Thesis (DSc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Examples of the use of NMR spectroscopy in the study of radical polymerization processes have been described. The studies presented have made a significant contribution to the understanding of the fundamental mechanistic processes in these polymerization systems. It is pointed out that NMR in conventional radical polymerization is of limited use due to the concurrent occurrence of all elementary reactions (initiation, propagation and termination). Conversely, for living radical polymerization, NMR has great value. In that case, the elementary reactions are somewhat more restricted to specific times of the polymerization process. This allows for example the detailed study of the early stages of chain growth in Reversible Addition-­‐Fragmentation Chain Transfer (RAFT) mediated polymerization. Two different studies are described. The first is related to the early stages of RAFT-­‐mediated polymerization. A process for which we coined the name initialization was studied via in situ 1H NMR spectroscopy. It is shown that in many cases, there is a selective reaction that converts the original RAFT agent into its single monomer adduct. A few different examples and their mechanistic interpretation are discussed. It is also shown that NMR spectroscopy can be a valuable tool for the assessment of a RAFT agent in conjunction with a specific monomer and polymerization conditions. In the second study, 15N NMR, 31P NMR and 1H NMR are used for two different types of experiments. The first is a conventional radical copolymerization in which the growing chains are trapped by a 15N labeled nitroxide to yield a stable product. In the second experiment, a similar copolymerization is conducted under nitroxide-­‐mediated conditions. The nitroxide of choice contains phosphorous, which enables the quantification of the terminal monomer in the dormant chains. Each of the experiments individually provides interesting information on conventional radical copolymerization and nitroxide-­‐mediated copolymerization, respectively. Combination of the experimental data reveals an interesting discrepancy in the ratio of terminal monomer units in active chains and dormant chains. Although not unexpected, this result is interesting and useful from a mechanistic as well as a synthetic point of view. In terms of future perspectives, it is expected that the advanced analytical techniques as described here will remain crucial in polymer science. Present developments in radical polymerization, such as investigations into monomer sequence control, rely on accurate knowledge of kinetic and mechanistic details of elementary reactions. It is expected that such detailed studies will be a main challenge for the next decade of polymer research. / AFRIKAANSE OPSOMMING: Voorbeelde van die gebruik van KMR-­‐spektroskopie in die studie van radikaalpolimerisasies word beskryf. Hierdie studies het ʼn beduidende bydrae gelewer tot die verstaan van die fundamentele meganistiese prosesse in hierdie polimerisasiesisteme. Dit het daarop gewys dat KMR beperkte gebruike het in konvensionele radikaalpolimerisasies as gevolg van die gelyktydige voorkoms van alle basiese reaksies (afsetting, voortsetting en beëindiging). Aan die anderkant het KMR groot waarde vir lewende radikaalpolimerisasie. In hierdie geval is die elementêre reaksies ietwat meer beperk tot spesifieke tye van die polimerisasieproses. Gedetailleerde studies kan byvoorbeeld van die vroeë stadiums van die kettinggroei in Omkeerbare Addisie-­‐Fragmentasie-­‐ KettingOordrag (OAFO)-­‐bemiddelde polimerisasie gedoen word. Twee verskillende studies is beskryf. Die eerste het betrekking op die vroeë stadiums van die OAFO-­‐bemiddelde polimerisasie. 'n Proses wat “inisialisering” genoem is, is bestudeer deur middel van in situ 1H KMR-­‐spektroskopie. Dit is bewys dat daar in baie gevalle 'n selektiewe reaksie is wat die oorspronklike OAFO-­‐agent in sy enkelmonomeeradduk verander voor polimerisasie. 