Polymer-Supported Phase Transfer Catalysis : Kinetics of a Bromide Ion Displacement Reaction and the Effect of Mass Transfer on the Global Rate of Reaction

概要

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The bromide ion displacement reaction of n-octyl methanesulfonate catalyzed by polymerbound phosphonium ion was studied and the effects of the phosphonium ion content and the degree of cross-linking on the intrinsic activity and the intraparticle diffusion were examined. The catalysts were prepared by quaternization of chloromethylated polystyrene with tri-n-butylphosphine. All experiments were carried out in a stirred tank reactor in the temperature range from 60 to 90℃ and at ambient pressure. The intrinsic rate of reaction was proportional to the concentration of n-octyl methanesulfonate, and gradually increased with the concentration of potassium bromide in the aqueous phase. The intrinsic activity decreased with increases in the phosphonium ion content and the degree of cross-linking. The liquid-to-solid mass transfer resistance was insignificant at stirring speeds above 400 rpm under the present conditions. The intraparticle diffusion of n-octyl methanesulfonate was found to be an important factor controlling the global rate of reaction. The effective diffusivity of n-octyl methanesulfonate in polymer resin decreased remarkably with increase in the degree of cross-linking.
社団法人日本薬学会の論文
1984-02-25