In Chapter 1, theories cited background of these studies as well as chemical synthesis methods used are introduced. / In Chapter 2, theories of static and dynamic light scattering (LLS) as well as details of the LLS instrumentation are introduced, especially the application of LLS to polymer solutions. / In Chapter 3, we present the study of the self-assembly of oligo( p-phenyteneethynylene)-based coil-rod-coil and rod-coil-rod triblock copolymers in the solvent mixture of toluene and hexane by using a combination of static and dynamic laser light scattering. UV-vis spectroscopy and fluorescence spectroscopy. Our results reveal that the aggregation in the solvent mixture is strongly influenced by the triblock copolymer structure. For the coil-rod-coil (PS-OPE-PS) triblock copolymer, small well-defined aggregates are formed in the solvent mixture with different toluene/hexane ratios. The coiled PS blocks entangle with the OPE block to restrict possible pi-pi stacking and make the OPE chain backbone more planar. The red-shift in the UV-vis and fluorescence spectra indicates the formation of 3-type aggregates. The rod-coil-rod (OPE-PS-OPE) triblock copolymer chains form large "disk-like" micelles with an ordered OPE core and a collapsed PS shell. The blue-shift in the UV-vis and fluorescence spectra shows the formation of H-type aggregates; namely, the OPE block in the core are parallel to each other so that there is stronger interchain pi-pi interaction. / In Chapter 4, we present the study of the aggregation of C60-PEO-C 60 chains in the chloronaphthalene/benzene solvent mixture with different ratios by using a combination of static and dynamic laser light scattering. Chloronaphthalene is a good solvent for C60 but a poor solvent for the PEO chain. On the other hand, benzene is a good solvent for the PEO chain but a poor solvent for Co. Individual polymer chains or small micelles coexist with large aggregates in solvent mixture. Our results show that the structures of the aggregates strongly depend on the composition of the solvent mixtures, which reflects in different ratios of <Rg>/<R h>, where <Rg> and <Rh> are z-average root-mean-square radius of gyration and hydrodynamic radius, respectively. / In Chapter 5, we present a study of reversible formation and decomposition of star polymer clusters. First, we synthesized 4-aim bromide-end star polystyrene chains by using atom transfer radical polymerization (ATRP), and then modified the end group from bromide to thiol since it can be slowly oxidized in air to induce the clustering among 4-arm star polystyrene chains. The clustering is reversible under a reduction condition. Such formation and fragmentation (decomposition) of the polymer clusters in toluene was followed by LLS. To induce the reduction, DTT was added. Our results reveal that in the clustering, the fast mode is attributed to the cooperative diffusion of individual 4-arm star polystyrene chains (unimers), while the slow mode is related to the diffusion of large clusters. In the fragmentation, the slow mode becomes fast and its intensity contribution decreases as the reduction time increases, reflecting the decreases of the size and the number of large polymer clusters. Our results suggest that the clusters fragmentation induced by thiol-functionalized 4-PS chains in toluene dilute solution follows the universal RLCA regime, but in a reversed fashion. / In this thesis, we did the following studies: (1) The association of two rod-coil triblock copolymers: polystyrene-oligo(p-phenyleneethynylene)-polystyrene (PS-OPE-PS) and oligo(p-phenyleneethynylene)-polystyrene-oligo( p-phenyleneethynylene) (OPE-PS-OPE) in a toluene/hexane mixture as well as of C60-Poly(ethylene oxide)-C60 in a chloronaphthalene/benzene mixture. (2) The formation and fragmentation of 4-arm-PS-SH cluster in toluene via the oxidization in air to form disulfide crosslink as well as the decomposition of the resultant cross-linked 4-arm star polystyrene clusters with reversible disulfide groups in toluene via reduction to thiol group by 2,3-dihydroxy-1,4-butanethiol (DTT). / Huo, Hong. / "August 2007." / Adviser: Chi Wu. / Source: Dissertation Abstracts International, Volume: 69-02, Section: B, page: 1037. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (p. 109). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract in English and Chinese. / School code: 1307.

Thesis (Ph.D.)--University of Wollongong, 2003. / Typescript. Includes bibliographical references.

