Solid state properties of poly-β-hydroxybutyrate and of its oligomers

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Abstract
The solid state properties of poly-β-hydroxybutyrate (PHB) were investigated for samples with degrees of polymerization [Formula: see text] from 4 to 994. The observed melting points ranged from 47 °C to 180 °C. Electron diffractograms on carefully prepared single crystals of a high molecular weight sample provided data which confirmed the reported a and b parameters from X-ray fiber diffraction and provided clear justification for the P212121 space group. The observed intensities in the electron diffractogram, corresponding to (hk0) reflections, were compared with the predicted intensities for two proposed structures in the literature. The observed and calculated structure factors for both structures were in good agreement. Small angle X-ray diffraction of the meridional maximum for annealed "cold drawn" and "hot drawn" fibers showed a distinctly different dependence on temperature than the maximum for stacks of lamellar single crystals. For oligomers a long spacing was observed which was about twice the length of the sample [Formula: see text] multiplied by the crystalline advance per monomer.

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