Some properties of poly[bis(halophenoxy)phosphazenes

Abstract

The morphology and structure of poly[bis(halophenoxy)phosphazenes] (PBHPP) with F, Cl and Br substituents in the para- or meta-phenoxy positions have been investigated. The size and position of halogen atoms have a significant influence on the thermotropic transition of the polymer. Most PBHPP exhibit polymorphism. Monoclinic and orthorhombic three-dimensional crystalline forms and the location of the two-dimensional mesophase depend upon the chemistry and thermal history of each polymer specimen. Most of the physical properties may be related to the location of the thermotropic transition of the polyphosphazene, which can be expressed as a linear function of the substituent size. Polyphosphazene crystallization behaviour appears to depend upon the position and size of halogen atoms, and the growth of well defined crystals becomes difficult with enhanced side-group size. Surprisingly, thick or bulk specimens of PBHPP comprise globules of comparatively uniform size, which depend upon the sample preparation conditions and the kind of halogen atom present in the side-group. The dimensions of these globules may be increased by heat treatment and with an increase in crystallinity of each polymer specimen. The globules exhibit a bundle-like texture even in drawn PBHPP films.