Crystallization of hydroxybutyrate oligomers: 1. morphology and folding

Exact length hydroxybutyrate oligomers containing 24 and 32 repeat units have been prepared and their crystallization behaviour and crystal morphology observed. The oligomers form crystals from dilute solution and from the melt that have similar overall morphologies to crystals of the polymer, poly(hydroxybutyrate). Electron diffraction indicates that the chains are closely perpendicular to the basal planes of the crystals. Wide angle X-ray diffraction suggests that all crystals, no matter what their thickness, have a high degree of crystallinity and the same crystal structure. The crystals have a range of thicknesses, as measured by small angle X-ray diffraction. The most common thicknesses correspond to the extended stem length and to one half or, surprisingly, two thirds of that value. A model is proposed for the non-integer fraction crystals in which half of the chain ends are incorporated in the crystals themselves. (C) 2004 Elsevier Ltd. All rights reserved.