'n Paar ander voorbeelde en hul meganistiese interpretasie is bespreek. Dit is ook bewys dat KMR-­‐spektroskopie 'n waardevolle hulpmiddel kan wees vir die assessering van 'n OAFO-­‐agent in samewerking met 'n spesifieke monomeer en polimerisasie toestande. In die tweede studie is 15N KMR, 31P KMR en 1H KMR gebruik vir twee verskillende tipes van die eksperiment. Die eerste is 'n konvensionele radikaalkopolimerisasie waarin die groeiende kettings vasgevang word deur 'n 15N-­‐gemerkte nitroksied om 'n stabiele produk te lewer. In die tweede eksperiment is 'n soortgelyke kopolimerisasie gedoen onder nitroksied-­‐ bemiddelde toestande. Die gekose nitroksied bevat fosfor wat die kwantifisering van die terminale monomeer in die dormante kettings moontlik maak. Elkeen van die individuele eksperimente lewer interessante inligting oor konvensionele radikale kopolimerisasie en nitroksied-­‐bemiddelde kopolimerisasie, onderskeidelik. ʼn Kombinasie van die eksperimentele data toon 'n interessante verskil aan in die verhouding van die terminale monomeereenhede in die aktiewe en sluimerende kettings. Alhoewel dit nie onverwags is nie, is die resultate interessant en van waarde vanuit 'n meganistiese-­‐ sowel as 'n sintetiese oogpunt. In terme van toekomstige perspektiewe word daar verwag dat gevorderde analitiese tegnieke soos hier beskryf, belangrik sal bly in polimeerwetenskap. Huidige ontwikkelinge in radikaalpolimerisasie, soos ondersoeke na die beheer van monomeervolgorde, maak staat op akkurate kennis van kinetiese en meganistiese besonderhede van die basiese reaksies. Daar word verwag dat sulke gedetailleerde studies ʼn uitdaging sal bied vir die volgende dekade van polimeernavorsing.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: In materials chemistry, surface-initiated reversible deactivation radical polymerisation (SI-RDRP) has emerged as one of the most versatile routes to synthesising inorganic/organic hybrid materials consisting of well-defined polymers. The resultant materials often exhibit a remarkable improvement in bulk material properties even after the addition of very small amounts of inorganic modifiers like clay. A novel cationic reversible addition–fragmentation chain transfer (RAFT) agent with the dual purpose of modifying the surface of Laponite clay and controlling the polymerisation of monomer therefrom, was designed and synthesised. Its efficiency to control the polymerisation of styrene was evaluated and confirmed through investigating the molar mass evolution and chain-end functionality. The surface of Laponite clay was modified with the cationic chain transfer agent (CTA) via ion exchange and polymerisation performed in the presence of a free non-functionalised CTA. The addition of the non-functionalised CTA gave an evenly distributed CTA concentration and allowed the simultaneous growth of surface-attached and free polystyrene (PS). Further analysis of the free and grafted PS using analytical techniques developed and published during the course of this study, indicated that the free and grafted PS chains were undergoing different polymerisation mechanisms. For the second monomer system investigated n-butyl acrylate, it was apparent that the molar mass targeted and the monomer conversions attained had a significant influence on the simultaneous growth of the free and grafted polymer chains. Additional analysis of the grafted polymer chains indicated that secondary reactions dominated in the polymerisation of the surface-attached polymer chains. A new approach to separating the inorganic/organic hybrid materials into their various components using asymmetrical flow field-flow fractionation (AF4) was described. The results obtained not only gave an indication of the success of the in situ polymerisation reaction, but also provided information on the morphology of the material. Thermogravimetric analysis (TGA) was carried out on the polymer-clay nanocomposite samples. The results showed that by adding as little as 3 wt-% of clay to the polymer matrix, there was a remarkable improvement in the thermal stability. / AFRIKAANSE OPSOMMING: Oppervlakgeïnisieerde omkeerbare deaktiveringsradikaalpolimerisasie (SI-RDRP) is een van die veelsydigste roetes om anorganiese/organiese hibriedmateriale (wat bestaan uit goed-gedefinieerde polimere) te sintetiseer. Die produk toon dikwels ʼn merkwaardige