PVP在水/丙酮混合溶剂中分子运动行为的研究

摘要/Abstract

摘要：

通过对粘度、自旋-自旋弛豫时间以及¹H NMR谱的测定，研究了PVP在不同体积配比的水/丙酮溶液中的特性粘数变化和分子运动规律，并讨论了引起这些变化的原因. 结果表明：随着丙酮的不断加入，PVP的特性粘数[η]先增加后减小，而T_2H先减小后增大. [η]出现最大值也是T_2H出现最小值的时候，丙酮的体积百分数为40%. 丙酮的加入破坏了水分子间自身氢键相互作用形成的网状结构，解离出来的水分子被PVP优先吸附到大分子链上，部分与羰基形成氢键，另一部分以自由水的形式被包裹在大分子线团内. 水分子的不断进入以及与水形成新的氢键使PVP链逐渐伸展，引起特性粘数的增大，分子运动受阻. 当丙酮含量增加到一定程度时，水的含量不足以使大分子链继续膨胀，故链呈卷缩状态，使大分子运动逐渐恢复自由. ¹H NMR谱中各质子的化学位移变化也证实了此过程中的氢键变化规律. 

关键词: 核磁共振(NMR), 特性粘数, T₂, PVP, 混合溶剂

Abstract:

Intrinsic viscosity (η) and molecular motion in ternary solution of poly (N-vinyl pyrrolidone) (PVP) in mixed solvents H₂O/C₃H₆O with different volume fractions of C₃H₆O were studied by viscosity and T_2H measurements and ¹H NMR spectroscopy. It was found that: η increased first and then decreased rapidly with increasing volume fraction of C₃H₆O. T_2H decreased first and then increased with the increasing volume fraction of C₃H₆O. A maximum value of η appeared at a C₃H₆O volume fraction of 40% at which point T_2Hhad a minimum value. Adding C₃H₆O destructed hydrogen bonds among the H₂O molecules, and dissociated free H₂O molecules could be adsorbed by PVP. Some of them might stay in the interior of PVP chain, while others might come to bind -CO of PVP chain. This would lead to increases in coil dimension and η of PVP. On the other hand, hydrogen bonds between PVP and H₂O could cause restriction in molecular motion. With a C₃H₆O fraction volume of 40%, the content of water were not high enough to extend PVP coils. Instead, the existence of water might shrink the PVP coils, making molecules motion faster.

Key words: NMR, intrinsic viscosity, T₂, PVP, mixed solvent

中图分类号:

O482.53

王琳琳, 赵新, 孙万赋. PVP在水/丙酮混合溶剂中分子运动行为的研究[J]. 波谱学杂志, 2010, 27(4): 540-547.

WANG Lin-Lin, ZIAO Xin, SUN Wan-Fu. Studies on Molecular Motion of PVP in Mixed Solvents H₂O/C₃H₆O[J]. Chinese Journal of Magnetic Resonance, 2010, 27(4): 540-547.

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