Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008. / The Reversible addition fragmentation chain transfer (RAFT) technique is a robust and versatile technique that enables the synthesis of polymers of controlled molecular weight and polydispersity. The application of the RAFT technique in heterogeneous aqueous media has attracted great interest in academics and industry due to it being more environmentally friendly, besides its other advantages. To date, the synthesis of well-defined high molecular weight polymers via the RAFT process under industrially relevant conditions still remains a challenge for polymer chemists. The study addresses the application of the RAFT process in heterogeneous media, namely in miniemulsion polymerization, for the synthesis of AB diblock copolymers of n-butyl methacrylate and styrene. AB diblock copolymers of high molecular weight were successfully prepared via a twostep method. In the first step, a dithiobenzoate monofunctional RAFT agent was used in bulk polymerization with the first monomer, n-butyl methacrylate. After the polymerization, the majority of the polymer chains contained the thiocarbonyl-thio RAFT agent functionality, which makes the chains potentially active for chain extension. The polymeric RAFT agent (also referred to as the starting block) obtained in the first step was chain extended in the second step, in miniemulsion, upon further addition of fresh initiator and the second monomer, styrene. The effects of the initiator/RAFT agent concentration ratio on the miniemulsion systems were investigated. The miniemulsion systems used for the high molecular weight AB diblock copolymers exhibited living features despite the high polydispersity indices. Kinetic results showed an increase in the rate of polymerization throughout the polymerization. Size exclusion chromatography (SEC) results indicated significant broadening in the molecular weight distributions and a steep increase in the polydispersity during the polymerization. It was concluded that the broad molecular weight distributions and steep increase in the polydispersity was not only related to the initiator concentration but possibly due to other factors such as inhomogeneity in the miniemulsion system and a transition in the kinetic behavior during the polymerization. Secondary particle formation emerged from kinetic data and transmission electron microscopy (TEM) results, but this were not supported by the SEC results. The effect of the use of a water-soluble initiator on the miniemulsion system was also investigated. Results indicated a similar behavioral pattern as observed in the AIBNinitiated systems, and not much improvement in terms of the molecular weight distributions and polydispersity was seen. The effect of the molecular weight of the diblock copolymers on the miniemulsion system was investigated. Poly(n-butyl methacrylate)-b-poly(styrene) diblock copolymers of lower molecular weight were synthesized via the two-step process. Kinetic results indicated a similar behavioral trend as to that of the high molecular weight diblock copolymers synthesized, however SEC chromatograms showed narrower molecular weight distributions and low polydispersity indices.

Thesis (DSc (Chemistry and Polymer Science))--University of Stellenbsoch, 2006. / The synthesis and characterization of a new tertiary alcohol (2-octyl-2-dodecanol) and “bushy-tailed”, hydrophobic acrylic monomer (2-octyl-dodecyl acrylate) from a 1-decene dimer (2-octyl-1-dodecene) precursor that was synthesized with metallocene technology is reported. Some preliminary applications of the newly synthesized 2-octyl-dodecyl acrylate were investigated. These applications included the use of 2-octyl-dodecyl acrylate as a reactive hydrophobe in mini-emulsion polymerizations, and as a reactive (internal) plasticizer. In an attempt to selectively dimerize 1-decene, the effect of various factors on the oligomerization of 1-decene was investigated. These factors include the following: i. Different temperatures: 5, 35, 70 and 90°C ii. Different co-catalyst [methylaluminoxane (MAO)] concentrations iii. Different catalysts: bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2) and bis(cyclopentadienyl)hafnium dichloride (Cp2HfCl2) iv. Different reaction times. In all instances the final product obtained, under the abovementioned conditions, was a mixture of residual monomer, the dimer and trimer of 1-decene. These findings were corroborated with GC-MS and 1H-NMR spectroscopy. The isolation and further processing of the dimer of 1-decene (2-octyl-1-dodecene) was investigated. The efficiency, in terms of the final product-composition for the amount of catalyst used and reaction time, of Cp2ZrCl2 compared to bis(cyclopentadienyl)hafnium dichloride (Cp2HfCl2; hafnocene) as catalyst for the oligomerization of 1-decene is also reported on. The results obtained indicated that Cp2ZrCl2 is the more efficient catalyst for the oligomerization of 1-decene. The effect of different reaction times (1, 3, 6, 24 hours) on the final product-composition for the oligomerization of 1-decene was also investigated. Longer reaction times (24 hours) seemed to be excessive. A reaction time of 6 hours was optimal. The purified 1-decene dimer (2-octyl-1-dodecene) was converted to the new tertiary alcohol (2-octyl-2-dodecanol) using the oxymercuration-demercuration procedure. The 2-octyl-dodecyl acrylate was synthesized by the esterification of the tertiary alcohol with acryloyl chloride in the presence of triethylamine. The new tertiary alcohol and acrylate were characterized by FT-IR and 1H-NMR spectroscopy. Stable polymer latex particles were successfully synthesized with the novel reactive hydrophobe 2-octyl-dodecyl acrylate in the mini-emulsion polymerization of butyl acrylate, methyl methacrylate and styrene. Phase-separation experiments showed that the presence of 2-octyl-dodecyl acrylate in the dispersed phase retards Ostwald ripening. The novel acrylic monomer, 2-octyl-dodecyl acrylate, was copolymerized with styrene via conventional free radical polymerization. Both low and high molecular weight copolymers were prepared. Thermal analysis of the copolymers showed that 2-octyl-dodecyl acrylate does act as a reactive (internal) plasticizer. Blends of commercial virgin polystyrene and the synthesized low and high molecular weight copolymers were prepared. Partially miscible blends were obtained. Decreases in the glass transition temperatures of the blends compared to the virgin polystyrene were observed. The higher molecular mass styrene/2-octyl-dodecyl acrylate copolymers produced larger decreases in glass-transition temperatures.

