Photoinitiation and electroinitiation in the polymerization of 2‐vinylnaphthalene

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Abstract
The zinc chloride‐catalyzed polymerization of 2‐vinylnaphthalene (VN) with both photoinitiation and electronitiation methods was examined. Good yields were obtained with both methods, the electroinitiated process being somewhat faster. The mechanism for polymerization initiation was investigated through a detailed comparison of the kinetics. Both initiation methods show a similar response to increasing input energy and to change in salt to monomer mole ratio. Both methods indicate formation of a ZnCl2–(2‐VN)2 complex as intermediate with the formation of the species being rate‐determining. These results, together with other similar investigations, are then used to deduce a mechanism that involves the formation of an electronically excited donor–acceptor complex. It is argued that in certain salt‐stabilized, electron‐delocalized, aromatic systems, such excitation is possible in electroinitiation.