Journal of Macromolecular Science Part A - Chemistry · 1984 · 53 citations · 12 references
Natural SciencesChemical EngineeringChemistryChemical KineticsPolymer ChemistryReaction EngineeringPolymer SynthesisPolymerization ChemistryPolymerization KineticsPolymerization ProcessesRadical ReactionsChain TransferChain Transfer ReactionsElectrolytesInitiation KineticsRadical CyclizationRadical Reaction KineticsReaction Rate EquationsRedox Reaction Kinetics
Abstract A survey is made of the present knowledge about the kinetics and mechanism of the radical cyclopolymerization of dimethyl diallyl ammonium chloride which results in soluble, strong cationic poly-electrolytes. The kinetic analysis, taking into consideration nearly complete cyclization, a linear increase of kp /kt, 0.5 with [M], and different mechanism of initiation depending on the nature of the initiator, leads to rate equations which fit the experimental data well. Initiation with S2O82- has the following peculiarities: formation of primary radicals by redox reaction with chloride ions and interaction with the monomer cation, additional termination by chlorine atoms, and an experimental chain transfer constant to monomer which includes transfer to monomer and termination by chlorine radicals.
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George B. Butler, Rudolph J. Angelo · Journal of the American Chemical Society · 1957 · 329 citations