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温敏性SA/P(NIPAM-co-AM)凝胶分子运动的固体核磁共振研究
(华东师范大学物理与材料科学学院,上海市磁共振重点实验室)
Solid-state NMR study on the molecular motion of thermal sensitive SA/P(NIPAM-co-AM) Hydrogel
(School of Physics and Materials, Shanghai Key laboratory of Magnetic Resonance, East China Normal University)
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投稿时间:2018-05-08    修订日期:2018-05-08
中文摘要: 将不同比例的N-异丙基丙烯酰胺(NIPAM)和丙烯酰胺(AM)引入到聚阴离子海藻酸钠(SA)网络中,采用原位自由基聚合法制备了具有温敏特性的互穿网络SA/P(NIPAM-co-AM)水凝胶。采用固体NMR研究了P(NIPAM-co-AM)分子链在不同温度,尤其是临界温度附近不同基团的运动状态变化。当温度低于低临界溶解温度(LCST)时,体系中分子链运动较快,当温度高于LCST后,由于疏水作用增强,水凝胶结构收缩,分子链运动减慢。实验还发现,不同的基团在不同频段的运动对于温度的响应并不是同步的,而是有着一定的顺序。利用低场核磁共振(LF-NMR)原位研究了复合水凝胶的溶胀过程。结果表明,水分子的扩散和大分子链段的松弛同步进行,符合non- Fickian模型的溶胀特征。
中文关键词: 水凝胶  温敏性  分子运动  核磁共振
Abstract:The SA/P(NIPAM-co-AM) hydrogel was prepared by in situ free radical copolymerization with different content of N-isopropyl acrylamide (NIPAM) and acrylamide (AM) in sodium alginate (SA) network. By changing the composition ratio, a series of thermo-sensitive hydrogels with different lower critical solution temperature (LCST) can be prepared. And under the condition of a low AM/NIPAM ratio, the LCST of the gel is linearly correlated with the increase of the ratio. Meanwhile, the presence of carboxyl group and amino group also makes the gel responsive to pH value, which can expand the application of the hydrogels. Solid-state NMR was used to study the molecular dynamics at different temperature, especially near the LCST. When the temperature is lower than the LCST, the mobility of molecular chain is quickly, when temperature is higher than LCST, the molecular mobility decreased due to the collapse of the network. It also can be found that the mobility of different groups in different frequency do not change synchronized, but in certain sequence. The high-frequency motion of the main chain was first affected by temperature (298K), followed by high-frequency motion of the side chain (301K), and finally the low-frequency motion of the side chain (304K). The low-frequency motion of the main chain is not significantly affected by temperature. The macroscopic changes occurred after the reduction of the mobility of all the groups (305K). In addition, using the low field nuclear magnetic resonance (LF-NMR) the swelling process of composite gel was studied in situ. It was found that the diffusion of water molecules and the relaxation of macromolecular chains are synchronized, which conform to the swelling model of non-Fickian diffusion.
文章编号:20180508002     中图分类号:O631. 22    文献标志码:
基金项目:国家自然科学基金(21544003,51273067)资助
引用本文:
戎晨亮,侯立峰,黄海龙,徐敏.温敏性SA/P(NIPAM-co-AM)凝胶分子运动的固体核磁共振研究[J].功能高分子学报,DOI:10.14133/j.cnki.1008-9357.20180508002.
RONG Chen-liang,HOU Li-feng,HUANG Hai-long,XU Min.Solid-state NMR study on the molecular motion of thermal sensitive SA/P(NIPAM-co-AM) Hydrogel[J].Journal of Functional Polymers,DOI:10.14133/j.cnki.1008-9357.20180508002.