双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器

doi:10.16085/j.issn.1000-6613.2021-2052

化工进展 ›› 2022, Vol. 41 ›› Issue (8): 4406-4416.DOI: 10.16085/j.issn.1000-6613.2021-2052

双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器

邱艺娟¹(), 林佳伟¹, 秦济锐¹, 吴嘉茵¹, 林凤采², 卢贝丽¹, 唐丽荣³, 黄彪¹()

^1.福建农林大学材料工程学院，福建福州 350108
^2.闽江学院材料与化学工程学院，福建福州 350108
^3.福建农林大学金山学院，福建福州 350108

收稿日期:2021-09-30 修回日期:2021-11-19 出版日期:2022-08-25 发布日期:2022-08-22
通讯作者: 黄彪
作者简介:邱艺娟（1996—），女，硕士研究生，研究方向纳米纤维素复合材料。E-mail：1721987739@qq.com。
基金资助:
国家自然科学基金(32171726);福建省自然科学基金(2019J01388);国家自然科学基金青年项目(32001267);福建省高等学校“竹资源创新利用”科技创新团队项目(KJG200031A)

Double dynamic covalent bond crosslinked nano-cellulose conductive hydrogel for a flexible sensor

QIU Yijuan¹(), LIN Jiawei¹, QIN Jirui¹, WU Jiayin¹, LIN Fengcai², LU Beili¹, TANG Lirong³, HUANG Biao¹()

^1.College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350108, Fujian, China
^2.College of Material and Chemical Engineering, Minjiang University, Fuzhou 350108, Fujian, China
^3.Jinshan College, Fujian Agriculture and Forestry University, Fuzhou 350108, Fujian, China

Received:2021-09-30 Revised:2021-11-19 Online:2022-08-25 Published:2022-08-22
Contact: HUANG Biao

摘要/Abstract

摘要：

自愈合导电水凝胶因其良好的自愈合性能与导电性能，在柔性可穿戴设备中具有巨大的应用前景。以4-甲酰基苯硼酸（Bn）交联聚乙烯醇（PVA）和聚乙烯亚胺（PEI）构建基于硼酸酯键和亚胺键的双重动态交联水凝胶网络，引入聚吡咯修饰的纤维素纳米纤维（PPy@CNF）构建了具有良好自愈合和导电性的PBP-PPy@CNF纳米复合水凝胶。结果表明，当PPy@CNF的质量分数为0.8%时，水凝胶的力学性能最佳，其最大应力可达6.65kPa，断裂拉伸应变可达2080%，电导率为2174μS/m。基于该水凝胶的电阻式传感器具有良好的稳定性和重复性，在应变检测范围0~800%内，灵敏因子GF可分为三个线性响应区域，分别是0~200%（GF₁=2.82）、200%~600%（GF₂=7.15）和600%~800%（GF₃=12.85），该传感器能有效检测人体不同部位的运动，可应用于可穿戴传感设备。

关键词: 纳米纤维素, 动态共价键, 自愈合, 水凝胶, 传感器

Abstract:

Self-healing conductive hydrogels have great potential applications in flexible wearable devices because of their good self-healing properties and electrical conductivity. A double dynamic cross-linked hydrogel network based on borate ester bond and imine bond was synthesized via cross-linking polyvinyl alcohol (PVA) and polyethylenimine (PEI) with 4-formylbenzoboric acid (Bn). Then, PPy@CNF (grafted polypyrrole (PPy) on the surface of CNF) was incorporated to construct PBP-PPy@CNF nanocomposite hydrogels with good self-healing and electrical conductivity. The results indicated that when the content of PPy@CNF was 0.8wt%, the mechanical properties of the hydrogel were the best. The maximum stress and the fracture tensile strain can be up to 6.65kPa and 2080%, respectively with electrical conductivity of 2174μS/m. In the strain range of 0—800%,the gauge factor GF can be divided into three linear response regions,namely 0—200% (GF₁=2.82), 200%—600% (GF₂=7.15) and 600%—800% (GF₃=12.85). The strain sensors integrated by PBP-PPy@CNF hydrogel with good stability and repeatability can efficiently identify and monitor the various human motions,showing promising applications in the field of wearable sensing devices. This study provided a new way for the design of conductive hydrogel and broadens the application of nanocellulose in sensor field.

Key words: nanocellulose, dynamic covalent bond, self-healing, hydrogel, sensor

中图分类号:

TQ325.9

邱艺娟, 林佳伟, 秦济锐, 吴嘉茵, 林凤采, 卢贝丽, 唐丽荣, 黄彪. 双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器[J]. 化工进展, 2022, 41(8): 4406-4416.

QIU Yijuan, LIN Jiawei, QIN Jirui, WU Jiayin, LIN Fengcai, LU Beili, TANG Lirong, HUANG Biao. Double dynamic covalent bond crosslinked nano-cellulose conductive hydrogel for a flexible sensor[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4406-4416.

图/表 13

图1 PBP-PPy@CNF水凝胶的制备流程及交联机理

表1 PBP-PPy@CNF水凝胶的配比

样品编号	PVA质量分数/%	PEI质量分数/%	PPy@CNF质量分数/%	Bn质量分数/%
PBP-PPy@CNF0	5.0	5.0	0	0.8
PBP-PPy@CNF0.2	5.0	5.0	0.2	0.8
PBP-PPy@CNF0.4	5.0	5.0	0.4	0.8
PBP-PPy@CNF0.6	5.0	5.0	0.6	0.8
PBP-PPy@CNF0.8	5.0	5.0	0.5	0.8
PBP-PPy@CNF1.0	5.0	5.0	1.0	0.8

图2 SEM图

图3 CNF、PPy@CNF、PPy、PBP-PPy@CNF0和PBP-PPy@CNF0.8的FTIR图谱

图4 PBP-PPy@CNF水凝胶的拉伸-应变曲线

表2 PBP-PPy@CNF水凝胶的屈服强度、断裂强度及拉伸应变

样品	屈服强度/kPa	断裂强度/kPa	拉伸应变/%
PBP-PPy@CNF0	1.37	0.34	6287
PBP-PPy@CNF0.2	1.78	0.44	5467
PBP-PPy@CNF0.4	2.35	0.57	4746
PBP-PPy@CNF0.6	5.22	3.16	4002
PBP-PPy@CNF0.8	6.65	4.90	2080
PBP-PPy@CNF1.0	5.24	4.42	1766

图5 25℃时PBP-PPy@CNF水凝胶的动态黏弹性

图6 水凝胶的自愈合过程

图7 PBP-PPy@CNF水凝胶动态交替应变-时间变化曲线

图8 PBP-PPy@CNF水凝胶循环交替应变变化曲线

图9 PBP-PPy@CNF水凝胶的导电性

图10 水凝胶传感器在不同拉伸应变下的相对电阻变化

图11 水凝胶传感器在检测人体运动方面的应用

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双重动态共价键交联纳米纤维素导电水凝胶及其柔性传感器

Double dynamic covalent bond crosslinked nano-cellulose conductive hydrogel for a flexible sensor

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