CN113698532B - Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及水凝胶技术领域和导电材料科学领域,尤其涉及一种可穿戴传感器用多功能(优异的机械适用性、高灵敏性、抗菌性和抗冻性等)聚合物双阳离子水凝胶的制备方法。The invention relates to the field of hydrogel technology and the field of conductive material science, in particular to a multifunctional (excellent mechanical applicability, high sensitivity, antibacterial and antifreeze properties, etc.) polymer dicationic hydrogel for wearable sensors method of preparation.
背景技术Background technique
随着智能终端的发展,人们对生活质量要求的不断提高,各种传感器技术和智能设备的发展使得实时便捷地采集人体行为成为可能。为了实现对人体活动长时间的连续监测,需要将具有传导性能的电子设备安装在人体的表面。传统的电子设备主要组成是硬质高分子材料以及无机半导体材料,由于其本身的脆性和刚性,难以实现可穿戴。With the development of smart terminals and the continuous improvement of people's quality of life requirements, the development of various sensor technologies and smart devices has made it possible to collect human behavior in real time and conveniently. In order to realize long-term continuous monitoring of human activities, electronic devices with conductive properties need to be installed on the surface of the human body. The main components of traditional electronic devices are hard polymer materials and inorganic semiconductor materials. Due to their brittleness and rigidity, it is difficult to realize wearable devices.
为了满足复杂人体运动的需求,灵活性、人性化的设计逐渐成为可穿戴电子设备的重要组成部分。柔性可穿戴传感器是模仿人类皮肤的特征而制备的具备感知功能的设备,近年来在人工智能、机器感知和人机交互等领域展现出巨大的应用潜能,但绝大多数柔性基材作为传感器材料在导电性方面面临很大困难,这影响了其作为可穿戴传感器的灵敏度和稳定性。填充导电材料是解决此类问题最常见的方法,其中有机导电聚合物(聚苯胺、聚吡咯等)常被填充用于构建导电网络,良好的界面相容性可制备均匀的导电性聚合物弹性体,但填充物固有的颜色影响了柔性传感器的透明度,限制了其在可视化电子器件领域的应用。填充无机导电粒子(石墨烯、金属纳米线等)的柔性材料导电性较高,但填充物和基质之间的相分离通常会降低其应变性、韧性和疲劳性,甚至影响柔性材料的力学性能。因此目前已报道的大多数可穿戴传感器仍然停留在机械性和导电性的艰难选择上。In order to meet the needs of complex human motion, flexible and humanized design has gradually become an important part of wearable electronic devices. Flexible wearable sensors are devices with sensing functions prepared by imitating the characteristics of human skin. In recent years, they have shown great application potential in the fields of artificial intelligence, machine perception, and human-computer interaction. However, most flexible substrates are used as sensor materials. It faces great difficulties in conductivity, which affects its sensitivity and stability as a wearable sensor. Filling conductive materials is the most common method to solve such problems, in which organic conductive polymers (polyaniline, polypyrrole, etc.) are often filled to build a conductive network, good interfacial compatibility can prepare uniform conductive polymer elasticity body, but the inherent color of the filler affects the transparency of the flexible sensor, limiting its application in the field of visual electronics. Flexible materials filled with inorganic conductive particles (graphene, metal nanowires, etc.) have high conductivity, but the phase separation between the filler and the matrix usually reduces its strainability, toughness and fatigue, and even affects the mechanical properties of flexible materials . Therefore, most of the reported wearable sensors are still stuck in the difficult choice of mechanical and electrical conductivity.
水凝胶是具有网络结构的亲水性材料,高含量的水可以为导电离子提供一条运输路径,还可以通过定向设计获得其满意的弹性和韧性。而导电水凝胶可以构建带自由离子的导电网络,离子传导方式在生物系统中随处可见,还兼有优良的生物相容性,更是成为一种很有前途的可穿戴传感器的候选物。因此,开发水凝胶基可穿戴材料是目前用于人体运动检测、健康监测、软机器人的最佳选择。Hydrogel is a hydrophilic material with a network structure. A high content of water can provide a transport path for conductive ions, and its satisfactory elasticity and toughness can also be obtained through directional design. Conductive hydrogels can build a conductive network with free ions, and ion conduction can be seen everywhere in biological systems, and they also have excellent biocompatibility, making them a promising candidate for wearable sensors. Therefore, the development of hydrogel-based wearable materials is currently the best choice for human motion detection, health monitoring, and soft robotics.
