The overall objective is to obtain mechanistic information on copper mediated living radical polymerisation, ATRP. At present as the reaction is assumed to proceed via a free radical mechanism kinetic rate constants are often utilised to analyse first order plots to derive radical concentrations. In addition as many of the catalysts utilised are often insoluble, especially the copper (II) species the use of the elegant persistent radical effect theories to these systems may not always be trivial to apply. Information obtained from this project will help establish similarities and any differences between free radical polymerisation of vinyl monomers and ATRP. Preliminary studies already carried out at Warwick already have demonstrated clear differences between reactivity ratios of monomers with the ability to coordinate to copper with respect to free radical polymerisation and 13C kinetic isotope experiments have also shown clear differences of the 13C kinetic isotope effects.
1. Comparison of the copper (I) complexes with Diaz butadiene, pyridine imines and bipyridyl legends.
2. Synthesis and characterisation of at least three different rigid choral legend systems and a study of the effect of the legend stereochemistry on stereochemistry of the polymer.
3. A study into the reactivity ratios of MMA and coordinating monomers and a direct comparison with free radical polymerisation systems. The project will use high field variable temperature NMR to look at exchange processes at the mental centre at the reaction temperature. The use of coordinating solvents and monomers on the nature of the catalyst will be investigated. Diaz butadiene pyridine imines, and bipyridyl legends.
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