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A donor–acceptor complex consisting of tetrahydrofuran and maleic anhydride initiates photochemical and thermal polymerization of methyl methacrylate. The mechanism of the transformation of this complex was investigated by studying changes in its electrical conductivity, its chemiluminescence, and various influences on its initiating capability (water, air, DPPH, substitution of styrene for methyl methacrylate and of 1,4‐dioxane for tetrahydrofuran). It has been shown that initiation by radicals cannot be clearly excluded and that ionic radicals form in the system and can initiate the anionic growth of the chain.

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