Abstract
The mean-square radii of gyration <S2> of two polystyrene (PS) samples with weight-average molar masses Mw of 2.18 × 104 and 3.88 × 104 in toluene and 2-butanone and of a cyclic amylose tris(phenylcarbamate) (cATPC) with a Mw of 4.73 × 104 in tetrahydrofuran were determined by synchrotron radiation small-angle X-ray scattering measurements over a wide range of temperatures from −77 °C to 70 °C. Both PS and cATPC are sufficiently soluble to enable SAXS measurements even at −77 °C in the solvents used. The <S2> of cATPC does not depend on temperature over the range investigated here. This result may be reasonable for such rigid ring polymers. In contrast, the radii of PS depend on temperature to a significant degree, whereas the second virial coefficient is mostly temperature independent. The resulting characteristic ratio C∞ for PS in toluene decreases monotonically with increasing temperature, as predicted both by the rotational isomeric state (RIS) and by (helical) wormlike chain models. However, C∞ in 2-butanone exhibits a minimum ∼10 °C and increases with increasing temperature, suggesting that the RIS energy parameters should be affected by the intermolecular interactions between the polymer and solvent.
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Acknowledgements
The synchrotron radiation experiments were performed at the BL40B2 in SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos. 2012A1059, 2012B1050 and 2013A1046) and at the BL-10C in KEK-PF under the approval of the Photon Factory Program Advisory Committee (No. 2011G557). We thank Dr Noboru Ohta (SPring-8) for his help in setting up the SAXS apparatus in SPring-8, Ms Xin Yue Jiang (Osaka University) for performing preliminary SAXS measurements, and Professor Takahiro Sato (Osaka University) for fruitful discussion. This work was supported by JSPS KAKENHI Grant Numbers 23750128 and 25410130.
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Terao, K., Morihana, N. & Ichikawa, H. Solution SAXS measurements over a wide temperature range to determine the unperturbed chain dimensions of polystyrene and a cyclic amylose derivative. Polym J 46, 155–159 (2014). https://doi.org/10.1038/pj.2013.76
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DOI: https://doi.org/10.1038/pj.2013.76
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