Thesis (DSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Commercial polyolefins degrade under the influence of light, heat, chemical and mechanical factors. They are therefore stabilised to ensure that they maintain performance characteristics during their service life. Degradation results in changes in the molar mass, molar mass distribution, chemical composition and chemical composition distribution. Classical analytical techniques only provide averaged values of these properties. Much information is available in the open literature on the changes in molar mass, molar mass distribution and chemical composition of polypropylene upon degradation, but no information was available on the changes in chemical composition distribution (CCD) during degradation. This study describes the use of the following analytical techniques to study this: temperature rising elution fractionation (TREF), crystallisation analysis fractionation (CRYSTAF) and coupled size exclusion chromatography-Fourier transform infrared analysis (SEC-FTIR). The CRYSTAF results complimented those obtained by classical techniques: there was a broadening of the crystallisation peak (CCD), an increase in the soluble fraction and a decrease in crystallisation temperatures. SEC-FTIR analysis showed that most of the degraded products were concentrated in the low molar mass regions. TREF analysis was used to separate a degraded sample into fractions of different degrees of degradation. It was then possible to study the spatial heterogeneity in a thick, degraded polypropylene sample using SEC, FTIR and CRYSTAF. The degradation behaviour of selected Sasol propylene-1-pentene random copolymers was investigated. CRYSTAF, SEC-FTIR and TREF analyses provided information on the thermo-oxidative degradation behaviour differences between unstabilised polypropylene homopolymers and these propylene-1-pentene copolymers. It was found that the pentene copolymers degraded significantly faster compared to the homopolymers, even at low levels of pentene (< 3%). The reduction in stability was virtually linear with an increase in pentene content (up to 8 mol% pentene), indicating that higher levels of primary stabilisers are needed to ensure similar life spans for the Sasol propylene-1-pentene copolymers. The extrusion stability of the propylene-1-pentene copolymers was, however, similar to that of the polypropylene homopolymers, indicating that similar processing stabiliser packages may be used.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Propylene/1-pentene random copolymers are a relatively new family of random copolymers being prepared by Sasol Polymers and reveals high impact strength, good tensile properties, excellent optical properties, good rheological properties and a large pool of processing possibilities. These commercial copolymers are being prepared with stereospecific heterogeneous Ziegler-Natta catalytic systems containing multiple active sites and therefore producing copolymers with a varying degree of stereoregularity. Two different groups of propylene/1-pentene random copolymers were received by Sasol Polymers and investigated in this project. The first group (Group 1, Polymers A - F) consisted of six totally different batches of commercial propylene/1-pentene copolymers which were produced by different catalyst systems. All had different melt flow indices (MFIs) and different 1-pentene contents and all of the copolymers, except for one, were nucleated. The second group (Group 2, Polymers G - J) were produced by the same catalyst, but with varying donor:catalyst ratios and also differing in their 1-pentene content. Investigation of the Group 1 copolymers was used in order to construct a “molecular toolbox” which was then used to study the Group 2 copolymers. The original commercial copolymers were all studied by various analytical techniques: high-temperature carbon thirteen nuclear magnetic resonance spectroscopy (13C-NMR), high-temperature gel permeation chromatoghraphy (HT-GPC), crystallization analysis fractionation (CRYSTAF), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and positron annihilation lifetime spectroscopy (PALS). The random copolymers were all fractionated by preparative TREF and the fractions analyzed utilizing the following analytical techniques: 13C-NMR, HT-GPC, CRYSTAF and DSC. The results of these analyses were used to investigate inter alia the distribution of 1-pentene in the copolymers. In order to investigate the low molecular weight material of the copolymers, which were part of the room temperature fraction during TREF, solvent extractions were carried out using different solvents and different extraction techniques. A complete structural analysis study was carried out on the extracts. The percentages of xylene-solubles were also determined during the quantitative xylene extraction study of the copolymers. Characterization of the xylene non-soluble material was carried out using 13C-NMR, HT-GPC, CRYSTAF, DSC and WAXD in order to compare the properties of the unextracted copolymers with the material after removal of the xylene soluble fraction. Positron annihilation lifetime spectroscopy (PALS) was used as an alternative investigation method for the Group 1 copolymers and their XNS fractions in order to determine what type of information this novel analytical method could generate and how the results compared with those of previous PALS studies on poly-olefins. A new fractionation technique, preparative solution fractionation (SF), was developed and evaluated. The commercial propylene/1-pentene copolymers were fractionated using this novel technique, the fractions were analyzed by 13C-NMR, HT-GPC, CRYSTAF and DSC and the results were compared with previously existing fractionation methods, namely TREF and CRYSTAF. A final study was done on the random copolymers by blending one of the commercial Ziegler-Natta catalyzed propylene/1-pentene copolymers with a tailored, low 1-pentene content, metallocene propylene/1-pentene copolymer in different ratios. The blends were analyzed by molecular weight, thermal and crystal phase analysis in order to investigate the effect of the tailored, highly isotactic propylene/1-pentene copolymer on the properties the commercial random copolymers. Throughout the project the influence of the 1-pentene as well as the donor:catalyst ratio on the copolymers was investigated. This study, in its entirety, therefore allow a better understanding of the effects that the commercial, heterogeneous, transition metal catalysts have on the make up of the copolymers and, by extension, the ultimate properties of the materials.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009 / Polypropylene is an extremely versatile material and has a broad spectrum of applications due to the variations in properties which are possible with this material. The variations in the properties of the material are governed by the microstructure of the chains constituting the polymer. The microstructure varies according to the production methods, i.e. the polymerisation conditions. Varying the manner in which the polymer is produced therefore changes the properties of the material allowing the polymers’ use for different applications. The most important factor affecting the way in which the polymers are produced is the nature of the active sites on the catalyst. Changing the chemical environment of the active sites changes the way in which the polymerisation is controlled and greatly affects the types of chains produced and thus polymer properties. The study examines the structure-property relationships of polyolefins with specific focus on the polypropylene homopolymer. The temperature rising elution fractionation (TREF) technique is used extensively in order to isolate specific fractions of the polymer. The importance of specific TREF fractions is investigated via a two pronged investigative methodology. On the one hand specific TREF fractions are removed from a sample, allowing the analysis of the properties of the material without that specific fraction, thereby revealing the influence which the fraction in question has on the properties. The other branch of the study investigates the chemical modification of the active sites of a Ziegler-Natta catalyst so as to be able to modify the properties of the polymer in the reactor, in a similar manner to physically removing fractions. The techniques are related and it was discovered that the amount of the fractions of the polymer, found to be important using the one technique, also turned out to be important using the other method. Initial method development work utilised a polypropylene-1-pentene copolymer since the molecular heterogeneity of this material is such that large differences are observed upon removal of fractions. The technique was then applied to a Ziegler-Natta catalysed polypropylene homopolymer. Each TREF fraction is successively removed and the residual material analysed. Specific TREF fractions were found to play a significant role in determining the polymer properties since there was a drastic reduction in properties upon removal of these fractions. The polymerisation of propylene was also performed at a variety of conditions in order to investigate different ways in which the catalyst system could be modified. Specific reaction conditions were chosen for in-depth analysis and structure-property correlation. The chemical modification of the active sites was accomplished via the introduction of an external Lewis base (electron donor) to the polymerisation system, and also by varying the external donor/catalyst ratio used. Two different external donors were used during the study namely Diphenyl-dimethoxysilane (DPDMS) and methyl-phenyl-dimethoxysilane (MPDMS). It is observed that there are definite links between the amounts of specific fractions present in the polymer and the polymer properties, as observed via both the physical removal of fractions and the chemical modification of active sites.

