Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis

摘要: The cerium(IV)–alcohol couple in an acidic medium is example of a redox system capable initiating free radical polymerization. When the alcohol has polymeric nature, outcome such process block copolymer, member class compounds possessing many useful properties. most common polymer with terminal –OH group poly(ethylene glycol) (PEG); however, detailed mechanism its reaction cerium(IV) remains underexplored. In this paper, we report our findings for based on spectrophotometric measurements and kinetic modeling. We find that both order net rate constant oxidation depend strongly nature used. to account experimental observations, postulate protonation PEG decreases affinity some cerium(IV)–sulfate complexes formed system.