Glassy poly(p-phenylene sulphide): determination of the local structure

Methods are described for obtaining conformational and packing information about para-linked phenylene polymers from wide-angle X-ray scattering. On the basis of these procedures, together with conformational energy calculations, a random chain conformation is determined for non-crystalline poly(p-phenylene sulphide), in which the phenylene groups are rotated away from the coplanar position by 40° and the conformation persists for ～15 Å. Whilst there is no evidence for parallel chain packing at any level, it is necessary to invoke local pairwise correlation of phenylene groups within an otherwise random chain packing system, to obtain satisfactory agreement with the experimental results.