Thesis (PhD)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: From the Sasol Fischer- Tropsch process, a variety of different a-olefins are produced. Sasol recently started presenting these a-olefins to polymer producers. To demonstrate the application possibilities of these a-olefins as comonomers for ethylene and propylene polymerization, it was necessary to first synthesize catalysts having a combination of high activity and good comonomer incorporation, and in the case of propylene copolymers, also sufficient stereospecificities. Different methods to produce catalysts conforming to these requirements were investigated and it was found that catalysts produced from a MgCb-support activated by a combination of chemical and mechanical means produced suitable catalysts. The amount of alcohol used during the support activation step and the time allowed for alkylation of the active centers were important. No clear correlation between total titanium content and activity was observed. The degree to which active sites are protected was evaluated from the amount of comonomer present in the final copolymer based on the amount added to the reaction. Cyclopentadiene was used to selectively deactivate the unprotected active sites to determine the ratio between protected and "open" active sites. High activity catalysts are not suitable for gas-phase copolymerization and were consequently "diluted" by dispersion in a pre-formed polymer powder and by prepolymerization. Catalyst activity based on titanium content was substantially decreased, but comonomer incorporation was not. Catalysts for producing crystalline polypropylene require the presence of both an internal and external electron donor. It was shown that isotacticity increased linearly with an increase in external modifier at the expense of catalyst activity and that a double treatment of the support or catalyst before the final TiCl4 fixation was more effective at increasing stereospecificity. The less stereospecific sites are more capable of accepting bulky comonomers in the coordination complex and thus by decreasing the amount of less-stereospecific active sites, the overall capability of the catalyst to incorporate comonomer was decreased. Comonomer sequence distributions and average lamellar thicknesses of different ethylene / a-olefin copolymers were calculated from CH2 dyad concentrations determined by I3C NMR spectroscopy. Ethylene sequences in the I-butene containing copolymers are generally longer than those where a higher a-olefin was used as comonomer which indicates that a more random comonomer distribution is obtained when the higher u-olefins are used. It was shown that an inverse relationship exists between branch size and density. For density, no effect resulting from the comonomer type was observed. This same inverse relationship was also observed for tensile strength. Modulus, hardness and impact strength, on the other hand, did show an effect resulting from the comonomer type. Modulus and hardness were not depressed as much and impact strength improved more than what was expected from calculations based on branch size. Homogeneous copolymers have broad melting peaks. It was shown that at sufficiently high comonomer content, peak broadening occurs when the higher cc-olefins are used as comonomer, which also indicates that more random comonomer distributions are obtained with the higher aolefins. From the chain propagation probabilities calculated it was observed that two types of active sites are present. Those responsible for producing mainly polyethylene have an alternating character while the sites capable of incorporating comonomer have a blocky character. It was expected that the additional introduction of a third a-olefin during ethylene / 1- pentene copolymerization will produce a terpolymer with density and related properties similar to the mathematical average between those of the relevant copolymers. This was only observed for the terpolymers containing l-heptene, 1- octene and l-nonene. The I-butene containing terpolymers have densities well below the expected values while the I-hexene containing terpolymers have values very similar to that of the ethylene / l-hexene copolymer densities, but still below the expected values. Properties related to density, such as tensile strength and modulus, follow this same trend. It is believed that the presence of l-pentene breaks up the tendency of the lower c-olefins to cluster which results in improved randomness. Compared to the copolymers, I-butene and l-hexene containing terpolymers seem to reach the impact strength maximum at a lower total comonomer content than that of the I-pentene copolymers which also indicates an enhanced effect from the combined use of I-pentene with these o-olefins. No substantial difference between impact strengths of co- and terpolymers prepared with higher a-olefins was observed. In general, the melting temperatures of the terpolymers are slightly lower and spread over a wider temperature range than those of the copolymers which can be realized if the comonomer units are less clustered and thus more randomly distributed. Decrease in melting temperature was, however, not as much as for the metallocene catalyzed terpolymers. From sequence length calculations from l3C NMR spectroscopy it was found that the crystallizable ethylene sequences of l-butene containing terpolymers were shorter than those of the corresponding copolymers, which confirms the notion that the introduction of a third comonomer resulted in an increase in randomness. Crystallizable sequence lengths became gradually shorter when higher cc-olefins were used in co- and terpolymers and those of the terpolymers are generally shorter. From the different types of active centers present on a