Synthesis and polymerization of some halogenated polycyclic alkenes

Abstract

This thesis describes work on the ring opening polymerisation of some lightly fluorinated and chlorinated polycyclic monomers. The thesis is divided into three chapters. The first chapter reviews the utility of the metathesis reaction in organic chemistry in general and polymer chemistry in particular. Present understanding of the value and limitations of the reaction is discussed along with related mechanistic and theoretical background. The second charter is concerned with the synthesis, characterization and polymerization of some new fluorinated monomers. The way in which the choice of catalyst can influence the details of polymer chain microstructure is discussed for the particular case of polymers prepared from 2,3-bis(trifluoromethyl)bicyclo[2.2.l]hepta-2,5-diene using tungsten and molybdenum based catalysts. Catalyst selectivity in the polymerization of endo/exo mixtures of isomeric monomers is also examined. The third chapter describes work directed towards the synthesis of polyarylenevinylenes. The main part of this chapter is concerned with the synthesis, characterization and examination for polymerizability by metathesis ring opening, of a range of chlorinated bicyclo[3.2.l]octa- 2,6-dienes. It is concluded that the presence of a 4-endo chlorine atom in such molecules acts as an inhibitor for polymerization without acting as a catalyst poison.