Thesis (MSc)-- Stellenbosch University, 2012. / ENGLISH ABSTRACT: Over the past two decades, field flow fractionation (FFF), as a polymer characterization technique, has become cutting edge technology. The demand for molar mass and size characterisation of complex polymer systems has increased, especially in cases where classical calibration techniques such as size exclusion chromatography (SEC) has shown several shortcomings. FFF is a technique resembling chromatography. It has several significant advantages over SEC, especially for the characterisation of ultrahigh molar mass (UHMM), branched and gel-containing polymers. In this study, polybutadienes, which often contain the abovementioned species, were analysed by SEC and asymmetric flow field flow fractionation (AF4). Both separation techniques were coupled to refractive index and multi-angle laser light scattering detection. Similarly, polyrotaxanes, which are polymers with complex and unique molecular architectures, were also investigated. Results showed that AF4 can explicitly be used as a superior tool over SEC. In the case of UHMM polybutadienes, much higher molar masses could be detected by AF4, due to the absence of shear degradation which is often encountered in SEC. Gel-containing species could be detected by AF4 as no filtering is required prior to injection. Abnormal retention behaviour, a phenomenon often encountered in UHMM branched polymers, was observed in SEC analysis of the polyrotaxanes materials. AF4 provided sufficient separation from low to high molar masses, without out any irregularities. / AFRIKAANSE OPSOMMING: Gedurende die afgelope twee dekades het veldvloeifraksionering (FFF) as ‘n polimeerkarakteriseringstegniek groot veld gewen. Die aanvraag na molekulêre massa en groottekarakterisering van komplekse polimeersisteme het toegeneem, veral in die gevalle waar klassieke kalibrasietegnieke soos grootte-uitsluitingschromatografie (SEC) etlike tekortkominge getoon het. FFF is ‘n tegniek soortgelyk aan chromatografie, en het voorheen bewys dat dit oor ‘n redelike aantal voordele bo SEC beskik, veral in die geval van ultrahoë molekulêre massa- (UHMM-), vertakte- en jelbevattende spesies. In die huidige studie is polibutadieenpolimere, wat dikwels bogenoemde spesies bevat, geanaliseer met behulp van SEC en onsimmetriese vloei-veldvloeifraksionering (AF4). Beide skeidingstegnieke is gekoppel aan ‘n brekingsindeks en multihoek-laserligverstrooiingsdetektors. Op dieselfde wyse is polirotaksane (polyrotaxanes) met komplekse molekulêre argitektuur bestudeer. Daar is bewys dat AF4 uitsluitlik gebruik kan word as ‘n meer geskikte tegniek bo SEC. Baie hoër molekulêre massas kon deur middel van AF4 vir UHMM polibutadieenpolimere raakgesien word as gevolg van die verminderde afbrekende degradasie wat dikwels voorkom met SEC. Jel-bevattende spesies is suksesvol geïdentifiseer met behulp van AF4 waartydens geen filtrering vir analise nodig was nie. Abnormale retensie was sigbaar tydens SEC analise van monsters van polirotaksane, wat dikwels voorkom in vertakte polimere. In teenstelling het AF4 bewys dat ‘n bevredigende skeiding van klein na groot molekulêre massas, sonder enige tekortkominge, moontlik is.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / This study involves the fractionation and characterisation of three propyleneethylene random copolymers. The fractionation technique used in the study was temperature rising elution fractionation (TREF). The TREF fractions were subsequently analysed offline by crystallisation analysis fractionation (CRYSTAF), differential scanning calorimetry (DSC), 13C NMR, high-temperature gel-permeation chromatography (HT-GPC), and wide-angle x-ray diffraction (WAXD). The effect of the ethylene comonomer on the crystallisability of the propylene was investigated, along with the effect of the comonomer on the type of crystal phase formed during the crystallisation. The results show that the comonomer inhibits the crystallisation of the copolymer and that as the ethylene content increases, the crystallisation and melting points decrease. It was also shown that the higher the ethylene content, the more of the γ-phase crystal type is formed. The distribution of the comonomer throughout the copolymers was also investigated. The results show that there is an uneven distribution of the comonomer with most of the comonomer accumulating in the amorphous areas, and very little actually being incorporated in the crystalline regions. It was also observed that the fractions eluting at the highest temperatures had considerably higher polydispersities and lower molecular weights than the fractions eluting just before them. The highest temperature fractions also have lower melting and crystallisation temperatures than the preceding fractions. This has been attributed to a nucleation effect by the sand support used during the TREF fractionation.

