Activity of a new polyoxime‐copper complex in the reversible uptake of molecular oxygen and carbon monoxide, in the polymerization of acrylonitrile, and in the addition reaction of alcohols to acrolein

Abstract

AbstractA new polyoxime‐copper complex was prepared from cupric acetate and a polyoxime which is considered to consist largely of 1,2‐bis(hydroxyimino)trimethylene units. The properties of the complex were studied. Its ESR spectrum was found to be similar to that of the low molecular weight copper(II) complex, whose intensity decreases with increasing copper content. The complex shows a catalytic activity in the Michael type addition reaction of alcohols to acrolein, yielding exclusively β‐alkoxypropionaldehyde. In addition, it initiates the polymerization of acrylonitrile under hydrogen pressure (40 to 90 kg/cm2). Furthermore, the complex with a composition ratio Cu: OX ≈ 1:4 (Cu: number of copper atoms, OX: number of hydroxyimino groups in the complex), after being treated with hydrazine hydrate in methanol under nitrogen, can reversibly take up and release ca. 3,2dm3 of molecular oxygen (in water) and 0,8dm3 of carbon monoxide (in methanol) per mole of copper. These activities decrease remarkably with decreasing copper content of the complex.