verbetering in die makroskopiese eienskappe – selfs na die toevoeging van klein hoeveelhede anorganiese modifiseerders soos klei. ʼn Nuwe kationiese omkeerbare addisie-fragmentasie kettingoordrag (RAFT) middel met die tweeledige doel om die modifisering van die oppervlak van Laponite klei en die beheer van die polimerisasie van die monomeer daarvan, is ontwerp en gesintetiseer. Die klei se doeltreffendheid om die polimerisasie van stireen te beheer is geëvalueer en bevestig deur die molêre massa en die funksionele groepe aan die einde van die ketting te ondersoek. Die oppervlak van Laponite klei is gemodifiseer met die kationiese kettingoordragmiddel (CTA) deur middel van ioonuitruiling en polimerisasie wat uitgevoer word in die teenwoordigheid van ʼn vrye nie-gefunksionaliseerde CTA. Die toevoeging van die nie-gefunksionaliseerde CTA het ʼn eweredig-verspreide konsentrasie CTA teweeggebring en die gelyktydige groei van oppervlak-gebonde en vry polistireen (PS) toegelaat. Verdere ontleding van die vrye- en geënte PS met behulp van analitiese tegnieke wat ontwikkel en gepubliseer is gedurende die verloop van hierdie studie, het aangedui dat die vry- en geënte PS-kettings verskillende polimerisasiemeganismes ondergaan. n-Butielakrilaat is in die tweede monomeer-stelsel ondersoek en dit was duidelik dat die molêre massa wat geteiken is en die geënte polimeerkettings. ʼn Nuwe benadering tot die skeiding van die anorganiese/organiese hibriedmateriale in hulle onderskeie komponente met behulp van asimmetriese vloeiveld-vloei fraksionering (AF4) is beskryf. Die resultate wat verkry is, het nie net 'n aanduiding gegee van die sukses van die in-situ polimerisasiereaksie nie, maar het ook inligting verskaf oor die morfologie van die materiaal. Termogravimetriese analise (TGA) is uitgevoer op die polimeer-klei nanosaamgestelde monsters. Die resultate het getoon dat daar 'n merkwaardige verbetering in die termiese stabiliteit was na die toevoeging van so min as 3 wt% klei by die polimeermatriks.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Impact Polypropylene Copolymers (IPCs) are extremely complex materials, consisting of a mixture of polypropylene homopolymer and copolymers having different comonomer (ethylene) contents and chemical composition distributions. IPC can only be effectively analysed by multidimensional analytical approaches. For this, initially, the individual components have to be separated according to any of their molecular characteristics, either by chemical composition distribution (CCD) or molar mass distribution (MMD), followed by further analysis of these separated fractions with conventional analytical techniques. The combination of preparative temperature rising elution fractionation (TREF) with several other analytical techniques have been reported for the thorough characterization of this material. However, even the combinations of these methods were of limited value due to the complex nature of this polymer. Therefore, novel analytical approaches are needed for a more detailed compositional analysis of IPCs. This work describes a number of multidimensional analytical techniques that are based on the combination of fractionation and hyphenated techniques. Firstly, preparative TREF was combined with high temperature size exclusion chromatography-FTIR (HT SEC-FTIR), HT SEC-HPer DSC (High Performance Differential Scanning Calorimetry) and high temperature two-dimensional liquid chromatography (HT 2D-LC) for the comprehensive analysis of a typical impact polypropylene copolymer and one of its midelution temperature TREF fractions. HT SEC-FTIR analysis provided information regarding the chemical composition and crystallinity as a function of molar mass. Thermal analysis of selected SEC fractions using a novel DSC method - High Speed or High Performance Differential Scanning Calorimetry (HPer DSC) - that allows measuring of minute amounts of material down to micrograms, yielded the melting and crystallization behaviour of these fractions which is related to the chemical heterogeneity of this complex copolymer. High temperature 2D-LC analysis provided the complete separation of this TREF fraction according to the chemical