byvoegings is uitgevoer deur drie verskillende metodes; naamlik vulskoot addisie, voer addisie en vooraf swelling (in die geval van emulsies). Chromatografiese analise is uitgevoer op die resulterende blokkopolimere deur vloeistof chromatografie by kritieke kondisie (LC-CC) en die aanlyn koppeling met grootte-uitsluiting vloeistof chromatografie, om twee-dimensionele informasie omtrent die verskille in heterogeniteit van hul molekulere verdeling te bepaal. Verdere analise sluit dinamiese verstrooing mikroskopie en transmissie elektron mikroskopie in. Die detaileerde analise onthul die samestelling van die verskillende produkte wat geproduseer is deur die verskillende klasse van OAFO agent. Potensiele oorsake vir die verskille is bespreek en moontlike areas vir toekomstige navorsing is benadruk. Die werk hier voorgestel is die mees gedetaileerde navorsing van hierdie tipe klas van polymerisasie tot op hede en beloof nuwe insig vir navorsers betrokke in hierdie dinamiese en belangrike navorsingsveld.