Abstract
2-Dimensional X-ray and neutron diffraction patterns have been successfully measured for deuterated and hydrogenated polyoxymethylene (POM) samples obtained by γ-ray induced solid-state polymerization reaction. More than 700 reflections were collected from the X-ray diffraction data at −150 °C by utilizing a high-energy synchrotron X-ray beam at SPring-8, Japan, from which the crystal structure of POM has been refined thoroughly including the extraction of hydrogen atomic positions as clearly seen in the difference Fourier synthesis map. As the first trial the nonuniform (9/5) helical model was analyzed with the reliability factor (R factor) 6.9%. The structural analysis was made also using the X-ray reflections of about 400 observed at room temperature (R 8.8%), and the thermal parameters of constituent atoms were compared between the low and high temperatures to discuss the librational thermal motion of the chains. The 2-dimensional neutron diffraction data, collected for the deuterated and hydrogenated POM samples using an imaging plate system specifically built-up for neutron scattering experiment, have allowed us to pick up the D and H atomic positions clearly in the Fourier synthesis maps. Another possible model, (29/16) helix, which was proposed by several researchers, has been also investigated on the basis of the X-ray diffraction data at −150 °C. The direct method succeeded in extracting this (29/16) model straightforwardly. The R factor was 8.6%, essentially the same as that of (9/5) helical model. This means that the comparison of the diffraction intensity between the data collected from the full-rotation X-ray diffraction pattern and the intensity calculated for both the (9/5) and (29/16) models cannot be used for the unique determination of the superiority of the model, (9/5) or (29/16) helix. However, we have found the existence of 001 and 002 reflections which give the longer repeating period 55.7 Å. Besides there observed a series of meridional 00l reflections forbidden for (9/5) helical model. These additional evidences support the nonuniform (29/16) helical model as the most plausible chain conformation of POM crystal.
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Tashiro, K., Hanesaka, M., Ohhara, T. et al. Structural Refinement and Extraction of Hydrogen Atomic Positions in Polyoxymethylene Crystal Based on the First Successful Measurements of 2-Dimensional High-Energy Synchrotron X-ray Diffraction and Wide-Angle Neutron Diffraction Patterns of Hydrogenated and Deuterated Species. Polym J 39, 1253–1273 (2007). https://doi.org/10.1295/polymj.PJ2007076
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DOI: https://doi.org/10.1295/polymj.PJ2007076