composition of each component along with its molar mass distribution. In a second step, the compositional characterization by advanced thermal analysis (HPer DSC, Flash DSC 1, and solution DSC) of the TREF-SEC fractions was extended to all semi-crystalline and higher temperature TREF fractions. By applying HPer DSC at scan rates of 5−200°C/min and Flash DSC 1 at scan rates of 10−1000°C/s, the metastability of one of the fractions was studied in detail. DSC measurements of TREF-SEC cross-fractions at high scan rates in p-xylene successfully connected reversely to the slow scan rate in TREF elution, if corrected for recrystallization. Finally, the exact chemical structure of all HT HPLC separated components was determined by coupling of HT HPLC with FTIR spectroscopy via an LCTransform interface. This novel approach revealed the capability of this hyphenated technique to determine the exact chemical composition of the individual components in the complex TREF fractions of IPCs. The HT HPLC–FTIR results confirmed the separation mechanism in HPLC using a solvent gradient of 1-decanol/TCB and a graphitic stationary phase at 160°C. FTIR analysis provided information on the ethylene and propylene contents of the fractions as well as on the ethylene and propylene crystallinities. / AFRIKAANSE OPSOMMING: Impak Polipropileen Kopolimere (IPKe) is uiters komplekse materiale, bestaande uit 'n mengsel van polipropileen homopolimeer en kopolimere met verskillende komonomeer (etileen) inhoud en chemiese samestelling verspreiding. IPKe kan slegs doeltreffend ontleed word deur multidimensionele analitiese benaderings te volg. Hiervoor moet die individuele komponente aanvanklik eers geskei word volgens enige van hul molekulêre eienskappe, hetsy deur die chemiese samestelling verspreiding (CSV) of molêre massa verspreiding (MMV), gevolg deur 'n verdere ontleding van hierdie geskeide fraksies met konvensionele analitiese tegnieke. Die kombinasie van voorbereidings temperatuur-verhogings eluasie fraksionering (TVEF) met verskeie ander analitiese tegnieke is gerapporteer vir die deeglike karakterisering van hierdie materiaal. Maar selfs die kombinasies van hierdie metodes was van beperkte waarde as gevolg van die komplekse aard van hierdie polimeer. Daarom word nuwe analitiese benaderings benodig vir 'n meer gedetailleerde komposisionele ontleding van IPKe. Hierdie studie beskryf 'n aantal multidimensionele analitiese tegnieke wat gebaseer is op die kombinasie van fraksionering en gekoppelde tegnieke. Eerstens is voorbereidings TVEF gekombineer met hoë temperatuur grootte-uitsluitingschromatografie-FTIR (HT GUC-FTIR), HT GUC-HPer DSK en hoë temperatuur twee-dimensionele vloeistof chromatografie (HT 2D-VC) vir die omvattende ontleding van 'n tipiese impak polipropileen kopolimeer en een van sy mid-eluasie temperatuur TVEF fraksies. HT GUC-FTIR analiese het inligting verskaf met betrekking tot die chemiese samestelling en kristalliniteit as 'n funksie van molêre massa. Termiese analiese van geselekteerde GUC fraksies deur gebruik te maak van 'n nuwe-DSK metode - Hoë Spoed of Hoë Prestasie Differensïele skandeer kalorimetrie (HPer DSK) - wat die meting van klein hoeveelhede materiaal tot by mikrogram hoeveelhede toelaat, het die smelt en kristallisasie gedrag van hierdie fraksies bepaal wat verwant is aan die chemiese heterogeniteit van hierdie komplekse kopolimeer. Hoë temperatuur 2D-LC analiese het die volledige skeiding van hierdie TVEF fraksie volgens die chemiese samestelling van elke komponent saam met die molêre massa verspreiding moontlik gemaak. In 'n tweede stap, is die komposisionele karakterisering deur gevorderde termiese analiese (HPer DSK, Flash DSK 1 en oplossing DSK) van die TVEF-GUC fraksies uitgebrei na alle semi-kristallyne en hoër temperatuur TVEF fraksies. Deur die gebruik van HPer DSK, teen ’n skandeerspoed van 5-200°C / min, en Flash DSK 1, teen ’n skandeerspoed van 10-1000°C / s, is die meta-stabiliteit van een van die fraksies in detail bestudeer. DSK metings van TVEF-GUC kruis-fraksies by 'n hoë skandeeerspoed in p-xyleen het suksesvol omgekeerd verbind aan die stadige skandeerspoed in TVEF eluasie, wanneer gekorrigeer vir