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A novel method (in-situ quantitative infrared spectroscopy of evolved C02) for studying photo-degradation has been developed and applied to the study of several different polymers including a series of polyethylene and poly (vinyl chloride) samples containing Ti02 pigments with different photo-activitics. Infrared (IR) analysis was used to monitor carbon dioxide emitted from samples exposed to ultraviolet irradiation (UV) in atmospheres of differing composition. The experiments were conducted in a specially constructed cell that permits simultaneous UV exposure of the sample and IR interrogation of the vapour in the cell. It has been demonstrated that the in-situ gas-phase method permits a fast and convenient way of assessing the durability of pigmented and unpigmented polymer. A single test on one material occupied about 7 hours - very much less than conventional artificial weathering exposures. Excellent correlation between the C02 method and the conventional method for measuring carbonyl groups in the polyethylene films has been demonstrated, The Ti02 pigments used included anatase and rutiles with different surface treatments. Anatase-pigmented material gave significantly higher C02 emission than unpigmented polyethylene. The rutile-pigmented polyethylenes either gave reduced C02 emission or enhanced emission, according to the surface treatment. The ranking of the pigments as protectants or pro-degradants coincided with that obtained from much more time consuming laboratory testing and field experience. Similar results were obtained for the poly (vinyl chloride). The CO2 method is a convenient way to study the factors (humidity, oxygen concentration and UV intensity or wavelength), which influence the rate of carbon dioxide evolution i. e. the rate of photo-oxidation of the polymers. Blown polyethylene(PE) film was exposed to UV irradiation while held under tensile stress in a specially designed metal frame. The chemical degradation was followed using the FTIR carbonyl index. Tests were conducted on unpigmented PE and on a series of five PEs containing TiO2 pigments with different photo-activities. The yield strengths measured in tensile tests on unexposed films were typically 10 % greater in the longitudinal( machine)direction than in the transverse direction. UV exposures were conducted with stress applied both parallel and transverse to the machine direction.For all six materials, tensile stress accelerated carbonyl group development, Some samples cracked during UV exposure in tension and did so in a shorter time if the stress was applied in the machine direction than if it was transverse to it. The carbonyl index at the onset of cracking was lower for longitudinal samples than for transverse samples. Unpigmented PE was slightly more sensitive to transverse strain and the anatasepigmented PE slightly more sensitive to longitudinal strain.

The development of biodegradable plastics from sustainable sources is at the forefront of chemical research. One such example is the production of polylactide (PLA) via the ring-opening polymerisation (ROP) of the cyclic ester lactide (LA). Current industrial metal initiators utilised for the ROP of LA do not allow control over the stereochemistry of the resulting product. This thesis will investigate various initiators containing a variety of ligand sets for the ROP of rac-LA. Chapter 1 introduces the ROP of rac-LA, the mechanisms utilised and the methods employed for characterisation of PLA. A review of the current literature of recent developments in the production of PLA via various metal initiators is also included. Chapter 2 reports the development of a series of group (IV) complexes containing various amine tris(phenolate) ligands, where the sterics and electronics have been varied. Such complexes were trialled for the ROP of rac-LA as well as the ROP of trimethylene carbonate (TMC). The ability of such initiators to produce copolymers of rac-LA/TMC and rac-LA/isosorbide was also investigated and discussed. Chapter 3 describes the synthesis of a range of group (IV) complexes containing Salalen ligands. The sterics of the ligands have been varied and the ability of the initiators to initiate the ROP of rac-LA in a stereocontrolled fashion has been investigated. Furthermore, the complexes have been trialled for the degradation of PLA into methyl lactate, an important starting material in the production of LA. Chapter 4 investigates the development of Al(III) Salalen complexes for the ROP of rac-LA, where the sterics and electronics of the ligand have been varied. Kinetic investigations have been carried out to aid the understanding of the polymerisation process. Chapter 5 provides details of the reaction procedures for the synthesis of ligands, complexes and polymers. Kinetic procedures are also reported together with details of the analytical techniques employed.