Abstract
Association of syndiotactic (s) poly(methyl methacrylates) (PMMAs) in toluene, benzene, and acetonitrile has been studied by NMR spectroscopy, osmometry, and viscometry. It was found that in solutions of highly syndiotactic PMMA in toluene, most of the polymer exists in the associated state. Association takes place by means of stereospecific intermolecular and intramolecular interactions of long parallel syndiotactic sequences. The minimum length of syndiotactic sequences necessary for association of s‐PMMA in toluene is 7–8 monomer units. Viscosity data indicate that in dilute solutions the associated structures appear as large formations which do not have the character of compact particles. The formation of the aggregates of PMMA is a relatively slow process. A model of the structure of the aggregates of s‐PMMA in toluene is proposed. As compared with that in toluene, the tendency to aggregation in benzene and acetonitrile is negligible. Integral parameters currently used for the characterization of polymer‐solvent interaction, like “good” or θ solvent, are not suitable for predicting the tendency of s‐PMMA to aggregation. The formation of aggregates evidently has some connection with the effect of the solvent upon the conformational structure of syndiotactic sequences.