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利用拉曼光谱研究丙烯酸基高吸水性聚合物吸水过程中水结构的变化以及水、CH和COO基团之间的相互作用。

Study of changes in water structure and interactions among water, CH, and COO groups during water absorption in acrylic acid-based super absorbent polymers using Raman spectroscopy.

作者信息

Nasu Tatsuro, Ozaki Yukihiro, Sato Harumi

机构信息

Graduate School of Human Development and Environment, Kobe University, 3-11 Tsurukabuto, Nada, Kobe, Hyogo 657-8501, Japan.

Molecular Photoscience Research Center, Kobe University, 1-1 Rokkodai, Nada, Kobe, Hyogo 657-8501, Japan; School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2021 Apr 5;250:119305. doi: 10.1016/j.saa.2020.119305. Epub 2020 Dec 11.

Abstract

The interactions of acrylic acid-based super absorbent polymers (SAPs) with water and the hydrogen bonding of water within its three-dimensional network were studied using Raman spectroscopy. The Raman spectra of SAP solutions suggested that both the COO and CH groups of SAPs interact with water. The Raman spectra of pure water and those of SAPs containing approximately 40, 50, and 60% water exhibited a broad band corresponding to the OH-stretching mode of water in the 4000-3000 cm region. This band was separated into three components using a curve-fitting method. The three components at 3200, 3400, and 3600 cm were assigned to the OH-stretching modes of strong hydrogen bonding (SHB), weak hydrogen bonding (WHB), and dangling bond (Dang) species of water, respectively. The fractional areas of the three components were calculated and compared. The changes in the hydrogen bonding of water were compared with those of the water present in SAPs, and their temperature-dependent variations were elucidated. At a water content of approximately 60%, the behavior of the fractional area versus temperature was similar to that of pure water. However, at a water content of approximately 40%, the behavior was significantly different. The fraction of SHB was smaller, and the fraction of WHB was larger than that of pure water. The difference in the CH and COO peak shifts of SAP, which is a result of the addition of a small percentage of water, was revealed by Raman spectroscopy. The position of the CH deformation peak changed linearly. However, the position of the COO rocking peak did not change significantly up to a water content of 30%, above which it exhibited a rapid shift to lower wavenumbers. This result indicates that the interactions of the CH and COO groups are different.

摘要

采用拉曼光谱法研究了丙烯酸基高吸水性聚合物(SAPs)与水的相互作用以及水在其三维网络中的氢键作用。SAP溶液的拉曼光谱表明,SAPs的COO和CH基团均与水相互作用。纯水以及含水量约为40%、50%和60%的SAPs的拉曼光谱在4000 - 3000 cm区域均呈现出对应于水的OH伸缩模式的宽带。使用曲线拟合方法将该宽带分离为三个组分。在3200、3400和3600 cm处的三个组分分别对应于水的强氢键(SHB)、弱氢键(WHB)和悬键(Dang)物种的OH伸缩模式。计算并比较了这三个组分的分数面积。将水的氢键变化与SAPs中存在的水的氢键变化进行比较,并阐明了它们随温度的变化情况。在水含量约为60%时,分数面积随温度的变化行为与纯水相似。然而,在水含量约为40%时,行为有显著差异。SHB的分数较小,WHB的分数比纯水的大。拉曼光谱揭示了由于添加少量水导致的SAP中CH和COO峰位移的差异。CH变形峰的位置呈线性变化。然而,在水含量达到30%之前,COO摇摆峰的位置变化不明显,超过该含量后,它迅速向低波数移动。该结果表明CH和COO基团的相互作用不同。

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