但以水为溶剂的水凝胶在零度以下会失去弹性、延展性和导电性,从而造成传感性能的丧失,严重阻碍了其在现实生活中的实际应用。因此,开发能够在零下温度发挥作用的水凝胶作为柔性可穿戴传感器十分必要。为实现这一目标人们设计了许多防冻方法,例如通过添加离子化合物或有机溶剂制备抗冻导电水凝胶。王小慧等(发明专利CN110760152 A)公开了一种抗冻水凝胶及其制备方法与应用,通过添加锂盐赋予水凝胶低温下的抗冻特性,但锂盐有一定的毒性,长期接触不利于人体健康。袁伟忠等(发明专利CN112521630 A)公开了一种绿色柔性导电抗冻水凝胶的制备方法和应用,是将甘油引入水凝胶中提高材料的抗冻性,然而这种方法会降低水凝胶的机械性能。因此,可穿戴传感器用水凝胶首先必须具备优异的机械性能和抗冻性能。However, hydrogels using water as a solvent lose their elasticity, ductility, and conductivity at subzero temperatures, resulting in loss of sensing performance, which seriously hinders their practical applications in real life. Therefore, it is necessary to develop hydrogels capable of functioning at subzero temperatures as flexible and wearable sensors. Many antifreeze methods have been designed to achieve this goal, such as the preparation of antifreeze conductive hydrogels by adding ionic compounds or organic solvents. Wang Xiaohui et al. (invention patent CN110760152 A) disclosed an antifreeze hydrogel and its preparation method and application. By adding lithium salt, the hydrogel has antifreeze properties at low temperature, but lithium salt has certain toxicity, and long-term contact is not effective. Beneficial to human health. Yuan Weizhong et al. (invention patent CN112521630 A) disclosed a preparation method and application of a green flexible conductive antifreeze hydrogel. Glycerin is introduced into the hydrogel to improve the antifreeze of the material. However, this method will reduce the mechanical properties. Therefore, hydrogels for wearable sensors must firstly possess excellent mechanical properties and antifreeze properties.
另外,柔性可穿戴电子器件需要长期附着在人体皮肤或组织上,容易引起过敏或细菌感染,开发能够减缓或防止微生物繁殖或者在表面形成生物膜的可穿戴电子器件也是非常必要的。常用的抗菌材料一般是通过与抗生素、抗菌性金属离子或抗菌肽结合达到抗菌的目的。赵雪峰等(发明专利CN 108498543 A)公开了一种银离子超分子抗菌水凝胶及其制备方法和用途,通过将银离子添加到鸟嘌呤衍生物中形成超分子水凝胶,实现了银离子的缓释进而达到了抗菌的目的。钱军民等(发明专利CN 112480434 A)公开了一种铜离子抗菌水凝胶及制备方法和应用,通过添加铜盐赋予水凝胶抗菌性,克服了含铜抗菌材料释放缓慢、释放速度不可控的问题。陈刚(发明专利CN 112899331 A)公开了一种抗菌肽的发酵制备方法、抗菌肽水凝胶及应用,以PEG纳米载体为基础实现了乳酸的控释。然而,抗生素的广泛使用容易导致细菌的耐药性,金属离子的释放容易导致金属中毒,抗菌肽的合成过程较为复杂且易引起溶血效应。因此,可穿戴传感器用水凝胶还必须具备广谱的抗菌性能。In addition, flexible wearable electronic devices need to be attached to human skin or tissue for a long time, which is easy to cause allergies or bacterial infections. It is also necessary to develop wearable electronic devices that can slow down or prevent microbial reproduction or form biofilms on the surface. Commonly used antibacterial materials are generally combined with antibiotics, antibacterial metal ions or antibacterial peptides to achieve antibacterial purposes. Zhao Xuefeng et al. (invention patent CN 108498543 A) disclosed a silver ion supramolecular antibacterial hydrogel and its preparation method and application. By adding silver ions to guanine derivatives to form a supramolecular hydrogel, silver ion The slow-release and then reached the purpose of antibacterial. Qian Junmin et al. (invention patent CN 112480434 A) disclosed a copper ion antibacterial hydrogel and its preparation method and application. By adding copper salt, the hydrogel is endowed with antibacterial properties, which overcomes the slow release and uncontrollable release rate of copper-containing antibacterial materials. The problem. Chen Gang (invention patent CN 112899331 A) disclosed a fermentation preparation method of antimicrobial peptides, antimicrobial peptide hydrogel and its application, and realized the controlled release of lactic acid based on PEG nanocarriers. However, the widespread use of antibiotics can easily lead to drug resistance of bacteria, the release of metal ions can easily lead to metal poisoning, and the synthesis process of antimicrobial peptides is relatively complicated and can easily cause hemolytic effects. Therefore, wearable sensor hydrogels must also possess broad-spectrum antimicrobial properties.
