Immobilization of reagents and catalysts by photochemical grafting onto polymers

The possibility of immobilizing reagents and catalysts by photochemical grafting of their composites with an epoxy-diacrylate resin has been investigated. Two model systems have been examined: (i) the catalytic decomposition of aqueous sodium hypochlorite by cobalt peroxide, with oxygen production; (ii) the reaction of alkali metals with alcohols. For case (i) the catalyst was embedded, in the form of a mixture with 90% of zeolite 13X, into the photografted polymer matrix; while for case (ii) the alkali metal reagent, supported onto 90% of zeolite 13X, was incorporated into the microporous membrane. Kinetics of reaction (i) were studied in standard conditions (1.0 M NaOCl; 1.0 M NaCl; 0.25 M NaOH) between 288.2 to 318.2 K, and the relation between pseudp-first order kinetic constants and amount of catalyst incorporated into the membrane determined. Isotope effects for reaction (ii), relative to H₂, D₂, HD production, were measured with mixtures of deuterated and non-deuterated CH₃OH(D), C₂H₅OH(D), n-C₃H₇OH(D), and i-C₃H₇OH(D) at 25 °C, as a function of volume percent of non-deuterated alkanols in the liquid phase.

For reaction (i) reactivity was found to be substantially the same in the membrane reactor as in ordinary chemical conditions: loss of catalytic activity did not exceed 15%. For reaction (ii) isotope effects, the origin of which is discussed, fully coincided with those measured in the absence of the polymer matrix.