A COMPARISON OF OLIGOMERS AND POLYMERS IN POLY(ARYL KETONE) - EFFECT OF CHAIN FOLDING ON CRYSTAL MORPHOLOGY AND GENERALIZATIONS THEREFROM

Single crystals were prepared from poly(phenyl ethyl ketone) (PEK) oligomers and compared with those of the corresponding polymer with respect to morphology, electron and X-ray diffraction patterns. The present comparison shows a drastic change in morphology when going from the extended chain oligomer to the folded chain polymer, the regular, lozenge-shaped crystals of the oligomer degenerating into irregular, knobbly laths for the polymer. At the same time the diffraction patterns are becoming more poorly defined, the reflections broadening and shifting to smaller angles (these effects being largest along the a direction) all indicating reduced lattice perfection. All these effects, the degeneration in the morphology and lattice order, must clearly be associated with chain folding in the polymer. The above is in sharp contrast with the behaviour of the paraffin-polyethylene system where the onset of chain folding with increasing chain length has no qualitatively noticeable effect on morphology and lattice order. We envisage the effects in PEK arising due to the more bulky and stiffer character of the chains which, while folding for kinetic reasons, cannot do so over a similarly short distance as in the paraffin-polyethylene system or other flexible polymers. The larger fold-spans then require larger volume along the fold surface exerting stresses on the underlying crystals. These stresses, being cumulative, will expand and distort the lattice and eventually set a limit to the size of the coherent structure entity in the growing crystal leading to the observed irregular, knobbly morphology. We venture to generalize this scheme to other members of main chain aromatic polymers, and beyond, to all regular polymers which crystallize slowly and with poorly defined morphologies with the difficulty in folding being the common factor. As a further step, we also invoke the degenerate morphologies of copolymers of otherwise fully flexible chains where exclusion of crystallographically incompatible comonomer units (e.g. branches) from the crystals would be expected to give rise to cumulative strain with analogous consequences.