On the mechanism of anionic polymerization of maleic anhydride, 2

Abstract

AbstractThe triphenyl and tributyl phosphine initiated polymerization of maleic anhydride was investigated. The structure of the macro zwitterions, formed under the given reaction conditions, depended on the initiator employed. If the polymerization was initiated by triphenyl phosphine, the macromolecules contained succinic anhydride units and cyclopentanone derivatives, formed from further rearrangement. If, however, tributyl phosphine was employed as initiator, the polymers were mostly made up of conjugated ketoolefinic units. IR, NMR and mass spectrometric measurements were carried out to determine the structure of the polymers. Existence of the macro zwitterions was proved by high voltage electrophoresis.The semi‐conductor properties of the polymers containing conjugated ketoolefinic units are discussed.Spectroscopic investigation of the kinetics of the triphenyl phosphine initiated polymerization of maleic anhydride showed that the initiation reaction of the ylide, formed with the monomer, proceeded about 90 times slower than the propagation reaction due to addition of the monomer to the growing chain‐end.