Abstract
Random copolymers of styrene and acenaphthylene, in THF solution, have been metallated with sodium. At low temperature, the characteristic green solutions of the radical-anion of acenaphthylene (τ) are obtained. The metallated copolymers degrade very rapidly when the temperature is raised above −50° yielding deep-red solutions. The ESR and ultraviolet spectrophotometric studies, as well as molecular weight decrease, give evidence that several mechanisms are involved in this degradation. In a first step, preferential metallation of neighbouring acenaphthylene units occurs and radical-anions are formed. Then an extremely fast chain scission takes place, with disappearance of the radicals and with formation of two anionic acenaphthylene chain-ends. After longer reaction-times, chain scission between isolated acenaphthylene units and styrene units occurs also. This reaction seems to be much slower than the degradation reaction between two neighbouring acenaphthylene units.
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