兼具优异机械适用性、高灵敏性、长久抗菌性和抗冻性的多功能水凝胶的开发,对于可穿戴传感器的广泛应用具有重要的意义。聚离子液体(由离子液体形成的聚合物)结合了离子液体的低挥发性、热和电化学稳定性及聚合物的机械耐久性等特性。因其在结构单元中带有电荷,已被广泛用作生物相容材料、抗污、防霜涂层等材料中。抗菌聚合物也因其固有的抗菌活性比其他抗菌材料更长久,对人体细胞的毒性更低而引起人们的关注。质子化的伯胺(季铵盐)作为阳离子抗菌剂可以通过静电引力与带负电荷的细菌膜相互作用,导致细菌细胞膜上电荷分布不均匀,进而打破细胞膜在自然状态下的电荷平衡,使其无法承受渗透压而破裂,水和蛋白质等物质便会渗出细胞,导致细菌死亡。张聪等(发明专利CN107970488 A)公开了一种壳聚糖季铵盐水凝胶抗菌敷料及其制备方法,通过壳聚糖季铵盐、有机硅季铵盐和蒲公英提取液搭配使用,实验了对大肠杆菌和金色葡萄球菌的生长抑制。王荣民等(发明专利CN 111217956 A)公开了一种阳离子型释迦果状丙烯酸酯共聚物抗菌微球的制备方法,以阳离子型季铵盐为抗菌单元制备的抗菌微球具有广谱的抗菌性,可推广应用于植物抗菌、涂层、油墨等产品的抗菌防腐。但将季铵盐作为阳离子抗菌剂应用在可穿戴传感器方面的研究很少。The development of multifunctional hydrogels with excellent mechanical applicability, high sensitivity, long-lasting antibacterial and antifreeze properties is of great significance for the wide application of wearable sensors. Polyionic liquids (polymers formed from ionic liquids) combine the low volatility, thermal and electrochemical stability of ionic liquids with the mechanical durability of polymers. Because of the charge in the structural unit, it has been widely used in biocompatible materials, anti-fouling, anti-frost coatings and other materials. Antimicrobial polymers have also attracted attention due to their inherent antimicrobial activity that lasts longer than other antimicrobial materials and is less toxic to human cells. Protonated primary amines (quaternary ammonium salts), as cationic antibacterial agents, can interact with negatively charged bacterial membranes through electrostatic attraction, resulting in uneven charge distribution on bacterial cell membranes, thereby breaking the charge balance of cell membranes in a natural state, making them Unable to withstand the osmotic pressure and rupture, substances such as water and protein will seep out of the cell, causing bacterial death. Zhang Cong et al. (invention patent CN107970488 A) disclosed a chitosan quaternary ammonium hydrogel antibacterial dressing and its preparation method. The chitosan quaternary ammonium salt, organosilicon quaternary ammonium salt and dandelion extract were used in combination to experiment. Growth inhibition of Escherichia coli and Staphylococcus aureus. Wang Rongmin et al. (invention patent CN 111217956 A) disclosed a method for preparing cationic custard-shaped acrylate copolymer antibacterial microspheres. The antibacterial microspheres prepared with cationic quaternary ammonium salts as antibacterial units have broad-spectrum antibacterial properties. It can be popularized and applied to the antibacterial and anticorrosion of plant antibacterial, coating, ink and other products. However, there are few studies on the application of quaternary ammonium salts as cationic antibacterial agents in wearable sensors.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种工艺简单、生物相容性好、安全可靠的可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法。The technical problem to be solved by the present invention is to provide a method for preparing a multifunctional polymer dicationic hydrogel for wearable sensors with simple process, good biocompatibility, safety and reliability.
