This thesis describes an experimental investigation of synthesis of polystyrene under various polymerization conditions such as solvent polarity, temperature, initial concentrations of initiator, catalyst, monomer and added salts or co-catalyst, which was achieved using the living cationic polymerization technology in conjunction with gel permeation chromatography (GPC) and NMR spectroscopy. Polymerizations of styrene were conducted using 1-phenyl ethylchloride (1-PEC) as an initiator and tin tetrachloride (SnCI4) as a catalyst in the presence of tetra-n-Butylammonium chloride (nBu4NCI). Effects of solvent polarity varied by mixing dichloromethane (DCM) and less polar cyclohexane (C.hex), temperature, initial concentrations of SnC14, 1-PEC and nBu4NCI on the polymerizations were examined, and the conditions under which a living polymerization can be obtained were optimised as: [styrene]o ~ 0.75 - 2 M; [1-PEC]o ~ 0.005 - 0.05 M; [SnCI4Jo ~ 0.05 - 0.4 M; [nBu4NCIJo ~ 0.001 - 0.1 M; DCM/C.hex ~ 50/0 - 20/30 v/v; T ~ 0 to -45°C. Kinetic studies of styrene polymerization using the Omnifit sampling method showed that the number average molecular weight (Mn) of the polymers obtained increased in direct proportion to monomer conversion and agreed well with the theoretical Mn expected from the concentration ratios of monomer to initiator. The linearities of both the 1n([MJoI[M]) vs. time plot and the Mn vs. monomer conversion plot, and the narrow molecular weight distribution (MWD) measured using GPC demonstrated the livingness of the polymerizations, indicating the absence of irreversible termination and transfer within the lifetimes of the polymerizations. The proposed 'two species' propagation mechanism was found to apply for the styrene polymerization with 1-PEC/SnCI4 in the presence of nBu4NCl. The further kinetic experiments showed that living styrene polymerizations were achieved using the 1-PEC/SnCI4 initiating system in mixtures of DCM/C.hex 30/20 v/v at -15°C in the presence of various bromide salts, tetra-n-butylammonium bromide, tetra-n-pentylammonium bromide, tetra-n-heptylammonium bromide, and tetra-n-octylammonium bromide, respectively. The types of the bromide salts were found to have no significant effect on monomer conversion, Mn, polydispersity and initiation efficiency. Living polymerizations of styrene were also achieved using titanium tetrachloride (TiCI4) as a catalyst and 1-PEC as an initiator in the presence of a small amount of 2,6-di-tert-butylpyridine or pyridine instead of nBu4NCl. GPC analysis showed that the polymers obtained had narrow polydispersities (P.D. < 1.3), and the linearities of both the In([MJo/[MJ) vs. time plot and the Mn vs. monomer conversion plot demonstrated that the polymerizations are living, when the ratio of DCM and C.hex was less than 40 : 10 and the reaction temperature was not lower than -15°C. The reaction orders relative to TiCl4 and 1-PEC were estimated from the investigations into the rate of polymerization to be 2.56 and 1.0 respectively. lH and 13C NMR analysis of the resultant polystyrene would suggest the end-functionality of the product polymers is chlorine for all living polymerizations.

The aim of this study was to use the transformation of anionic to metathesis polymerization to produce block co-polymers of styrene-b-pentenylene using WC16/PStLi and WC16/PStLi/AlEtC12 catalyst systems. Analysis of the products using SEC and 1H and 13C NMR spectroscopy enabled mechanisms for metathesis initiation reactions to be proposed. The initial work involved preparation of the constituent homo-polymers. Solutions of polystyryllithium in cyclohexane were prepared and diluted so that the [PStLi]o < 2x10-3M. The dilution produced initial rapid decay of the active species, followed by slower spontaneous decay within a period of days. This was investigated using UV/visible spectrophotometry and the wavelength of maximum absorbance of the PStLi was found to change with the decay from an initial value of 328mn. to λmax of approximately 340nm. after 4-7 days. SEC analysis of solutions of polystyrene, using RI and UV/visible (set at 254nm.) detectors; showed the UV:RI peak area was constant for a range of polystyrene samples of different moleculor weight. Samples of polypentenylene were prepared and analysed using SEC. Unexpectedly the solutions showed an absorbance at 254nm. which had to be considered when this technique was used subsequently to analyse polymer samples to determine their styrene/pentenylene co-polymer composition. Cyclohexane was found to be a poor solvent for these ring-opening metathesis polymerizations of cyclopentene. Attempts to produce styrene-b-pentenylene block co-polymers, using a range of co-catalyst systems, were generally unsuccessful as the products were shown to be mainly homopolymers. The character of the polymers did suggest that several catalytic species are present in these systems and mechanisms have been suggested for the formation of initiating carbenes. Evidence of some low molecular weight product with co-polymer character has been obtained. Further investigation indicated that this is most likely to be ABA block copolymer, which led to a mechanism being proposed for the termination of the polymerization.

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