| In the field of hybrid miniemulsion polymerization, work prior to this thesis was dominated by proof-of-concept studies. The incentive and objective of the current research was to address lingering issues from those prior studies and to develop a more fundamental understanding of the hybrid grafting mechanism and the connections between reaction phenomena and product characteristics.; A strong dependence was found between monomer structure and the degree of grafting possible in hybrid miniemulsion polymerization. Monomers that had a sterically hindered radical center were found to prefer resin attack through chain transfer where monomers with an uninhibited radical center were found to favor direct addition to resin double bonds. Based solely on those routes of attack, virtually complete grafting was achieved with direct addition to double bonds where a lower degree of grafting was observed when attack was facilitated through chain transfer. The lower degree of grafting in those systems was also exacerbated by homogeneous nucleation (from hydrophilic monomer) inherently creating particles absent of alkyd (due to its hydrophobicity and inability to transport to those new particles). |