为解决上述问题,本发明所述的可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法,其特征在于:在冰水浴条件下,于容器中依次加入去离子水、离子液体、季铵盐,搅拌直至形成40~300 g/L的均相溶液;然后迅速加入交联剂、光引发剂,搅拌10~60 min,得到含有引发剂的单体混合物;所述含有引发剂的单体混合物转移至所需模具中,在光照下反应6~12 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。In order to solve the above problems, the preparation method of the multifunctional polymer dicationic hydrogel for wearable sensors according to the present invention is characterized in that: under the condition of ice-water bath, deionized water, ionic liquid, quaternary Ammonium salt, stirred until a homogeneous solution of 40-300 g/L was formed; then quickly added cross-linking agent, photoinitiator, and stirred for 10-60 min to obtain a monomer mixture containing the initiator; the monomer mixture containing the initiator The body mixture was transferred to the required mold, and reacted for 6-12 h under light to obtain the multifunctional polymer dicion hydrogel for wearable sensors.
所述冰水浴的温度为-4℃~0℃。The temperature of the ice-water bath is -4°C to 0°C.
所述离子液体、所述季铵盐、所述交联剂的质量比为0.20~3.30:1.10~5.50:0.01~0.30。The mass ratio of the ionic liquid, the quaternary ammonium salt, and the crosslinking agent is 0.20-3.30:1.10-5.50:0.01-0.30.
所述离子液体是指1-丁基-3-乙烯基咪唑溴盐、1-丙基-3-乙烯基咪唑磺酸盐或1-乙基-3-(1-乙烯基咪唑-3-己基)咪唑溴盐中的一种。The ionic liquid refers to 1-butyl-3-vinylimidazole bromide, 1-propyl-3-vinylimidazole sulfonate or 1-ethyl-3-(1-vinylimidazole-3-hexyl ) One of the imidazolium bromide salts.
所述季铵盐是指N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵或γ-(异丁烯酰胺)丙基三甲基氯化铵。The quaternary ammonium salt refers to N,N,N-trimethyl-3-(2-methacrylamino)-1-propylammonium chloride or γ-(methacrylamide)propyltrimethylchloride Ammonium.
所述交联剂为N,N′-亚甲基双丙烯酰胺或乙二醇二丙烯酸酯。The crosslinking agent is N,N'-methylenebisacrylamide or ethylene glycol diacrylate.
所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯或2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮中的一种,其用量为所述离子液体与所述季铵盐质量之和的2%~10%。The photoinitiator is 2-hydroxyl-2-methyl-1-phenylacetone, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester or 2-hydroxyl-4'-(2- The one in hydroxyethoxy)-2-methyl propiophenone, its consumption is 2%~10% of the sum of described ionic liquid and described quaternary ammonium salt quality.
所述光照的条件是指250~400 nm的紫外光。The conditions of the illumination refer to ultraviolet light of 250-400 nm.
本发明与现有技术相比具有以下优点:Compared with the prior art, the present invention has the following advantages:
1、本发明以离子液体、季铵盐为共聚单体,通过光引发自由基聚合制备了可穿戴传感器用多功能聚合物双阳离子水凝胶,不但制备工艺简单,而且生物相容性好,可直接作用于人体皮肤,安全可靠。1. The present invention uses ionic liquids and quaternary ammonium salts as comonomers to prepare multifunctional polymer dicationic hydrogels for wearable sensors through photo-induced free radical polymerization. The preparation process is simple and the biocompatibility is good. It can directly act on human skin, safe and reliable.
