SUBSTITUENT EFFECTS ON RADICAL POLYMERIZATION BEHAVIOR OF 2,2-(4,4'-DISUBSTITUTED-DIPHENYL)-4-METHYLENE-1,3-DIOXOLANES

2,2-(4,4-Dimethoxydiphenyl)-4-methylene-l,3-dioxolane (5), 2,2-(4,4-dimethyldiphenyl)-4-methylene-l,3-dioxolane (6), 2,2-diphenyl-4-methylene-l,3-dioxolane (7), 2,2-(4,4-dichlorodiphenyl)-4-methylene-l,3-dioxolane (8), and 2,2-(4,4-dicyanodiphenyl)-4-methylene-l,3-dioxolane (9) were synthesized and polymerized using radical initiators at 60 and 120 °C to undergo predominantly ring-opening accompanying elimination of the corresponding 4,4-disubstituted benzophenones. It was found that the polymer yields decreased as electron-withdrawing character of the substituents increased. The substituent effects on the polymer yields were discussed in terms of EhVMO (eigenvalue of the lowest unoccupied molecular orbital) and EHomo(eigenvalue of the highest occupied molecular orbital) of the monomer and ESomo(eigenvalue of the singly occupied molecular orbital) of the radical. © 1990, American Chemical Society. All rights reserved.