Structure of some ethylene–phosphonic acid copolymers

Abstract

Abstract An x‐ray study has been made of the structure of a series of ethylene–phosphonic acid copolymers and the parent low‐density polyethylene from which they were derived. The phosphonic acid contents (groups per 100 carbon atoms) of the copolymers were: A, 0.8; B, 1.8; C, 2.8; and D, 8.0. Small‐angle x‐ray scattering (SAXS) results show that the phosphonic acid substituents do not incorporate into the crystal lattice to any appreciable extent, that the substituents have the effect of decreasing the average thickness of the crystal lamellae and increasing the breadth of the size distribution of thicknesses, and that a two‐phase model does not adequately account for the observed SAXS invariant. Wide‐angle x‐ray scattering (WAXS) results show that specimens, A, B, and C are partially crystalline with the polyethylene crystal structure and that D is amorphous. The observed broadenings of the 110 and 200 crystal reflections in the copolymers indicate that the substituents decrease the lateral dimensions of the crystalline lamellae and/or increase the deformation of the lattice due to external strain. Specimen D, completely amorphous according to the WAXS criterion, exhibits the largest value of the SAXS invariant of all the copolymers studied and must thus possess a multiphase structure consisting of small ordered regions and a disordered phase. The results of the study show the structure of the copolymers to be consistent with the fringe‐micelle model but do not rule out the folded‐chain model, although a regular fold surface is unlikely.