Metathesis ring-opening polymerization of some new aryl and fluoroaryl polycyclic alkenes, and related studies
This thesis describes work on the metathesis ring-opening polymerization of a series of seven aryl and fluoroaryl derivatives of bicyclo65[2.2.1]hepta-2,5-diene and a study of the potential of 5,6-dimethylenebicyclo[2.2.l]hept-2-ene as a monomer for metathesis and anionic polymerizations. The thesis is divided into four chapters. In the first chapter the background of olefin metathesis, as it relates to this work, is discussed. The second chapter describes the synthesis, characterization and polymerization of the monomers used in this study. The attempted metathesis, and anionic polymerizations of 5,6-dimethylenebi cyc]o[2. 2. l]hept-2-ene are discussed in chapter three. The fourth chapter describes the characterization of the new polymers obtained in this study, the chief analytical method has been (^13)C n.m.r. spectroscopy and it is shown that the polymer chain microstructure is a function of the catalyst (either WCl(_6)/(CH(_3))(_4)Sn or MoCl(_5)/(CH(_3))(_4)Sn in this work) and the monomer structure. Generally it appears that the molybdenum based catalyst leads to polymers with a higher proportion of cis vinylene units and a greater degree of stereoregulation than is found in polymers derived from the tungsten based catalyst.