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林业科学 ›› 2024, Vol. 60 ›› Issue (2): 128-138.doi: 10.11707/j.1001-7488.LYKX20220297

• 综合评述 • 上一篇    

纤维素自愈合水凝胶研究进展

张永跃1,2, 石江涛2, 付宗营1, 卢芸1   

  1. 1. 中国林业科学研究院木材工业研究所 北京 100091;
    2. 南京林业大学材料科学与工程学院 南京 210037
  • 收稿日期:2022-05-06 修回日期:2022-06-20 发布日期:2024-03-13
  • 通讯作者: 卢芸
  • 基金资助:
    国家自然科学基金优秀青年基金项目“木材超分子结构诠析与优异功能构筑”(32122058)。

Research Progress of Cellulose Self-Healing Hydrogels

Zhang Yongyue1,2, Shi Jiangtao2, Fu Zongying1, Lu Yun1   

  1. 1. Research Institute of Wood Industry, Chinese Academy of Forestry Beijing 100091;
    2. College of Material Science and Engineering, Nanjing Forestry University Nanjing 210037
  • Received:2022-05-06 Revised:2022-06-20 Published:2024-03-13

摘要: 水凝胶是由亲水性聚合物通过物理或化学交联方式形成的3D网络结构材料,通常具有亲水性、黏弹性、生物相容性等特点,广泛应用于生物工程、柔性电子等领域。传统水凝胶一般采用化石基聚合物为原料,其使用和废弃过程对人体和环境存在潜在威胁;同时水凝胶长时间使用后,在机械外力作用下易产生破坏,从而会对其结构完整性和性能产生影响。具有自我修复能力的水凝胶破损后利用超分子相互作用或可逆共价作用可以恢复到与起始状态几乎相同的机械性能,对延长水凝胶使用寿命具有重要意义。纤维素是一种天然有机聚合物,主要来源于自然界中的树木等天然材料,具有无毒、无害、生物相容性好等优点,符合绿色环保理念,应用前景广阔。纤维素链上丰富的含氧基团可与水分子形成氢键网络,有利于制备具自愈能力的水凝胶。对纤维素进行化学改性得到纤维素衍生物,如羧甲基纤维素、羟乙基纤维素等,可以扩大其在水凝胶领域的应用。本研究综述以纤维素以及纤维素衍生物为原料的一类自愈合水凝胶,总结传统自愈合水凝胶存在的缺点并提出相关改性策略。纤维素因自身晶体结构以及内部超分子相互作用导致其在水中难以溶解,故一般采用分散体系或溶解体系进行纤维素水凝胶的制备,通过调控水凝胶的三维结构,利用可逆共价作用(酰腙键、二硫键交换等)和非共价作用(氢键、疏水作用、主客体相互作用等)赋予其自我修复能力。由于这种可逆交联的存在,传统纤维素自愈合水凝胶一般机械性能较差,同时因现阶段对纤维素自愈合水凝胶的功能开发比较单一,限制其在各领域的应用。本研究介绍构建智能网络结构、仿生自然生物伤口愈合机制、功能化改性的方式,总结新型多功能智能纤维素自愈合水凝胶构筑的方式,结合自愈合水凝胶取得的相关研究成果,提出纤维素自愈合水凝胶现阶段仍需解决的问题,并对自愈合水凝胶的应用前景进行展望。

关键词: 纤维素, 水凝胶, 非共价键, 自愈合, 智能材料

Abstract: Hydrogels are 3D network structure material formed by physical or chemical cross-linking of hydrophilic polymers. It usually has the characteristics of hydrophilicity, viscoelasticity, biocompatibility, etc., and is widely used in bioengineering, flexible electronics and other fields. Traditional hydrogels generally use fossil-based polymers as raw materials, and there are potential threats to the human body and the environment during the use of hydrogels and the recycling of waste hydrogels. At the same time, the traditional hydrogel will be damaged due to the action of mechanical external force after a long time of use, and its structural integrity and performance will be affected. Hydrogels with self-healing ability can recover to almost the same mechanical properties as the initial state after breakage using supramolecular interactions or reversible covalent interactions, which is of great significance for prolonging the service life of hydrogels. Cellulose is a kind of natural organic polymer, with non-toxic, harmless, good biocompatibility and other advantages, mainly from natural materials such as trees in nature, in line with the concept of green environmental protection, has broad application prospects. The abundant oxygen-containing groups in cellulose chain can form hydrogen bond network with water, which is conducive to the preparation of hydrogels with self-healing ability. And by chemically modifying cellulose to obtain cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, etc., its application in the field of hydrogels can be expanded. This paper comprehensively introduces a class of self-healing hydrogels using cellulose and cellulose derivatives as raw materials, analyzes the shortcomings of traditional self-healing hydrogels, and proposes related modification strategies. Cellulose is difficult to dissolve in water due to its own crystal structure and internal supramolecular interactions, so cellulose hydrogels are generally prepared by using a dispersion system or a dissolving system. By regulating the three-dimensional structure of the hydrogel, reversible covalent interactions (acylhydrazone bond, disulfide bond exchange, etc.) and non-covalent interactions (hydrogen bonding, hydrophobic interaction, host-guest interaction, etc.) are used to endow the hydrogel with self-healing ability. Due to the existence of such reversible cross-linking, the general mechanical properties of traditional cellulose self-healing hydrogels are poor. At the same time, the functional development of cellulose self-healing hydrogels is relatively simple at present, which limits its application in various fields. Therefore, by introducing the construction of intelligent network structure, biomimetic natural biological wound healing mechanism and functional modification methods, this paper proposed a new multi-functional intelligent cellulose self-healing hydrogel construction method. Finally, combined with the relevant research results of self-healing hydrogels, the problems that still need to be solved at the present stage of cellulose self-healing hydrogels are put forward, and the application prospect of cellulose self-healing hydrogels in the fields of bioengineering, electronic materials and intelligent materials is forecasted.

Key words: cellulose, hydrogel, non-covalent interactions, self-healing, smart materials

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