AN ESR STUDY OF THE FILM FORMATION STEPS OF VAPOR-DEPOSITION POLYMERIZATION OF POLYAMIC ACID

A film of polyamic acid is formed by vapor deposition polymerization of pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenyl ether (ODA). We have taken ESR spectrum during the polymerization process and compared it with the ESR spectrum of films obtained from solution polymerization. In the intermediate polymers during vapor deposition polymerization, the amide bond (-CONH-) is coplanar with the benzene ring and two protons in the PMDA molecule. This intermediate polymer has one unpaired electron that interacts with the two nitrogen nuclei equally. On the other hand, in the polymer obtained by solution polymerization, the amide bond and the benzene ring of PMDA are not coplanar. In this polymer, too, some of the molecules have an unpaired electron that seems to have almost no coupling with NH groups. These results imply that the polymer formation via vapor deposition proceeds through different intermediates and different molecular configurations from that via the solution process.