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Complex polymer systems have multiple distributions with regard to molecular parameters such as molar mass, functionality, chemical composition, molecular architecture and microstructure. These distributions affect the properties of the polymers making it necessary to develop separation methods to be able to correlate structure to property. A single onedimensional chromatographic method is usually not sufficient to separate these complex polymers with respect to all the distributions. Hence, multidimensional liquid chromatography is necessary for the complete analysis of complex polymers using two or more chromatographic techniques before detection. In this work, two novel liquid chromatographic methods were developed to separate complex polymers according to microstructure. Comprehensive two-dimensional liquid chromatography (LC x LC) was carried out to observe the correlation between microstructure and molar mass. The separation according to microstructure was coupled to NMR (LC-NMR) to observe, identify and quantify the different microstructural components during chromatographic elution. The first chromatographic method separated hydrogenated and deuterated polystyrene homopolymers with respect to the isotope effect. For the LC x LC experiments, liquid chromatography at critical conditions (LCCC) was employed as the first dimension separating according to the isotope effect and size exclusion chromatography (SEC) as the second dimension separating according to molar mass. The LC x LC results of the blends showed that there was an improvement in isotopic separation with an increase in molar mass. The LCNMR coupling using both 1H and 2H NMR detection allowed for the identification of low molar mass blend components which were not sufficiently separated by liquid chromatography. The second chromatographic method separated stereoregular poly(methyl methacrylate)s (PMMAs) with respect to tacticity. The LC x LC experiments of stereoregular PMMAs utilised solvent gradient liquid chromatography as the first dimension to separate according to tacticity and size exclusion chromatography (SEC) as the second dimension to separate according to molar mass. The LC x LC results showed a change in the triad composition with elution of the stereoregular PMMAs with a slight influence of molar mass. The LC-NMR coupling allowed the observation of the triad composition during chromatographic elution. / AFRIKAANSE OPSOMMING: Komplekse polimeriese sisteme het meervoudige verspreidings ten opsigte van molekulêre parameters, soos byvoorbeeld, molêre massa, funksionaliteit, chemiese samestelling, molekulêre argitektuur en mikrostruktuur. Hierdie verspreidings beïnvloed die eienskappe van die polimere en dus is dit nodig om skeidingsmetodes te ontwikkel ten einde polimeerstruktuur met polimeereienskappe te kan korreleer. ‘n Enkele een-dimensionele chromatografiese metode is gewoonlik nie voldoende om hierdie komplekse polimere te skei met betrekking tot al die verspreidings nie. Multidimensionele vloeistofchromatografie, met die insluiting van twee of meer chromatografiese tegnieke, is dus nodig om polimere te skei voor waarneming kan plaasvind. Twee nuwe chromatografiese metodes is ontwikkel om komplekse polimere volgens mikrostruktuur te skei. Twee-dimensionele vloeistofchromatografie (LC x LC) is uitgevoer ten einde die korrelasie tussen mikrostruktuur en molêre massa te ondersoek. Daarna is die skeiding wat op mikrostruktuur gebasseer is, gekoppel aan KMR (LC-KMR) om die verskillende mikrostrukturele komponente gedurende chromatografiese eluering waar te neem, te identifiseer en te kwantifiseer. Die eerste chromatografiese metode het die gehidrogeneerde en gedeutereerde polistireen geskei met betrekking tot die isotoopeffek. Hier het die LC x LC skeiding bestaan uit vloeistofchromatografie onder kritiese kondisies (LCCC) as die eerste dimensie, wat skeiding bewerkstellig het gebasseer op die isotoopeffek, en grootte-uitsluitingschromatografie (SEC) as die tweede dimensie, wat skeiding bewerkstellig het gebasseer op die molêre massa. Die LC x LC resultate van die vermengings het ‘n verbetering in isotopiese skeiding met ‘n toename in molêre massa getoon. Deur gebruik te maak van die LC-KMR koppeling, waar beide 1H en 2H KMR waarneming gebruik is, was dit moontlik om die lae-molêre-massakomponente van vermengings wat nie volledig d.m.v. LC geskei kon word nie, te identifiseer. Die tweede chromatografiese metode het stereoreëlmatige polimetielmetakrilate (PMMAs) m.b.t. taktisiteit geskei. Die LC x LC skeiding van stereoreëlmatige PMMAs het bestaan uit oplosmiddel -gradiënt-LC as eerste dimensie om volgens taktisiteit te skei, en SEC as tweede dimensie om volgens molêre massa te skei. Die LC x LC resultate het ‘n molêre massa afhanklikheid van stereoreëlmatige PMMAs op taktisiteit getoon. Die LC-KMR koppeling het dit moontlik gemaak om die triade-samestelling gedurende chromatografiese eluering waar te neem.