2、本发明中季铵盐的加入可以有效抑制长期佩戴过程中细菌的增值,降低传感器的更换频率,从而延长可穿戴传感器的使用寿命。2. The addition of quaternary ammonium salts in the present invention can effectively inhibit the growth of bacteria during long-term wearing, reduce the replacement frequency of sensors, and prolong the service life of wearable sensors.
3、本发明中离子液体的加入既增加了水凝胶的导电性,还能赋予双阳离水凝胶优异的抗冻性,扩大其在恶劣环境中的应用。3. The addition of the ionic liquid in the present invention not only increases the conductivity of the hydrogel, but also endows the dicationic hydrogel with excellent frost resistance, expanding its application in harsh environments.
4、本发明所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶内部存在大量的疏水缔合作用、静电相互作用,从而可进一步增强水凝胶的机械性能。同时,该双阳离子水凝胶能够准确地将人体的不同运动转化为电信号,并实现稳定传输。4. There are a large number of hydrophobic associations and electrostatic interactions inside the multifunctional polymer dicationic hydrogel for wearable sensors prepared by the present invention, which can further enhance the mechanical properties of the hydrogel. At the same time, the dicationic hydrogel can accurately convert different movements of the human body into electrical signals and achieve stable transmission.
5、本发明所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶可通过模具将其设计成所需形状,便于携带和使用。5. The multifunctional polymer dicationic hydrogel for wearable sensors prepared by the present invention can be designed into a desired shape through a mold, which is easy to carry and use.
6、本发明所制得的可穿戴传感器用多功能聚合物双阳离子水凝胶具有优异的力学性能和导电敏感性,这些特性决定了可穿戴传感器用多功能聚合物双阳离子水凝胶能够灵敏地实现人体运动的实时监测。另外,该双阳离子水凝胶对金黄色葡萄球菌和大肠杆菌均具有良好的抗菌性能,在低温时依然保持透明和柔韧性,并能经受循环扭曲、弯曲和折叠,这些特性使得可穿戴传感器用多功能聚合物双阳离子水凝胶具有类似智能皮肤的综合性能,在人机交互和智能可穿戴设备方面具有潜在的应用价值。6. The multifunctional polymer dicationic hydrogel for wearable sensors prepared by the present invention has excellent mechanical properties and conductivity sensitivity, and these characteristics determine that the multifunctional polymer dicationic hydrogel for wearable sensors can be sensitive Realize the real-time monitoring of human movement. In addition, the dicationic hydrogel has good antibacterial properties against both Staphylococcus aureus and Escherichia coli, remains transparent and flexible at low temperatures, and can withstand cyclic twisting, bending and folding, these properties make wearable sensors suitable for Multifunctional polymer dicationic hydrogels have comprehensive properties similar to smart skin and have potential applications in human-computer interaction and smart wearable devices.
附图说明Description of drawings
下面结合附图对本发明的具体实施方式作进一步详细的说明。The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings.
图1为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的宏观照片(左图)与SEM图(右图)。Figure 1 is the macroscopic photo (left picture) and SEM picture (right picture) of the multifunctional polymer dicion hydrogel for wearable sensors prepared in Example 1 of the present invention.
图2为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的红外谱图。Fig. 2 is the infrared spectrum of the multifunctional polymer dicationic hydrogel for wearable sensors prepared in Example 1 of the present invention.
图3为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的核磁谱图。Fig. 3 is the NMR spectrum of the multifunctional polymer dicion hydrogel for wearable sensors prepared in Example 1 of the present invention.
图4为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的力学性能测试图。Fig. 4 is a graph showing the mechanical properties of the multifunctional polymer dicative hydrogel for wearable sensors prepared in Example 1 of the present invention.
图5为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的导电性能测试图。Fig. 5 is a test diagram of the electrical conductivity of the multifunctional polymer dicationic hydrogel for wearable sensors prepared in Example 1 of the present invention.
