Studies were made on the synthesis of halide-substituted poly(phthalidylideneary1ene)s by Friedel-Crafts polycondensations of 3-aryl-3-chlorophthalides containing substituents in +position of the phthalide cycle. As follows from the C" NMR spectra, those monomers can afford polymers containing two types of isomeric units substituted in 4-or 7-position. The possible routes of formation of the isomeric units are analyzed and a scheme is suggested for the monomer rearrangement in the synthetic course. The polymers containing those two types of units were shown to be highly thermostable and to contain about 30% of a crystalline phase.

The synthesis of poly(3,3-phthalidylidene-4,4' -biphenylylene) (PPB) by precipitative Friedel-Crafts homopolycondensation of 3-(4-biphenylyl)-3-chlorophthalide was studied. The polymer-catalyst complex precipitated from the initially homogeneous reaction mixture was shown to be active and providing the growth of macromolecular chains. The polymer obtained in the form of smooth, transparent glass-like particles, depending on the reaction parameters, may have either uni-or bimodal molecular weight distribution. Molecular characteristics were not found to depend on the size of the polymer particles. "Precipitative" PPB shows improved properties and higher crystallinity in comparison with "solution" PPB. ZUSAMMENFASSUNG: Die Synthese von Poly(3,3-phthalidyliden-4,4'-biphenylylen) (PPB) durch eine Friedel-Crafts-Fallungspolykondensation von 3-(Biphenyl-4-yl)-3-chlorphthalid wurdeuntersucht. Der aus der urspriinglich homogenen Reaktionsmischung ausgefallte Polymer-Katalysator-Komplex erwies sich als aktiv und forderte das Wachstum der Polymerketten. Die in Form von glatten, tranparenten, glasartigen Partikeln erhaltenen Polymeren zeigen, abhangig von den Reaktionsparametern, entweder uni-oder bimodale Molekulargewichtsverteilung. Die Polymereigenschaften sind unabhangig von der PartikelgroDe. Verglichen mit aus der Liisungspolymerisation erhaltenem PPB zeigt das mittels Fallungspolykondensation hergestellte PPB verbesserte Eigenschaften und hdhere Kristallinitat.