波谱学杂志 ›› 2010, Vol. 27 ›› Issue (4): 540-547.

• 恭贺沈联芳和杜有如两位先生八十华诞专栏 • 上一篇    下一篇

PVP在水/丙酮混合溶剂中分子运动行为的研究

王琳琳,赵新*,孙万赋   

  1. 新疆大学 理化测试中心,新疆 乌鲁木齐 830046
  • 收稿日期:2010-03-16 修回日期:2010-04-12 出版日期:2010-12-05 发布日期:2010-12-05

Studies on Molecular Motion of PVP in Mixed Solvents H2O/C3H6O

 WANG Lin-Lin, ZIAO Xin*, SUN Wan-Fu   

  1. The Center of Analysis and Measurement, Xinjiang University, Urumqi 830046, China
  • Received:2010-03-16 Revised:2010-04-12 Online:2010-12-05 Published:2010-12-05

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T2H先减小后增大. [η]出现最大值也是T2H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 T2H measurements and 1H NMR spectroscopy. It was found that: η  increased first and then decreased rapidly with increasing volume fraction of C3H6O. T2H  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 T2H had 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

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