Acrylonitrile Polymerization by Ceric Ion-Primary Alcohol Redox Systems in Aqueous Nitric Acid

The polymerization of acrylonitrile (AN) initiated by CeIV-primary alcohol redox systems has been studied in aqueous nitric acid under nitrogen in the temperature range 0 to 45° C. Taft's correlation can be applied to fit the kinetic results relative to a series of differently substituted primary alcohols. The polymerization is initiated by primary radicals formed in water from the dismutation of the CeIV -alcohol complex. This process has a high activation energy (21 kcal/mol) and gives rise to an induction period at temperatures lower than 40° C. PAN chains containing the alcohol residue are terminated predominantly on metal ions. The alcohol enhances the AN solubility in water and accordingly influences the polymerization kinetics. Variations in temperature and concentration of both components of the redox system allow control of the polymerization rate and of the molecular weight of the resulting PAN. © 1981, Taylor & Francis Group, LLC. All rights reserved.