Ziegler-Natta catalyst, it was reasoned that three main types of polymer chains can be present in the terpolymers: (a) ethylene homopolymer, (b) ethylene / lower a-olefin copolymer and (c) ethylene / lower a-olefin / higher a-olefin terpolymer. The ratio between these components in the final terpolymer depends primarily on the size of the higher a-olefin. The larger the third a-olefin becomes, the more active sites will reject it, resulting in a higher amount of ethylene / lower a-olefin copolymer. It was thus suggested that the large decrease in density and the associated change in related properties observed for ethylene / l-pentene / l-butene terpolymers can be related to the combined result of improved random comonomer incorporation together with the decrease in the amount of ethylene homopolymer. The possibilities of using the higher a-olefins having uneven carbon numbers were investigated in random propylene copolymers. Similar to that observed for the ethylene copolymers, less of the higher a-olefins was necessary to achieve a certain level of crystallinity. A good agreement was observed between tensile properties and comonomer type and content and the size of the branch and the resulting defect it causes in the crystal structure is the primary factor affecting tensile strength. For impact strength a close correlation between the size of the comonomer side chain and comonomer content was observed. It was shown that the effect of the heptyl branch derived from a l-nonene unit was 2.3 times that of the propyl group derived from the I-pentene unit. Properties of block copolymers can not be related directly to l-pentene content as is the case with random copolymers, mainly due to the heterogeneity of the block copolymers. The activating effect of hydrogen on catalyst activity was observed. It was also observed that the amount of l-pentene incorporated in the copolymer as well as the copolymer yield were higher in the presence of hydrogen than when the reaction was carried out in the absence of hydrogen. By using DSC it was possible to identify different crystalline phases in the propylene / I-pentene block copolymers due to the differences in their crystallization kinetics. A connection between the low-temperature peak and impact strength was observed. It was found that the presence of the low-temperature peak resulting from thin lamellae formed by chain containing many defects was undesirable when high impact strength is required. It was not possible to quantify the extent to which the intensity of this peak affected mechanical properties of the block copolymers. However, from sequence length calculations it was found that the ratio between the propylene and 1- pentene sequence lengths could be related quantitatively to impact strength, modulus, hardness and tensile strength of the polymers investigated. / AFRIKAANSE OPSOMMING: 'n Verskeidenheid van verskillende «-olefiene word in die Sasol Fischer- Tropsch proses vervaardig. Sasol het onlangs begin om hierdie a-olefiene aan polimeervervaardigers te bied. Om die toepassingsmoontlikhede van hierdie aolefiene as komonomere vir etileen en propileen polimerisasie te demonstreer was dit nodig om eerstens 'n katalis met 'n kombinasie van hoë aktiwiteit en goeie komonomeer invoeging te sintetiseer. In die geval van propileen word voldoende stereospesifisiteit ook vereis. Verskillende metodes om kataliste wat aan hierdie vereistes voldoen te vervaardig is ondersoek. Daar is gevind dat kataliste waarvan die MgCb basis deur 'n kombinasie van chemiese- en meganiese metodes geaktiveer is, die vereiste eienskappe besit. Die hoeveelheid alkohol gebruik tydens die basis aktivering stap en die tyd toegelaat vir die alkilering van die aktiewe spesies was belangrik. Geen duidelike verband tussen totale titaan inhoud en aktiwiteit is waargeneem nie. Die mate waartoe aktiewe spesies beskerm is, is bepaal vanaf die hoeveelheid komonomeer teenwoordig in die finale kopolimeer in verhouding met die hoeveelheid bygevoeg tydens die reaksie. Siklopentadieen is gebruik om onbeskermde aktiewe spesies selektief te deaktiveer om die verhouding tussen beskermde en oop aktiewe spesies te bepaal. Hoëaktiwiteit kataliste is nie geskik vir gasfase kopolimerisasie nie en is gevolglik verdun deur dit te versprei in 'n voorafgevormde polimeer poeier en deur prepolimerisasie. Katalis aktiwiteit gebaseer op titaan inhoud was aansienlik laer maar komonomeer invoeging was nie merkbaar beinvloed nie. Kataliste VIr die vervaardiging van kristallyne polipropileen vereis die teenwoordigheid van beide interne- en eksterne elektron donors. Daar is gewys dat isotaktisiteit liniêr verhoog met 'n toename in eksterne modifiseerder ten koste van katalis aktiwiteit en dat 'n dubbele behandeling van die basis of katalis, voor die finale titaan fiksering, meer effektief was om stereospesifisiteit te verhoog. Die spesies met laer stereospesifisiteit is meer bevoeg om bonkige komonomere in die koërdinasie kompleks toe te laat en deur dus die konsentrasie van hierdie spesies te verlaag is die bevoegdheid van die katalis om bonkige komonomeer te inkorporeer, verlaag. Komonomeer reeksverspreiding en gemiddelde lamellêre dikte van verskillende etileen / o-olefien kopolimere is bereken vanaf CH2 diad konsentrasie bepaal deur KMR spektroskopie. Etileen reekse in die kopolimere wat l-buteen bevat is oor die algemeen langer as dié waarin 'n hoër a-olefien as komonomeer gebruik was, wat aandui dat 'n meer egalige komonomeer verspreiding verkry word as hoër «-olefiene gebruik word. Daar is getoon dat 'n inverse verhouding tussen die grootte van die vertakking en digtheid bestaan. Geen effek komende van die komonomeer tipe kon waargeneem word nie. Hierdie soortgelyke inverse verhouding was ook waargeneem vir