Page 187 - 201810

第 35 卷第 10 期 精 细 化 工 Vol.35, No.10
2018 年 10 月 FINE CHEMICALS Oct. 2018

其他
基于分子修饰 C-COS 的高吸湿保湿机理

*
*
卜 鑫，裴继诚 ，产慧芳，张方东 ，刘海棠，
周志敏，甄小琴，王 菁
（天津科技大学 天津市制浆造纸重点实验室，天津 300457）

摘要：采用漆酶/2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）体系氧化壳寡糖制备了一种高吸湿保湿性羧基化壳
13
寡糖（C-COS）。利用低场核磁共振（LF-NMR）、FTIR 和 CNMR 考察了其分子间氢键的变化并进一步推测出
吸湿保湿机理。结果表明：在 C-COS 的吸湿过程中，聚合物分子与水之间存在着分子间氢键作用力。C-COS
–1
分子上极性较强的羧酸根产生了新的氢键效应，结合升温红外中 3363、1643 cm 处吸收峰强度的减小和同样波
–1
数下吸收峰频率的蓝移以及溶胀红外中 1643 cm 处吸收峰强度的增加，确定了 C-COS 分子中羧酸根与水之间
所形成的水合氢键（H—O—H···O—C==O）。另外，C-COS 的保湿机理在于聚合物溶解在水体系中能够形成一
种巨大的聚合物-水网状结构，促使水分子以氢键的形式被牢牢地锁住在这种网状结构中。
关键词：漆酶/TEMPO 体系；羧基化壳寡糖（C-COS）；吸湿保湿机理；氢键效应
中图分类号：O636.1 文献标识码：A 文章编号：1003-5214 (2018) 10-1795-06

High Moisture-absorption and Moisture-retention Mechanism of

Molecularly Modified C-COS

*
*
BU Xin, PEI Ji-cheng , CHAN Hui-fang, ZHANG Fang-dong ,
LIU Hai-tang, ZHOU Zhi-min, ZHEN Xiao-qin, WANG Jing
（Tianjin Key Lab of Pulp & Paper, Tianjin University of Science & Technology, Tianjin 300457, China）

Abstract: Carboxylated-chitooligomer (C-COS), which had a high moisture-absorption and moisture-
retention ability, was prepared by oxidation of chitooligomer using a laccase/ 2,2,6,6-tetramethylpiperidine-
1-oxyl (TEMPO) system. The intermolecular hydrogen bonding of C-COS was investigated by low-field
13
nuclear magnetic resonance (LF-NMR), FTIR and CNMR, and its moisture-absorption and moisture-
retention mechanism was deduced. The results showed that intermolecular hydrogen bonding were formed
between polymer molecules and water in the course of C-COS hygroscopic process. More polar carboxylate
ions on the C-COS molecule produced new hydrogen bonding effect. The decrease of the absorption peak
–1
intensity at 3363 and 1643 cm and blue shift of the absorption frequency at the same wave number in the
–1
heating IR, as well as the increase of the absorption peak at 1643 cm in the swelling IR, confirming that
information of hydrated hydrogen bonds (H—O—H···O—C==O) between water and carboxylate ions on
the C-COS molecule. In addition, moisture-retention mechanism of C-COS was obtained that the polymer
dissolved in the water system can form a huge polymer-water network structure, prompting the water
molecule in the form of hydrogen bonds was firmly locked in this network structure.
Key words: laccase/TEMPO system; carboxylated-chitooligomer (C-COS); moisture-absorption and
moisture-retention mechanism; hydrogen bonding effect
Foundation items: Natural Science Foundation of China (31700516)；College Student’s Laboratory
Innovative Fund of Tianjin University of Science and Technology (1715A305)

收稿日期：2017-10-19; 定用日期：2018-01-22; DOI: 10.13550/j.jxhg.20170841
基金项目：国家自然科学基金 (31700516)；天津科技大学大学生实验室创新基金（1715A305）
作者简介：卜 鑫（1993—），男，硕士生。联系人：裴继诚，教授，电话：022-60602006，E-mail：jcpei@tust.edu.cn；张方东，实
验师，电话：022-60601051，E-mail：fangdongzh@tust.edu.cn。