Syntheses of vinyl polymers containing a large π-electron cloud in the side chain

Several novel vinyl polymers containing five fused benzene rings in side chains were synthesized either by polymerization of the appropriate vinyl monomers or by chemical modification of the appropriate polymer. Thus, 3-(α-acryloyloxy)ethylperylene was prepared from perylene by Friedel-Crafts acylation with acetyl chloride and subsequent hydrogenation, followed by the reaction of the resulting alcohol with acryloyl chloride. 3-Acrylamido- or methacrylaminoperylene was prepared by the nitration of perylene, reduction of the resulting 3-nitroperylene, and the reaction with acryloyl or methacryloyl chloride. p-Vinylbenzal-3-acetylperylene was prepared by the condensation and dehydration reaction between p-vinylbenzaldehyde and 3-acetylperylene under alkaline medium, and, in the same manner, p-vinylbenzal-3-aminoperylene was prepared from p-vinyl benzaldehyde and 3-aminoperylene. All these monomers were polymerized with α,α′-azobisisobutyronitrile as catalyst in solution to afford the corresponding vinyl polymers. A vinyl polymer containing perylene-3-acetyl side chain was also prepared by the acetalization of poly(vinyl alcohol) with 3-formylperylene.