Photopolymerization without Light. Polymerization of Acrylates Using Oxalate Esters and Hydrogen Peroxide^†

We define the photopolymerization of acrylates without light as a process wherein the radical chain polymerization produced by photoinitiators are produced by nonphotochemical means. We use the chemical reactions of the chemiluminescent lightstick to accomplish this. An important potential application is in producing “photopolymers” in areas that are not light accessible as in the inside of a tube or behind a pipe. Polymerizable acrylate mixtures containing dissolved oxalate esters undergo radical chain polymerization when exposed to a flow of nitrogen gas saturated with hydrogen peroxide vapors. We propose aryloxyoxalyl hydroperoxides to be the reactive species.