Reaction of the 2-hydroxy-2-propyl radical with acrylate type molecules in aqueous solution: Radical addition or electron transfer

Abstract

The reaction of 2-hydroxy-2-propyl (IP) radical with 12 acrylate type monomers in aqueous solutions was investigated by means of pulse radiolysis: the molecular structure effects and the mechanisms were evaluated. Radicals were generated either in the reaction of hydrated electron with acetone and subsequent protonation or in the H abstraction reaction by OH radicals from i-propanol. IP radical reacts with acrylamides and acrylic acid esters in radical addition reaction of the type: (CH 3) 2(OH)C + CH 2 CH–C(O)R → (CH 3) 2(OH)C–CH 2–C H–C(O)R with rate coefficients between 3.2 × 10 7 and 1.9 × 10 8 mol −1 dm 3 s −1. Rate coefficients of the reaction with maleic acid (neutral), dimethyl- and diethyl maleate are between 1.3 × 10 8 and 4.7 × 10 8 mol −1 dm 3 s −1. The values for dimethyl- and diethyl fumarate are ca. one order of magnitude higher. However with maleates and fumarates there is also a few percent contribution from the electron transfer reaction of the type (CH 3) 2(OH)C + ROOC–CH CH–COOR + H 2O → ROOC–CH CH–C O −OR + (CH 3) 2CO + H 3O +. In neutral solutions and at pH ∼3 and ∼9, the same rate coefficients were measured. However, in dialkyl maleate and -fumarate solutions between pH 9.5 and 10.5, a base catalyzed decomposition of the IP radical adduct was observed forming electron adduct: ROOC–C((CH 3) 2(OH)C)H–C H–COOR + OH − → ROOC–CH CH–C O −OR + (CH 3) 2CO + H 2O. Molecular structure effects were evaluated using log k– σ p and log k–LUMO plots.