Poly(oxyphosphazenes): A unifying look at structure and morphology

Abstract

Variations in thermotropic behavior have been investigated for many crystalline polyphosphazenes. Experimental results obtained from DSC, solid-state MAS NMR, dilatometry, mechanical property (creep and dynamic) measurements, birefringence, X-ray (wide and small-angle), and electron diffraction have been made as a function of temperature in an attempt to elucidate the structure-morphology behavior in these polymers. Initially all polyphosphazenes described in this study crystallize from dilute or moderately concentrated solutions in the monoclinic form with relatively low crystallinity (≤50%). When heated, these specimens expand atT(1) and adopt a chain-extended 2D mesophase morphology in order to relieve congestion. Above this first-orderT(1) temperature a chain-extended −P=N− chain backbone morphology transforms into an isotropic phase at the melting temperatureTm. When cooled, samples transform into the mesostate. However, crystallization from the mesophase belowT(1) takes place into a 3D orthorhombic state. These two modes of ordering/disordering are in accordance with (i) a hexatic chain packing [betweenT(1) andTm] with variously mobile side groups that also exhibits smectic features when mesogenic side groups are present and (ii) a 3D orthorhombic structure of high crystallinity belowT(1). The initial monoclinic phase is accessible only via a solution crystallization route. Solid-state MAS NMR, crystallization kinetic measurements, and optical microscopy studies obtained from oriented and unoriented polymers have been especially germane in providing a unifying picture for mesophase formation and ordering in polyoxyphosphazenes. X-ray and electron diffraction evidence is complicated by critical overlapping peaks that are found under these same conditions. They demonstrate that (a) positional disorder exists along the chain direction and (b) the side chain above, as well as below, theT(1) transition is governed by the mobility, size, and type of side group in circumstances where phase transformations occur.