图6为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的抗冻性测试图。Fig. 6 is a graph showing the frost resistance test of the multifunctional polymer dication hydrogel for wearable sensors prepared in Example 1 of the present invention.
图7为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶抗菌对比图。其中:a为金黄色葡萄球菌(对照);b为金黄色葡萄球菌(48 h);c 为大肠杆菌(对照);d为大肠杆菌(48 h)。Fig. 7 is a comparison diagram of the antibacterial effect of the multifunctional polymer dicationic hydrogel for wearable sensors prepared in Example 1 of the present invention. Among them: a is Staphylococcus aureus (control); b is Staphylococcus aureus (48 h); c is Escherichia coli (control); d is Escherichia coli (48 h).
图8为本发明实施例1所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的动作监测图。Fig. 8 is an action monitoring diagram of the multifunctional polymer dicationic hydrogel for wearable sensors prepared in Example 1 of the present invention.
具体实施方式Detailed ways
可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、离子液体、季铵盐,搅拌直至形成40~300 g/L的均相溶液;然后迅速加入交联剂、光引发剂,搅拌10~60 min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至所需模具中,采用250~400 nm的紫外光在光照下反应6~12 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。The preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, ionic liquid, and quaternary ammonium salt to the container in sequence under the condition of -4°C~0°C ice-water bath, and stir until 40~ 300 g/L homogeneous solution; then quickly add crosslinking agent and photoinitiator, stir for 10-60 min to obtain monomer mixture containing initiator; transfer the monomer mixture containing initiator to the required mold, and use The ultraviolet light of 250-400 nm was reacted under light for 6-12 h to obtain a multifunctional polymer dicationic hydrogel for wearable sensors.
其中:离子液体、季铵盐、交联剂的质量比(g/g)为0.20~3.30:1.10~5.50:0.01~0.30。Among them: the mass ratio (g/g) of ionic liquid, quaternary ammonium salt and crosslinking agent is 0.20~3.30:1.10~5.50:0.01~0.30.
离子液体是指1-丁基-3-乙烯基咪唑溴盐、1-丙基-3-乙烯基咪唑磺酸盐或1-乙基-3-(1-乙烯基咪唑-3-己基)咪唑溴盐中的一种。Ionic liquid refers to 1-butyl-3-vinylimidazolium bromide, 1-propyl-3-vinylimidazole sulfonate or 1-ethyl-3-(1-vinylimidazol-3-hexyl)imidazole One of the bromine salts.
季铵盐是指N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵或γ-(异丁烯酰胺)丙基三甲基氯化铵。The quaternary ammonium salt refers to N,N,N-trimethyl-3-(2-methacrylamide)-1-propylammonium chloride or γ-(methacrylamide)propyltrimethylammonium chloride.
交联剂为N,N′-亚甲基双丙烯酰胺或乙二醇二丙烯酸酯。The crosslinking agent is N,N'-methylenebisacrylamide or ethylene glycol diacrylate.
光引发剂为2-羟基-2-甲基-1-苯基丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯或2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮中的一种,其用量为所述离子液体与所述季铵盐质量之和的2%~10%。The photoinitiator is 2-hydroxy-2-methyl-1-phenylacetone, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester or 2-hydroxy-4′-(2-hydroxyethyl Oxygen)-2-methyl propiophenone, its consumption is 2%~10% of the sum of described ionic liquid and described quaternary ammonium salt quality.
实施例1 可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、2.16 g 1-丁基-3-乙烯基咪唑溴盐、2.21 gN,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵,搅拌直至形成200 g/L的均相溶液;然后迅速加入0.02 g N,N′-亚甲基双丙烯酰胺、0.11 g 2-羟基-2-甲基-1-苯基丙酮,搅拌20min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至所需模具中,采用254nm的紫外光光照下反应9 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。Example 1 Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, 2.16 g 1-butyl-3- Vinylimidazolium bromide, 2.21 g N,N,N-trimethyl-3-(2-methacrylamino)-1-propylammonium chloride, stirred until a homogeneous solution of 200 g/L was formed; then Add 0.02 g N,N′-methylenebisacrylamide and 0.11 g 2-hydroxy-2-methyl-1-phenylacetone rapidly, and stir for 20 min to obtain a monomer mixture containing an initiator; The body mixture was transferred to the desired mold, and reacted under 254nm ultraviolet light for 9 h to obtain a multifunctional polymer dicationic hydrogel for wearable sensors.