treksterkte. Modulus, hardheid en impaksterkte aan die ander kant, hét 'n effek komende van die komonomeer tipe getoon. Modulus en hardheid was nie soveel verlaag, en impak sterkte soveel verhoog as wat verwag is vanaf berekeninge gebaseer op vertakking grootte nie. Homogene kopolimere toon breë smeltpieke. Daar is gewys dat by voldoende komonomeer inhoud 'n verbreding van die pieke voorgekom het wanneer hoër a-olefiene as komonomere gebruik is, wat ook aandui dat 'n meer egalige komonomeer verspreiding met hierdie c-olefiene verkry kan word. Vanaf berekening van die ketting voortplantingsmoontlikhede is waargeneem dat twee tipes aktiewe spesies teenwoordig is. Die verantwoordelik vir die vorming van polietileen het 'n alternerende karakter terwyl die sentra wat komonomeer kan inkorporeer 'n blokagtige karakter het. Daar is verwag dat die addisionele byvoeging van 'n derde o.-olefien tydens etileen / I-penteen kopolimerisasie, 'n terpolimeer met digtheid en verwante eienskappe soortgelyk aan die wiskundige gemiddelde tussen dié van die relevante kopolimere tot gevolg sal hê. Dit was egter slegs waargeneem vir terpolimere wat I-hepteen 1- okteen en l-noneen bevat. Die I-buteen bevattende terpolimere het digthede ver onder die verwagte waardes terwyl die I-hekseen bevattende terpolimere waardes soortgelyk aan die etileen / l-hekseen kopolimeer digthede het' wat steeds onder die verwagte waardes is. Eienskappe verwant aan digtheid, soos treksterkte en modulus, volg dieselfde neiging. Dit word geglo dat die teenwoordigheid van l-penteen die neiging van die laer a-olefiene om saam te bondelopbreek wat 'n verbeterde egaligheid in komonomeerverspreiding tot gevolg het. Vergeleke by die kopolimere blyk dit dat die terpolimere wat l-buteen en I-hekseen bevat, die impaksterkte maksimum by 'n laer totale komonomer inhoud bereik as dié van die 1-penteen polimere. Dit dui ook op 'n verbeterde effek as gevolg van die gekombineerde gebruik van l-penteen met ander a-olefiene. Geen duidelike verskil tussen die impaksterktes van ko- en terpolimere, wat met die hoër a-olefiene berei was, is waargeneem me. In die algemeen is die smeltingstemperature van die terpolimere effens laer, en versprei oor 'n wyer temperatuurgebied as dié van die kopolimere wat verklaar kan word as komonomere minder saamgebondel is en dus meer homogeen versprei is. Die afname in smelt temperatuur was egter nie soveel as dié van die metalloseengekataliseerde terpolimere nie. Vanaf reekslengte berekeninge met behulp van KMR spektroskopie is daar gevind dat die kristalliseerbare etileen reekse van die l-buteen bevattende terpolimere korter was as dié van die ooreenkomstige kopolimere, wat die gevoel dat die byvoeging van 'n derde komonomeer 'n verbeterde komonomeerverspreiding tot gevolg het, bevestig. Vanaf die verskillende aktiewe spesies teenwoordig in 'n Ziegler-Natta katalis is daar geredeneer dat drie hooftipes polimeerkettings in die terpolimere teenwoordig kan wees: (a) etileen hompolimeer, (b) etileen / laer a-olefien kopolimeer en (c) etileen / laer a-olefien / hoër a-olefien terpolimeer. Die verhouding tussen hierdie komponente in die finale terpolimeer hang primêr van die grootte van die hoër aolefien af. Hoe groter die derde a-olefien is, deur hoe meer van die aktiewe spesies sal dit verwerp word wat 'n groter hoeveelheid etileen / laer a-olefien kopolimeer tot gevolg sal hê. Daar word dus voorgestel dat die groot afname in digtheid en die geassosieerde veranderings in die toepaslike eiensappe waargeneem vir etileen / 1- penteen / I-buteen terpolimeere, herlei kan word na die gekombineerde effek van verbeterde komonomeerverspreiding tesame met die afname lil die hoeveelheid etileen homopolimeer. Die moontlikheid om hoër cc-olefiene met onewe koolstofgetalle te gebruik in homogene propileen kopolimere is ondersoek. Soortgelyk aan dit wat waargeneem is vir die etileen kopolimere, was minder van die hoër cc-olefiene nodig om 'n spesifieke vlak van kristalliniteit te bereik. 'n Goeie ooreenkoms tussen trek-eienskappe en . komonomeer tipe- en inhoud is waargeneem en die grootte van die vertakking en die gevolglike defek wat dit veroorsaak in die kristal struktuur is die primêre faktor wat treksterkte beinvloed. Vir impaksterkte is 'n noue verband tusssen die grootte van die vertakking en komonomeer inhoud waargeneem. Daar is aangetoon dat die effek van die heptiel vertakking vanf die l-noneen eenheid 2.3 keer dié van die propiel groep van die l-penteen eenheid is. Eienskappe van blok kopolimere kan nie direk na l-penteen inhoud herlei word soos die geval met die homogene kopolimere was nie, hoofsaaklik as gevolg van die heterogeniteit van die blok kopolimere. Die aktiverende effek van waterstof op katalis aktiwiteit is waargeneem. Daar is ook gesien dat die hoeveelheid l-penteen geïnkorporeer in die kopolimeer, sowel as die kopolimeer opbrengs, hoër was in die teenwoordigheid van waterstof as wanneer die reaksie sonder waterstof uitgevoer is. Deur DSC te gebruik was dit moontlik om verskillende kristallyne fases in die propileen / l-penteen blok kopolimere vanaf die verskille in hulle krisallisasie kinetika, te identifiseer. 'n Verbintenis tussen die lae-temperatuur piek en impaksterkte is waargeneem. Daar is gevind dat die teenwoordigheid van die laetemperatuur piek, komende van die dun lamellas gevorm, deur kettings wat baie defekte bevat, ongewens is wanneer hoë impaksterkte vereis word. Dit was nie moontlik om die bereik waartoe die intensiteit van hierdie piek die meganiese eienskappe van die blok kopolimere affekteer, te kwantifiseer nie. Vanaf reekslengte bepalings is daar gevind dat die verhouding tussen die propileen en I-penteen reekslengtes kwantitiatief herlei kan word na impaksterkte, modulus, hardheid en treksterkte van die ondersoekte polimere.