dekristallisatie. Ten slotte is die presiese chemiese struktuur van al die HT HPVC geskeide komponente bepaal deur die koppeling van HT HPVC met FTIR spektroskopie deur middel van 'n LC-transform-koppelvlak. Hierdie nuwe benadering het die vermoë van die gekoppelde tegniek om die presiese chemiese samestelling van die individuele komponente in die komplekse TVEF fraksies of IPKe te bepaal aan die lig gebring. Die HT HPVC-FTIR resultate het die skeidingsmeganisme in HPVC bevestig deur die gebruik van ’n oplosmiddelgradiënt van 1-dekanol/TCB en 'n graphitiese stasionêre fase by 160°C. FTIR analiese verskaf inligting in verband met die etileen en propileen inhoud van die fraksies sowel as die etileen en propileen krystalliniteit.

Thesis (MSc)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: In the ongomg search for better and faster ways to characterize complex polymer systems, it is often necessary to couple different analytical techniques in order to obtain information on more than one distributed property. In this study, the coupling of chromatography and spectroscopy to atomic force microscopy (AFM) was attempted for the first time, and thus the term "LC-FTIR-AFM" was coined. This new hyphenated technique combines the separation power of liquid chromatography (LC) and the ability of infrared spectroscopy (IR) to identify almost any organic compound, with the AFM's ability to be used for thermal analysis of individual phases in polymer mixtures. The first two steps of this new technique comprise (i) the separation of compounds in a mixture via gradient polymer elution chromatography (GPEC) and (ii) the identification of each compound by means of LC-FTIR analysis. In the final step, LC-FTIR analysis is coupled to AFM through the use of the LC-FTIR interface. A number of polymer mixtures were analysed by means of the novel technique that was developed, in order to establish its validity and value as a characterization technique of the future. The influence of fllm thickness and molar mass on the thermal parameters of individual components in mixtures, measured by this technique, were also investigated. This technique adds a new dimension to conventional thermal analysis methods, since it allows the thermal transitions of individual polymer phases in multiphase polymers to be resolved directly after separation and identification. / AFRIKAANSE OPSOMMING: In die voortdurende soektog na beter en vinniger maniere om komplekse polimeersisteme te karakteriseer, is dit soms nodig om verskillende analitiese tegnieke met mekaar te koppel ten einde inligting aangaande twee of meer verspreide eienskappe te bekom. Gedurende hierdie studie is daar gepoog om chromatografie en spektroskopie met atoominteraksie-mikroskopie (atomic force microscopy, AFM) te koppel. Gevolglik het die term "LC-FTIR-AFM" ontstaan. Hierdie nuwe koppelingstegniek kombineer die kragtige skeidingspotensiaal van vloeistofchromatografie en die vermoë van infrarooispektroskopie om byna enige organiese verbinding positief te identifiseer, met die atoominteraksie-mikroskoop se potensiaal om as 'n termiese analise metode vir individuele fases in polimeermengsels te dien. Die eerste twee stappe van die tegniek behels (i) die skeiding van verbindings in 'n mengsel deur middel van gradient-hoë-druk-vloeistofchromatografie en (ii) die identifisering van afsonderlike verbindings deur vloeistofchromatografie gekoppel aan infrarooispektroskopie. Gedurende die finale stap word vloeistofchromatografie en infrarooispektroskopie aan die atoominteraksie-mikroskoop gekoppel deur gebruik te maak van die LC-FTIR koppelingsapparaat. 'n Aantal polimeermengsels is geanaliseer deur die nuwe tegniek hierbo beskryf, ten einde die geldigheid en waarde daarvan as 'n analitiese metode vir die toekoms vas te stel. Die invloed van film diktes en molekulêre massa op die termiese oorgange van individuele komponente in mengsels, soos gemeet deur hierdie metode, is ook ondersoek. Hierdie tegniek voeg 'n nuwe dimensie tot konvensionele termiese analise metodes deurdat dit die bepaling van termiese oorgange van individuele polimeerfases III multifase polimere, direk na afloop van skeiding en identifikasie moontlik maak.