Statistical copolymers of acrylonitrile (AN) and methyl acrylate (MA) were successfully prepared and characterized using reversible addition-fragmentation chain transfer (RAFT) copolymerization. A typical copolymer was charged with 15 wt. % MA content. This thesis describes a systematic variation of the RAFT copolymerization variables to optimize this system. In particular, the effects of chain transfer agent, initiator, temperature, and solvent on the copolymer properties were studied. / Master of Science

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Thesis submitted in partial fulfillment of the requirements for the degree of Master of Science (Polymer Science) at University of Stellenbosch. / ENGLISH ABSTRACT: The preparation of poly(acrylonitrile/methyl acrylate) [poly(AN-co-MA)] copolymers and poly(AN-co-MA)/clay nanocomposites, via emulsion polymerization, their characterisation, and the relationships between their molecular structures and physical properties are described. The copolymer composition was varied, and the properties of the products were analysed and correlated to copolymer composition. The free volume properties of the copolymer were dependent on the glass transition temperature (Tg), which is dependant on the copolymer composition. The copolymer crystallinity decreased with increasing MA content. The decrease in crystallinity and increase in both o-Ps lifetime and o-Ps intensity with decreasing Tg was caused by the enhanced chain mobility brought about by the incorporation of methyl acrylate. The poly(acrylonitrile-co-methyl acrylate)/clay nanocomposites with 60% AN:40% MA (mol:mol) ratio were prepared using montmorillonite clay modified via adsorption, using 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), via in-situ intercalation polymerization. The poly(AN-co-MA)/clay nanocomposites with different clay loadings showed no difference in morphology. They exhibited improved thermomechanical properties and higher thermal stability than the neat copolymers. The melt rheology results of these nanocomposites showed an improved storage modulus as well as increased shear thinning behaviour with increasing clay content. However, the nanocomposites exhibited long-time relaxation behaviour and their chemical structures evolved during analysis. This was attributed to cyclisation reactions taking place at the temperature used during the oscillatory tests. The sorption isotherms of water vapour in these nanocomposites followed a dualmode sorption behaviour (BET type II mode). Hysteresis was observed in sorption/desorption isotherms of these nanocomposites. The equilibrium water uptake was higher in the nanocomposites compared to the neat copolymers, and it increased with increasing clay content, especially at high water activities (0.8). Although diffusion and permeability decreased with increasing clay content the solubility increased due to the hydrophilic nature of the clay. Despite the decrease in diffusion and permeability parameters the free volume hole radius of the nanocomposites remained constant, but a slight decrease in free volume hole number was observed. / AFRIKAANSE OPSOMMING: Die bereiding van poli(akrilonitriel/metielakrilaat) [poli(AN-ko-MA)] kopolimere en poli(AN-ko-MA)/klei nanosamestellings deur middel van emulsiepolimerisasie, hul karakterisering asook die ooreenkoms tussen hul molekulêre strukture en fisiese eienskappe is beskryf. Die kopolimeersamestelling is gevarieer, en eienskappe is geanaliseer en dan gekorreleer met die kopolimeersamestelling. Die vrye-volume eienskappe van die kopolimeer was afhanklik van die glasoorgangstemperatuur (Tg) wat weer afhanklik is van die kopolimeersamestealling. Die kristalliniteit van die kopolimeer het verminder met die hoeveelheid MA teenwoordig. Die afname in kristalliniteit en toename in beide die o-Ps leeftyd en o-Ps intensiteit met afname in Tg is veroorsaak deur die beter kettingbeweegbaarheid wat veroorsaak is deur die byvoeging van metielakrilaat. Die poli(akrilonitriel-ko-metielakrilaat)/klei nanosamestellings met 60% AN:40% MA (mol:mol) verhouding is berei deur die gebruik van montmorillonietklei, gemodifiseer deur die adsorpsie van 2-akrielamido-2-metiel-1-propaansulfoonsuur (AMPS) deur middel van 'n in-situ interkaleringspolimerisasie. Die poli(AN-ko-MA)/klei nanosamestellings het, ten spyte van die verskillende hoeveelhede klei wat gebruik is, geen verandering in morfologie getoon nie. Hulle het wel beter termodinamiese eienskappe en hoër termiese stabiliteit as die oorspronklike kopolimere getoon. Die smeltreologie resultate van hierdie nanosamestellings het ‘n beter stoormodulus getoon, sowel as toenemende skuifverdunningsgedrag met 'n verhoogde klei inhoud. Tog het die nanosamestellings lang tyd-ontspanningsgedrag getoon en die chemiese struktuur het verander tydens analise. Dit word toegeskryf aan die sikliese reaksies wat plaasvind by die temperatuur wat gebruik is tydens die ossillatoriese toetse. Die sorpsie isoterme van waterdamp in hierdie nanosamestellings het ‘n dubbel-styl sorpsiegedrag gevolg (BET tipe II styl). Histerese is waargeneem in sorpsie/desorpsie isoterme van hierdie nanosamestellings. Die ewewig in wateropname van die nanosamestellings was hoër as vir dié van die oorspronklike kopolimere en dit het toegeneem met 'n toenemende klei inhoud, veral by hoë humiditeit (0.8). Al het die diffusie en deurlaatbaarheid afgeneem met 'n toename in die klei inhoud, het die oplosbaarheid toegeneem as gevolg van die hidrofiliese karakter van die klei. Ten spyte van die afname in diffusie en deurlaatbaarheidsparameters, het die radius van die vryevolume openinge van die nanosamestellings konstant gebly, maar ‘n klein afname in die aantal vrye-volume openinge is gevind.