Effects of trivalent phosphorus compounds on vinyl polymerizations—VII. A nonstationary state radical polymerization of methylmethacrylate in the presence of phenyldichlorophosphine

Ogawa, Teiichiro; Gállego, José T.; Inoue, Motomichi

doi:10.1016/0014-3057(78)90181-7

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The interaction of poly(methacrylate) radicals with diphenyldiacetylenes

Canizal

Burillo

Muñoz

et al. 1994

J. Polym. Sci. A Polym. Chem.

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SYNOPSISThe free radical polymerization of methyl methacrylate (MMA) in the presence of p,p'disubstituted diphenylbutadiynes was studied. Both the rate and degree of polymerization are somewhat lowered by the presence of the diynes, but the propagating radicals were stabilized giving clear ESR signals of the interacted polyMMA radicals at the polymerization temperature of 70°C. The magnitude of the interaction depended on the electron density of the diynes; in the cases of diphenylbutadiyne and dimethoxycarbonyldiphenylbutadiyne, the interaction was more enhanced showing ESR signals with smaller spectra widths and increasing the number of radicals with the polymerization time, while in the cases of electron donor-substituted diynes the interaction was weaker and the radical concentration remained constant during the polymerization. These systems are considered to be examples of the stabilization of transient radicals by the direct interaction of radicals with additives without formation or breaking of chemical bonds. No diacetylenic group was found in the polyMMA obtained.

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