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Silica supported chromium oxide catalysts, known as Phillips catalysts, are used in the production of over 40% of the world's high-density polyethylene. The original catalyst comprised CrO(_3) impregnated onto silica. Due to the carcinogenic nature of chromium(VI), chromium(m) catalyst precursors which are oxidised during calcination are now preferred. Two such precursors have been employed throughout the studies reported in this thesis; one is prepared by the aqueous impregnation of a silica support with basic chromium(in) acetate, whilst the other comprises a dry-blended mixture of chromium(m) acetylacetonate with silica. Calcination of the two precursors has been studied using a combination of temperature-programmed quadrupole mass spectrometry and infrared spectroscopy. The chromium(III) acetylacetonate precursor is postulated to disperse near its melting point and react via an acetate intermediate. Both precursors may therefore be expected to produce the same catalyst following calcination. The study of subsequent CO reduction of these calcined catalysts by quadrupole mass spectrometry supports this observation. The reduction is found to proceed via a Langmuir-Hinshelwood mechanism, both precursors demonstrating the same behaviour. Activation energies for the catalyst reduction have been determined from the corresponding Arrhenius plots. Quadrupole mass spectrometry techniques have identified 1-hexene production during the early stages of polymerization using the CO reduced catalysts. This indicates the formation of a chromacyclopentane intermediate species which may also be involved in the mitiation of polymerization. The continuous fragmentation of the catalyst support and polymer growth have been investigated using contact mode and phase-imaging atomic force microscopy. Non-equilibrium plasma oxidation of the two catalyst precursors has been studied by quadrupole mass spectrometry. An active catalyst is obtained from the chromium(m) acetate catalyst, however the dry-blended chromium(in) acetylacetonate precursor is unable to achieve the dispersion required, and the oxidised species are inactive for ethylene polymerization.

This report details the work carried out on the synthesis and characterisation of branched polyesters. The experimental effort concentrated on the branching of PET-type polymers with a variety of potential branching agents, such as trimesic acid, and the control of branching with end-capping agents, such as benzyl alcohol. The polymers synthesised were then characterised by solution viscosity, end-group analysis, DSC analysis, theological analysis and light scattering. Extensive branching of polymers has been observed and controlled via end-capping agents. One group of polyesters synthesised with increasing levels of brancher, were characterised by absolute Mw values which increased from -10K to -350K. Despite this, all of the macromolecules displayed roughly the same solution viscosity. Though the corresponding melt viscosity increased with Mw, the values achieved were far below those expected for analogous linear polymers of comparable Mw. A second group of polyesters synthesised with a fixed level of brancher and increasing levels of end-capper were characterised by a much narrower range of Mw values. These polymers however had melt viscosities lower than those of linear polymers yet had Mw's of between -3 and - 15 times greater than those of linear polymers.

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Thesis (M. Phil.)--Chinese University of Hong Kong. / Bibliography: leaves 37-38.

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Layer-by-layer assembly has received much attention over the last fifteen years. This assembly process can be carried out using different methods including hydrogen-bonding, electrostatic, and to a lesser extent, covalent interactions. However, these assemblies are rarely seen on polyolefin substrates due to the lack of functionality on the surface. “Click” chemistry has become very popular in recent years as a means to join modular compounds together. This thesis is the first published report to use “click” chemistry as a means for layer-by-layer assembly on a polymeric substrate. By designing polymers that contain alkyne or azide groups, it is possible to assemble them layer-by-layer on a polyethylene substrate. Polymers based on tert-butyl acrylate were initially designed for use in organic solvents such as tetrahydrofuran. The copper catalyst that facilitated the 1,3-dipolar cycloaddition was air sensitive and expensive. To capture the true essence of “click” chemistry, a new system was designed based on N-isopropyl acrylamide (NIPAM)-based polymers. These polymers were water soluble and allowed for “click” chemistry to be performed in water and open to air in benign conditions. With the development of a water soluble polymer system that could be modified to contain either azide groups or alkyne groups, layer-by-layer assembly was carried out in water. A polyethylene film was modified in a series of reactions to have an alkyne-functionalized surface. The poly(N-isopropyl acrylamide)-based polymers were layered in an alternating fashion to form multilayer assemblies. A series of control reactions were also performed, showing that these layers were interconnected via triazole linkages. These assemblies were monitored by attenuated total reflectance spectroscopy. Once the layers were assembled, the polyvalent nature of the polymers allowed for further functionalization. Various surface functionalizations were established using fluorescence microscopy and contact angle analysis. By using spectroscopic and chemical means, layer-by-layer assembly on polyethylene films was proven. Control reactions showed the necessity of components for triazole formation. Therefore, layer-by-layer assembly using “click” chemistry was achieved.

Layer-by-layer assembly has received much attention over the last fifteen years. This assembly process can be carried out using different methods including hydrogen-bonding, electrostatic, and to a lesser extent, covalent interactions. However, these assemblies are rarely seen on polyolefin substrates due to the lack of functionality on the surface. “Click” chemistry has become very popular in recent years as a means to join modular compounds together. This thesis is the first published report to use “click” chemistry as a means for layer-by-layer assembly on a polymeric substrate. By designing polymers that contain alkyne or azide groups, it is possible to assemble them layer-by-layer on a polyethylene substrate. Polymers based on tert-butyl acrylate were initially designed for use in organic solvents such as tetrahydrofuran. The copper catalyst that facilitated the 1,3-dipolar cycloaddition was air sensitive and expensive. To capture the true essence of “click” chemistry, a new system was designed based on N-isopropyl acrylamide (NIPAM)-based polymers. These polymers were water soluble and allowed for “click” chemistry to be performed in water and open to air in benign conditions. With the development of a water soluble polymer system that could be modified to contain either azide groups or alkyne groups, layer-by-layer assembly was carried out in water. A polyethylene film was modified in a series of reactions to have an alkyne-functionalized surface. The poly(N-isopropyl acrylamide)-based polymers were layered in an alternating fashion to form multilayer assemblies. A series of control reactions were also performed, showing that these layers were interconnected via triazole linkages. These assemblies were monitored by attenuated total reflectance spectroscopy. Once the layers were assembled, the polyvalent nature of the polymers allowed for further functionalization. Various surface functionalizations were established using fluorescence microscopy and contact angle analysis. By using spectroscopic and chemical means, layer-by-layer assembly on polyethylene films was proven. Control reactions showed the necessity of components for triazole formation. Therefore, layer-by-layer assembly using “click” chemistry was achieved.