Polymerization of unsaturated aldehydes with nitrite catalysts

Alpha, beta-ethylenically unsaturated aldehydes are polymerized by contacting the aldehyde, with or without another monomer, with a catalytic amount of an alkali or alkaline earth nitrite. Suitable aldehydes are acrolein, alphamethyl, alpha-ethyl, alpha-propyl, alpha-isobutyl, alpha-n-amyl, alpha-n-hexyl, alphabromo, alpha,beta - dimethyl, alpha - methylbeta - ethyl, alpha - methyl - beta - isopropyl or alpha - ethyl - beta - propyl acrolein, crotonaldehyde, or alpha-chloro, beta-chloro, alphabromo, beta-bromo or alpha, gamma-dichloro crotonaldehyde. Monomers which may be copolymerized with the aldehyde are styrene, alpha-methyl styrene, vinyl chloride, vinylidene chloride, methyl methacrylate, ethyl acrylate, acrylonitrile, methacrylonitrile, allyl acetate, vinyl acetate, chloroallyl caproate, allyl alcohol, isobutylene, allyl glycidyl ether, vinyl methyl ether, allyl glycolate, methyl allyl oxyacetate, allyloxyacetic acid, vinyl pyridine, glycidyl methacrylate, hydroxyethyl methacrylate, octyl acrylate, vinyl pyrollidone, allyl dimethyl cyanurate, allyl butyl phthalate and dialkyl maleates. Polymerization may be effected in bulk, solvent or aqueous emulsion or suspension systems, preferably in a solvent, and preferably in the presence of a solvent or diluent containing at least one OH group in the molecule. Solvents and diluents specified are benzene, toluene, ethanol, methanol, dioxane, acetonitrile, isopropyl ether, an acetone-water mixture, propanol, ethylene glycol, diethylene glycol, isopropanol and butanol. The polymeric aldehydes may be reacted with urea or thiourea to form resins or may be hydrogenated to form polyhydric alcohols, which may be reacted with aldehydes to form acetals, with nitric acid to form nitrate explosives, with unsaturated acids to form drying oils, or may be used to produce polyesters by heating with a polybasic acid or anhydride, such as phthalic anhydride, alone or with modifying agents such as non-drying or drying oil fatty acids, e.g. coconut fatty acids; the polyesters prepared with the modifying agents may be used as additives for baking enamels containing urea and melamine-form-aldehyde resins. Specification 596,620, [Group IV], is referred to.