Abstract: A new class of compounds: R-W-R' where R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, peroxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorus containing group.Examples:Di[1,3-dimethyl-3-(t-butylperoxy)butyl] carbonate;Di[1,3-dimethyl-3-(n-butoxycarbonylperoxy)butyl] carbonate;2,2-Bis[3,3-di(t-butylperoxy)butoxy] propane;Di[1,3-dimethyl-3-(t-butylperoxy)butyl] ethyl phosphate.They are free radical affording compounds useful in crosslinking of polyolefins and unsaturated polymers, and for the polymerization of vinyl monomers and diolefinic monomers.

Abstract: Ethylenically unsaturated material susceptible to free-radical polymerization, e.g., vinyl chloride monomer, is polymerized, e.g., in an aqueous medium, with an initiator system comprising, in combination, alkaline reagent, e.g., sodium bicarbonate, organic acid anhydride, e.g., isobutyric anhydride, peroxygen compound selected from organic peroxy acid (peracid), e.g., peracetic acid, and hydrogen peroxide, and alkyl pyrocarbonate, e.g., diethyl pyrocarbonate. The initiator system is added to the polymerization medium in amounts sufficient to polymerize the ethylenically unsaturated material.

Abstract: Ethylenically unsaturated material susceptible to free radical polymerization, e.g., vinyl chloride monomer, is polymerized, e.g., in an aqueous medium, with an initiator system comprising, in combination, dialkyl pyrocarbonate, hydrogen peroxide, and alkaline reagent, e.g., sodium bicarbonate. The initiator system is added to the polymerization medium in amounts sufficient to polymerize the ethylenically unsaturated material.