GB877244A - Peroxides and a process for their manufacture - Google Patents

Abstract

The invention comprises peroxides of the formula <FORM:0877244/IV (b)/1> in which Y is hydrogen or C1-C6 alkyl, X is chlorine or bromine, R1 is hydrogen or a C1-C10 monovalent radical, R2 is a C1-C10 monovalent radical or a divalent radical forming with the adjacent oxygen atom a 5- or 6-membered ring system, or R1 and R2 together with the oxygen atom adjacent to R2 form a 5- or 6-membered ring system, and R is hydrogen or a monovalent radical, or a radical of the formula <FORM:0877244/IV (b)/2> The monovalent radical R may be an aliphatic radical, preferably a tertiary alkyl radical containing 4 to 8 carbon atoms, or a substituted e.g. halogenated, aliphatic radical, or a heterocyclic radical. Thus R may be t-butyl, t-amyl, or a monovalent radical having an indan, cumene, tetrahydro-naphthalene, p-menthane, or tetrahydrofuran nucleus. R1 and R2 as monovalent radicals may be the same or different aliphatic, cycloaliphatic, or aromatic radicals, or unsaturated aliphatic, substituted aliphatic, aryl, or heterocyclic radicals, e.g. they may be methyl, propyl, butyl, amyl, hexyl, cyclohexyl, b -chloro-ethyl, phenyl-ethyl, diphenyl methyl, phenyl, naphthyl, tetrahydrofurfuryl, or tetrahydropyranyl radicals. The halogenated peroxides may be obtained by reacting at a temperature of minus 60 DEG C. to plus 70 DEG C. a vinyl ether of the formula <FORM:0877244/IV (b)/3> with a hydroperoxide of the formula R.OOH and with an organic hypohalite of the formula B.OX in which B is a straight-chain or branched alkyl radical or substituted alkyl radical having 2 to 10 carbon atoms e.g. t-butyl or t-amyl hypochlorite. Bis-(a -halogenacetal)-peroxides may be obtained by reacting 1 mol of hydrogen peroxide with 2 mols of a vinyl ether and 2 mols of organic hypohalite. The hydrogen peroxide may be used as such or as a solution in an inert solvent, or it may be used in the form of an addition product with urea or silica. Sodium bicarbonate or other acid-binding agent may be present as a catalyst. The halogenated peroxides may be used as polymerization and hardening catalysts in the production of unsaturated polyester resins and polyvinyl compounds. Examples describe the production of 1(1-ethoxy-2-chloro-)ethyl t-butyl peroxide, 1(1-isobutoxy-2-chloro-)ethyl-t-butyl peroxide, a (b -chloro-tetrahydropyranyl) - t - butyl peroxide, 1(1-ethoxy-2-chloro-)ethyl hydroperoxide, bis-(1 - ethoxy - 2 - chloro - ethyl)peroxide, 1(1-isobutoxy-2-chloro-)ethyl hydroperoxide, and bis [a (b -chloro-tetrahydropyranyl)]peroxide.