对所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶进行结构表征与性能分析:Structural characterization and performance analysis of the prepared multifunctional polymer dicationic hydrogel for wearable sensors:
⑴扫描电镜分析:⑴ Scanning electron microscope analysis:
用数码相机和扫描电镜(SEM)观察了本发明所制备的可穿戴传感器用多功能聚合物双阳离子水凝胶的宏观形貌(左图)和微观形貌(右图),结果如图1所示。可以看出,可穿戴传感器用多功能聚合物双阳离子水凝胶具有很好的可塑性,表面光滑柔韧,可以根据需求很容易地通过模具将其设计成所需要的形状。The macroscopic morphology (left image) and microscopic morphology (right image) of the multifunctional polymer dicationic hydrogel for wearable sensors prepared by the present invention were observed with a digital camera and a scanning electron microscope (SEM). The results are shown in Figure 1 shown. It can be seen that the multifunctional polymer dicationic hydrogel for wearable sensors has good plasticity, smooth and flexible surface, and can be easily designed into the desired shape through the mold according to the demand.
从SEM照片可以看出该材料显现出典型的多孔结构,且孔径较为均匀,大约为8 µm左右,这种结构可以分散承担来自各方面的外力,可提高材料对拉伸和挤压力的分散,且多孔的结构也有利于离子的迁移。此外,多孔结构也有利于增加水凝胶与细菌的接触面积,对其抗菌性能的提升具有积极作用。From the SEM photos, it can be seen that the material shows a typical porous structure, and the pore size is relatively uniform, about 8 µm. This structure can disperse external forces from all sides, and can improve the material's dispersion of tensile and extrusion forces. , and the porous structure is also conducive to the migration of ions. In addition, the porous structure is also conducive to increasing the contact area between the hydrogel and bacteria, which has a positive effect on improving its antibacterial performance.
⑵红外光谱分析:⑵Infrared spectrum analysis:
可穿戴传感器用多功能聚合物双阳离子水凝胶的红外光谱如图2所示。从图中可以看出在3438 cm-1处的吸收峰为-NH的伸缩振动;3032 cm-1和2956 cm-1附近的峰分别为C-H的不饱和饱和伸缩振动吸收峰;酰胺中羰基(C=O)的伸缩振动吸收峰位于1645 cm-1处;1484 cm-1处为-CH2-N+(CH3)3亚甲基的弯曲振动特征吸收峰。另外,3138 cm-1处的吸收峰是由咪唑中C-H的伸缩振动所致,1568 cm-1和1456 cm-1处的吸收峰归属于咪唑的骨架振动。由此证明所有单体均参与了反应,可穿戴传感器用多功能聚合物双阳离子水凝胶已制备成功。The infrared spectrum of the multifunctional polymer dication hydrogel for wearable sensors is shown in Fig. 2. It can be seen from the figure that the absorption peak at 3438 cm -1 is the stretching vibration of -NH; the peaks around 3032 cm -1 and 2956 cm -1 are the unsaturated saturation stretching vibration absorption peaks of CH; the carbonyl ( The stretching vibration absorption peak of C=O) is located at 1645 cm -1 ; the bending vibration characteristic absorption peak of -CH 2 -N + (CH 3 ) 3 methylene is at 1484 cm -1 . In addition, the absorption peak at 3138 cm -1 is caused by the stretching vibration of CH in imidazole, and the absorption peaks at 1568 cm -1 and 1456 cm -1 are attributed to the skeleton vibration of imidazole. This proves that all monomers participate in the reaction, and the multifunctional polymer dicationic hydrogel for wearable sensors has been successfully prepared.