Thesis (PhD)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: The study focused on the analysis of a variety o f synthesised tailored copolymers. During the investigation o f the samples new and innovative analytical techniques were developed to be able to identify the presence of certain predicted or expected copolymerisation products. Emphasis was placed on the versatility of CRYSTAF as a method for the analysis of semi-crystalline copolymers. Changes in the crystallisation temperature were used as an indicator, while the type o f method, solvent and sample weight served as variables in the system. The percentage comonomer content distribution for an unknown sample was determined from the standard curve plotted with the aid o f copolymers with known comonomer content. Ethylene/higher a-olefin and propylene/higher a-olefm copolymers were synthesised by means o f a metallocene precatalyst. In both cases, NMR spectroscopy, DSC, GPC, and CRYSTAF were used as analytical tools. In the ethylene series it was shown that the sample mixture was homogenous in the molar mass axis (GPC) but not in the chemical composition axis (CRYSTAF) regarding the comonomer content. For the propylene series, an increase in stereoerrors was observed by NMR and this was correlated with crystallisation on heating a DSC for the range o f copolymers. In the case where ethylene/methyl methacrylate block copolymers were synthesised using metallocene precatalyst, novel detection and separation methods were used and developed. This included the use o f CRYSTAF fitted with a carbonyl filter, high temperature gradient HPLC and high temperature liquid chromatography under critical conditions (LCCC). The last two techniques were the first where separation could be achieved with samples only dissolving at high temperature. All previous mentioned techniques, as well as the coupling of FTIR to GPC and high temperature gradient HPLC via LC-Transform revealed that the samples consisted o f varying ethylene and MMA block lengths. / AFRIKAANSE OPSOMMING: Die doelstelling van die navorsing was die analise van spesiaalvervaardigde kopolimere. Nuwe analitiese tegnieke is vir die bevestiging van sekere voorgestelde kopolimerisasie-produkte ontwikkel. Klem is gelê op die veelsydigheid van CRYSTAF as ’n metode vir die analise van gedeeltelik-kristallyne kopolimere. Veranderinge in die kristallisasie-temperature is as respons gebruik, terwyl die metode van sintese, die oplosmiddel en die hoeveelheid monster as veranderlikes in die sisteem beskou is. ‘n Standaardkurwe vir komonomeerinhoud is opgestel met behulp van kopolimere met ‘n bekende komonomeerinhoud. Hierdie kurwe is gebruik om die komonomeerinhoudsverspreiding van onbekende monsters te bepaal. Etileen/hoër a-olefien- en propileen/hoër a-olefien-kopolimere is met behulp van ‘n metalloseen pre-katalis gesintetiseer. In beide gevalle is KMR spektroskopie, DSC, GPC en CRYSTAF gebruik om die analises uit te uitvoer. Met verwysing na komonomeerinhoud is daar in die geval van die etileenreeks bevind dat die monstermengsel homogeen is met betrekking tot die molere massa, maar nie met betrekking tot die chemiese samestelling nie. Vir die propileenreeks is ’n verhoging in die stereofoute met behulp van KMR waargeneem. Dit is gekorrelleer met kristallisasie weens verhitting tydens DSC-bepalings vir die reeks kopolimere. In die geval van die sinteses van etileen/metielmetakrilaat-blokkopolimere met metalloseen as pre-katalis, moes nuwe waamemings- en skeidingstegnieke ontwikkel word. Dit het die gebruik van CRYSTAF met ’n karbonielfilter, hoetemperatuurgradient- HPLC en hoë-temperatuurvloeistofchromatografie onder kritiese toestande ingesluit. Laasgenoemde twee tegnieke het vir die eerste keer skeiding van monsters wat net by hoe temperature oplos, moontlik gemaak. Bogenoemde tegnieke, sowel as die koppeling van FTIR met GPC en hoë-temperatuur-gradient-HPLC via LC-transformasie het getoon dat die monsters etileen- en MMA-blokke met verskillende lengtes bevat het.

Thesis (PhD)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Most polypropylene copolymers commercially available have ethylene, and to a lesser degree t-butene as comonomers. Commercially available higher a-olefins, mostly even-numbered, are seldom used for the production of pp copolymers, probably due to cost. Sasol's Fischer- Tropsch oil-from-coal process produces many linear and branched a-olefins as by-products that can be isolated and purified by a relatively cheap refinery process, including the odd-numbered 1- pentene olefin. Sasol's gas-phase Novolen pp plant at Secunda, South Africa is ideally suited to the manufacture of high quality pp random copolymers. As such an opportunity was identified to research the use of higher a-olefins, and more specifically 1-pentene, in the gas-phase production of pp random copolymers. Different methods to produce propylene / 1-pentene random copolymers in the slurry phase on bench-scale were investigated. A procedure was subsequently developed to produce propylene / 1-pentene random copolymers in the gas-phase in 10 litre autoclaves. It was found that commercially available fourth generation supported catalysts successfully incorporated the bulky 1-pentene monomer into the propylene backbone, both during slurry and gas-phase polymerisations. Software modelling was employed to determine the dew points of selected gas mixtures typically found during the production of pp random copolymers. The results indicated that typical process conditions could be employed during the gas-phase polymerisation of propylene and 1-pentene without the risk of condensation taking place inside the reactor. Propylene / 1-pentene random copolymers were subsequently successfully produced on the 800 litre BASF pilot plant in Germany followed by the first commercial production of the copolymer on Sasol's 50m3 Novolen gas-phase plant at Secunda. Using commercially available software the impact of introducing 1-pentene as comonomer during the production of random copolymers on the condenser cooling capacity was evaluated. Feasible and safe plant operating conditions were established for the production of propylene / 1-pentene random copolymers. The relationship between operating pressure and powder morphology was investigated to optimise process conditions. Operating at higher pressure in the gas-phase increases the monomer concentration in the reactor and as such improves the space/time/yield ratio of the 50m3 reactors. It was shown that higher operating pressures could be employed through the introduction of 1-pentene as comonomer during the production of PP random