Phase equilibrium in solutions of rodlike polymers.

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  • 棒状高分子溶液の相平衡
  • ボウジョウ コウブンシ ヨウエキ ノ ソウ ヘイコウ

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Abstract

Sedimentation equilibrium measurements were made on solutions of poly (γ-benzyl L-glutamate) in N, N-dimethylformamide using three samples of different molecular weights. The data were analyzed to obtain the partial concentration derivative [∂ (Δμ0) /∂υ1] SED of (Δμ0) SED corresponding to the excess chemical potential of the solvent, where υ1 is the volume fraction of the polymer. The values of (Δμ0) SRD corrected for sample's polydispersity were in good agreement with the solvent chemical potentials derived from osmotic pressure data of Kubo and Ogino for the same system. The chemical potential data for each sample were analyzed by the Flory-Abe theory, yielding a negative interaction parameter χ decreasing with increasing υ1. For large axial ratios w the isotropic-liquid crystal phase boundary concentrations υ1′ and υ1″ were larger than those predicted by the Flory theory with χ=0, increased with decreasing χw, more gradually than the theoretical prediction, and appraoched the values predicted by the Onsager theory below χw=30. A similar trend in chemical potential and discrepancy in phase diagram between theory and experiment were noted also for aqueous schizophyllan. The discrepancy was resolved by incorporating an anisotropic interaction term G2 (G2 <0) in the Flory theory with negative χ.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 43 (4), 191-200, 1986

    The Society of Polymer Science, Japan

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