Structural investigations on lewis acid mediated solubilization of poly(p‐phenylenebenzobisthiazole) in an aprotic solvent

Abstract

AbstractInvestigations on aluminum chloride‐mediated solubilization of poly(p‐phenylenebenzo‐bisthiazole), PBZT, in nitromethane revealed that, in general, dilute solutions of the polymer prepared in nitromethane with a large molar excess of the Lewis acid with respect to PBZT were relatively stable and thus suitable for processing into films and coatings via regeneration with hydroxylic nosolvents while polymer solutions with minimum stoichiometrically required (PBZT:AlCl3 molar ratio 1:4) or marginal molar excess of AlCl3 relative to PBZT tended to gel during handling. Structural studies on polymer–Lewis acid complex solutions were performed using 1H and 27Al NMR. 1H NMR of the protonated structure of the model compound 2,6‐diphenylbenzo [1,2‐d:4,5‐d′] bisthiazole was useful for confirming the 1H NMR assignments of PBZT‐AlCl3 complex solution in CD3NO2. 27Al NMR was particularly useful in probing the different tetrahedrally coordinated environments of the Al nucleus in the polymer solution, pointing to a complexation interaction between the polymer molecule and the Lewis acid and also between the solvent and the Lewis acid. Direct evidence in the solid state for the presence of a reversible electron donor–acceptor complex (EDA complex) was obtained from FTIR spectra of complexed films, isolated and handled in an inert atmosphere. The structural changes upon PBZT complexation caused significant frequencly shifts in both aromatic as well as heteroring stretching modes relative to PBZT itself, and intensity variations indicative of changes in the resonance configuration between the 1,4‐phenylene moiety and the aromatic heterocyclic ring were also observed upon complexation. A preliminary comparison between the pristine PBZT fibers and regenerated PBZT by dilute solution viscometry indicates that the process results, to some extent, in polymer degradation leading to a decrease in the molecular weight of the polymer © 1993 John Wiley & Sons, Inc.