copolymer. The dramatic increase in catalyst productivity observed during the 800 litre pilot plant trials, up to a comonomer ratio of about 5%, supported the results obtained from a kinetic study carried out in bench-scale autoclaves. A comprehensive study was undertaken to compare the rheological, thermal, crystallisation, physical and mechanical properties of propylene / 1-pentene random copolymers with those of commercially available pp random copolymers. A series of propylene homo- and random copolymers with 1-pentene and ethylene as comonomers respectively, was prepared. NMR and IR techniques were developed to facilitate the determination of copolymer composition for the new family of 1-pentene random copolymers. The effect of comonomer content, molecular weight and temperature on the properties of the series of polymers was investigated. The propylene / 1-pentene random copolymers show unique rheological behaviour associated with the short propyl branches in the polymer backbone with minimum zero shear viscosity at about 2% 1-pentene content. The effect of molecular structure changes with comonomer content were analysed by the calculation of square average end-toend distance, packing length, tube diameter, molecular mass between entanglements and critical molecular mass. The viscosity of the 1-pentene random copolymers shows higher shear and temperature sensitivity compared to propylene homo- and ethylene random copolymers. The thermodynamic melting point of the propylene / 1-pentene random copolymers showed a significant decrease with increasing comonomer content in the 0 to 5% range. A wider melting range and higher peak melting point depression rate was observed compared to ethylene random copolymers at similar and increasing comonomer content measured on a weight % basis. It was found that the crystal structure of the propylene / 1-pentene random copolymers contains both the Q- and the y-modifications with the ratio of the respective crystal forms a function of both comonomer content and crystallisation temperature. The glass temperature decreased slightly with increasing comonomer (1-pentene) content. It is proposed that the short branch (propyl) "defects" in the polymer backbone are .incorporated into the crystal lattice resulting in increased rate of melting point depression with increasing (wt%) comonomer content compared to other random copolymers while maintaining relative high stiffness. The propylene / 1-pentene random copolymers exhibit the lowest haze values compared to all commercially available pp random copolymers at corresponding levels of comonomer content on a wt% basis. The stiffness to haze ratio of propylene / 1-pentene random copolymers are unique for all the members of the pp family. An inverse relationship between comonomer content and the measured tensile yield strength and modulus is observed. Application studies conducted on the propylene / 1-pentene random copolymers highlighted several interesting characteristics. Films produced from these copolymers exhibited very low haze and xylene soluble values while maintaining mechanical integrity. In the BOPP application the combination of processability and premium film properties presents a unique opportunity for the family of propylene / 1-pentene random copolymers. Blow moulding and injection moulding trials highlighted several advantages of product properties manufactured with propylene / 1-pentene random copolymers if compared to other commercially available random copolymers. The 1-pentene randoms presented lower in-mould as well as total shrinkage than ethylene based random copolymers. Stabilisation and nucleation studies conducted on the propylene / 1-pentene random copolymers showed that a typical combination antioxidant package and nucleating agent, at normal loading levels, could be used. In the larger pp random copolymer family 1-pentene imparts a better balance of properties than other comonomers. The combination of low melting point and xylene solubles with high stiffness and clarity is unique to propylene / 1-pentene random copolymers. / AFRIKAANSE OPSOMMING: Die oorgrote meerderheid van kommersieel beskikbare polipropileen (PP) kopolimere het etileen, en tot 'n mindere mate buteen, as komonomeer. Die relatief hoë koste van kommersieel beskikbare hoër alfa-olefiene is moontlik die rede waarom hulle selde gebruik word vir die vervaardiging van PP kopolimere. Die Sasol Fischer-Tropsch proses, waartydens olie uit steenkool vervaardig word, lewer verskeie liniêre en vertakte alfa-olefiene as neweprodukte wat geïsoleer en gesuiwer kan word in 'n relatiewe goedkoop rafineringsproses. Dit sluit ook die onewe-koolstofgetal 1-penteen-olefien in. Sasol se gasfase Novolen PP aanleg in Secunda, Suid-Afrika, is besonder geskik vir die vervaardiging van hoë standaard PP statistiese kopolimere. Voortvloeiend hieruit is die geleentheid geidentifiseer om die gebruik van hoër alfa-olefiene, en meer spesifiek 1-penteen, na te vors tydens die gasfaseproduksie van PP statistiese kopolimere. Verskeie metodes om propeleen / 1-penteen statistiese kopolimere in 'n koolwaterstofoplosmiddel op laboratoriumskaal te produseer, is ondersoek. 'n Prosedure is daarna ontwikkel om propileen / 1-penteen statistiese kopolimere ook in die gasfase te vervaardig in 10-liter drukvate. Die bevinding was dat kommersieel beskikbare vierde-generasie ondersteunde kataliste die swaarder 1-penteenmonomeer suksesvol geïnkorporeer het in die propileenketting tydens beide die koolwaterstof oplosmiddel- en gasfase polimerisasiereaksies. Rekenaargebaseerde modellering is gebruik om die kondensasiekondisies van tipiese gasmengsels, teenwoordig tydens die produksie van PP statistiese kopolimere, te bepaal. Die resultate het aangedui dat normale proseskondisies tydens die gasfasepolimerisasie van propileen en 1-penteengeen risiko van kondensasie in die reaktor inhou nie. Propileen / 1-penteen statistiese kopolimere is gevolglik met groot sukses vervaardig by die 800-liter BASF loodsaanleg in Duitsland, gevolg deur die eerste kommersiële vervaardiging van die kopolimeer op die Sasol50m3 Novolen gasfase-aanleg in Secunda. Deur gebruik te maak van kommersieel beskikbare sagteware, is die impak van 1-penteen as komonomeer tydens die vervaardiging van statistiese kopolimere op die verkoelingskapasiteit van die kondensator bepaal. Veilige en uitvoerbare aanlegkondisies is uitgestip vir die vervaardiging van propileen /1-penteen statistiese kopolimere. Die verhouding tussen die reaktordruk en poeiermorfologie is ondersoek om die prosestoestande te optimiseer. Vervaardiging van kopolimere in die gasfase by hoër drukke lei tot verhoogde monomeerkonsentrasie in die reaktor en gevolglik hoër produksiedeursette. Daar is bewys dat tydens die produksie van PP statistiese kopolimere, met 1-penteen as komonomeer, hoër reaktordruk ingespan kan word. Die dramatiese toename in katalisproduktiwiteit waargeneem tydens die 800- liter loodsaanleg proefloop, tot en met 'n komonomeer inhoud van ongeveer 5%, word ondersteun deur die resultate van 'n kinetiese studie uitgevoer in laboriumskaal drukvate. 