Effects of cyclization and electrostatic interactions on the termination rate of macroradicals in free-radical crosslinking copolymerization


KESKINEL M., Okay O.

POLYMER BULLETIN, vol.40, pp.491-498, 1998 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 40
  • Publication Date: 1998
  • Doi Number: 10.1007/s002890050281
  • Title of Journal : POLYMER BULLETIN
  • Page Numbers: pp.491-498

Abstract

Effects of cyclization and ionic group contents on the termination rate of macroradicals formed at zero monomer conversion were investigated. For this purpose, the pregel regime of free-radical methyl methacrylate / ethylene glycol dimethacrylate (MMA/EGDM) and acrylamide / N,N'-methylenebisacrylamide (AAm/BAAm) copolymerization systems was studied by means of the dilatometric technique. To eliminate the chain-length dependent variation of the termination rates, different sets of experiments were carried out each at a fixed monomer and initiator concentration. At low crosslinker contents, the termination rate of zero-conversion macroradicals was enhanced in crosslinking copolymerizations compared to linear polymerization. This is due to the cyclization reactions which reduce the size of the macroradical coils and thus, enhance the termination rates due to the lowering of the thermodynamic excluded volume effect. As the amount of the crosslinker increases, an enhancement in the initial rate of polymerization is observed in all series of experiments, indicating that steric effects on segmental diffusion dominate at high crosslinker contents. The results also indicate a slower rate of termination of ionic macroradicals compared to the non-ionic radicals of the same molecular weight and points the significance of the thermodynamic excluded volume effect on rising the ionic group content.