'n Omvattende studie, om die reologiese, termiese, kristallyne, fisiese en meganiese eienskappe van propileen / 1-penteen statistiese kopolimere te vergelyk met kommersieel beskikbare PP statistiese kopolimere, is uitgevoer. 'n Reeks propileen homo- en statistiese kopolimere, met 1-penteen en etileen as komonomere onderskeidelik, is berei. KMR- en IR- tegnieke is ontwikkel om die bepaling van komonomeersamestelling vir die nuwe familie van 1- penteen statistiese kopolimere te fasiliteer. Die invloed van komonomeersamestelling, molekulere gewig en temperatuur op die eienskappe van die reeks polimere is ondersoek. Die propoleen / 1- penteen statistiese kopolimere toon unieke reologiese eienskappe wat geassosieer kan word met die propielsykettings in die polimeerruggraat. Die viskositeit van die propileen / 1-penteen statistiese kopolimere toon 'n hoër wrywings- en temperatuursensitiwiteit in vergelyking met propileen homo- en etileen statistiese kopolimere. 'n Drastiese verlaging in die termodinamiese smeltpunt van die propileen / 1- penteen statistiese kopolimere met 'n toename in komonomeerinhoud is waargeneem tot en met 'n 5% komonomeerinhoud. Die propileen / 1-penteen statistiese kopolimere toon 'n breër smeltgebied en 'n hoër tempo in die piek smeltpuntafname in vergelyking met etileen statistiese kopolimere met soortgelyke komonomeer inhoud, gemeet op 'n massabasis. Daar is bewys dat die kristalstruktuur van die propileen / 1-penteen statistiese kopolimere beide die alfa en gamma modifikasies bevat. Die verhouding van die onderskeie kristalvorms is 'n funksie van komonomeerinhoud en kristalisasietemperatuur. 'n Afname in die glastemperatuur met verhoogde komonomeer inhoud is waargeneem. Die aanname dat die kort propielsykettings in die polimeerruggraat in die kristalstruktuur geïnkorporeer word, is gemaak. Dit verklaar die hoë afname in die tempo van die smeltpunt met toenemende komonomeer inhoud relatief tot ander statistiese kopolimere, met die handhawing van hoë moduluswaardes. Die besondere deursigtigheid van die propileen / 1-penteen statistiese kopolimere tesame met relatief hoë modulus waardes is uniek. 'n Omgekeerde verhouding tussen komonomeer inhoud en treksterkte asook moduluswaardes is waargeneem. 'n Toepassingstudie uitgevoer met die propileen / 1-penteen statistiese kopolimere het verskeie interessante resultate gelewer. Films vervaardig van hierdie kopolimere toon besonderse deursigtigheid en lae waarde van xileenoplosbaarheid, terwyl meganiese integriteit gehandhaaf word. Voordele in die vervaardigingsproses van BOPP-films asook bogemiddelde filmeienskappe hou unieke moontlikhede vir propileen / 1-penteen statistiese kopolimere in. Verskeie voordele tydens blaas- en spuitvormingsprosesse is waargeneem relatief tot ander beskikbare statistiese kopolimere. Die 1-penteen statistiese kopolimere toon 'n laer in-vorm sowel as totale krimping relatief tot etileen- gebaseerde kopolimere. 'n Studie het aangetoon dat tipiese bymiddelpakette by normale toevoegingsvlakke geskik is vir propileen / 1-penteen statistiese kopolimere. Gesien in die groter pp statistiese kopolimeer familie toon 1-penteen 'n beter balans van eienskappe as ander komonomere. Die kombinasie van laer smeltpunt en xileen-oplosbares met hoë moduluswaardes en helderheid is uniek aan propileen /1-penteen statistiese kopolimere.

No description available.

This thesis reports the preparation of novel multi-responsive and multiply stimulable triblock copolymers. The resultant polymers were used to coat cotton fabrics and glass to render them amphiphobic. Further, a method was developed for the preparation of poly(ethylene glycol)-block-poly(hydroxyethyl methacrylate) (PEG-b-PHEMA) via anionic polymerization. The multi-responsive copolymer refers to poly(ethylene glycol)-orthonitrobenzyl-poly[2-(perfluorooctyl)ethyl methacrylate)-block-poly(2-cinnamoloxyethyl methacrylate) (PEG-ONB-PFOEMA-b-PCEMA, or P1). P1 was synthesized via atom transfer radical polymerization (ATRP) of FOEMA and a precursory monomer of CEMA using a PEG macroinitiator. The copolymer was multi-responsive or dual light-responsive because the ONB junction cleaves and PCEMA block becomes crosslinked upon UV photolysis. The multiply stimulable copolymers are a series of poly(ethylene glycol)-disulfide-poly[2-(perfluorooctyl)ethyl methacrylate)-block-poly(2-cinnamoloxyethyl methacrylate) (PEG-S2-PFOEMA-b-PCEMA) copolymers. These polymers were synthesized by the end-coupling Py-S2-PFOEMA-b-PHEMA and PEG-SH, and subsequent cinnamation of the PHEMA block. These polymers are multiply stimulable because the S2 junction and PCEMA block respond to different stimulations, such as reducing agents and light, respectively. These synthetic strategies will advance the field of stimuli-responsive polymers by providing novel functional polymers for the generation of durable self-cleaning surfaces. The above polymers form micelles in water or water/organic solvent mixtures because of the water-soluble PEG blocks. Polymer-coated cotton was obtained by immersing cotton in micellar copolymer solutions before subsequent drying and annealing treatment. Upon photolysis, the PEG block was cleaved and the PCEMA anchoring layer became crosslinked. Such a crosslinked and stable layer was rendered amphiphobic because of the exposed PFOEMA block. A similar coating can be obtained from P2. Two types of stimulations including photolysis and reduction treatment need to be applied to yield amphiphobic textiles. This coating strategy is unique and environmentally friendly because the water- and oil-repellent coatings were prepared from an aqueous solution for the first time. In a further study, a novel and long-sought method was developed for the anionic polymerization of PEG-b-PHEMA. A PEG-DPE macroinitiator was synthesized and subsequently converted into an active initiator by reaction with sec-butyl lithium. Consequently, the active initiator underwent polymerization with HEMA-TMS to yield PEG-b-P(HEMA-TMS). Upon post-polymerization modification, PEG-b-PHEMA was obtained with a low polydispersity of 1.08. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-04-29 12:25:54.593