⑶核磁谱图分析:⑶ NMR spectrum analysis:
可穿戴传感器用多功能聚合物双阳离子水凝胶的固体核磁碳谱如图3所示。176.70 ppm和161.06 ppm处的特征峰属于羰基的质子化学位移;咪唑环的特征共振峰出现在137.36 ppm和123.33 ppm处;53.83 ppm处的特征峰为季铵盐末端甲基的质子化学位移。由此可以证明所有单体均参与了聚合反应,进一步证明可穿戴传感器用多功能聚合物双阳离子水凝胶制备成功。The solid-state carbon NMR spectrum of the multifunctional polymer dicationic hydrogel for wearable sensors is shown in Figure 3. The characteristic peaks at 176.70 ppm and 161.06 ppm belong to the proton chemical shift of the carbonyl group; the characteristic resonance peaks of the imidazole ring appear at 137.36 ppm and 123.33 ppm; the characteristic peak at 53.83 ppm is the proton chemical shift of the terminal methyl group of the quaternary ammonium salt. It can be proved that all the monomers participated in the polymerization reaction, which further proves that the multifunctional polymer dicationic hydrogel was successfully prepared for wearable sensors.
⑷力学性能:⑷Mechanical properties:
在万能试验机上对可穿戴传感器用多功能聚合物双阳离子水凝胶进行了拉伸性能测试。The tensile properties of the multifunctional polymer dication hydrogels for wearable sensors were tested on a universal testing machine.
首先,将样品切成矩形切片(长= 50 mm,宽= 10 mm,厚=2 mm),单轴拉伸速率设定为50 mm/min。其次,将剪切好的凝胶矩形切片分别固定在万能试验机的上下两个夹具上,并旋紧夹具,注意旋夹的力度与凝胶两端夹入夹具的长度,以防止夹碎凝胶或者在拉伸过程中滑出。在进行单轴拉伸测试时中途不能中断,直至拉至凝胶断裂。如图4所示测试结果为可穿戴传感器用多功能聚合物双阳离子水凝胶的应力-应变(Stress-Strain)曲线。First, the sample was cut into rectangular slices (length = 50 mm, width = 10 mm, thickness = 2 mm), and the uniaxial tensile rate was set at 50 mm/min. Secondly, fix the cut gel rectangular slices on the upper and lower clamps of the universal testing machine, and tighten the clamps. Pay attention to the strength of the screw clamps and the length of the two ends of the gel clamped into the clamps to prevent the gel from being crushed. Glue or slip out during stretching. The uniaxial tensile test cannot be interrupted halfway until the gel breaks. The test results shown in Figure 4 are the stress-strain curves of the multifunctional polymer dicationic hydrogel for wearable sensors.
从图中可以看出可穿戴传感器用多功能聚合物双阳离子水凝胶具有优异的力学性能,最大应变超过500%,应力可达900 kPa,完全可满足柔性可穿戴传感器的弹性(0.4~1.9 MPa)和柔韧性(伸长率大于180 %)的要求。It can be seen from the figure that the multifunctional polymer dicationic hydrogel for wearable sensors has excellent mechanical properties, the maximum strain exceeds 500%, and the stress can reach 900 kPa, which can fully meet the elasticity of flexible wearable sensors (0.4~1.9 MPa) and flexibility (elongation greater than 180%) requirements.
⑸功能测试:⑸Function test:
①导电性能:①Conductive properties:
通过将可穿戴传感器用多功能聚合物双阳离子水凝胶作为导线与一个LED灯泡和一个3 V的外接电源连成完整电路来验证其导电性。测试过程:将双阳离子水凝胶接入电路中,LED灯泡就被点亮(图5a),这是由于双阳离子水凝胶具有良好的导电性。切断双阳离子水凝胶,电路就会断开,LED灯泡随即熄灭(图5b)。这证明了可穿戴传感器用多功能聚合物双阳离子水凝胶具有出色的电稳定性和敏感性,因此可作为可穿戴传感器用于人体运动的监测。The conductivity of the wearable sensor was verified by connecting the wearable sensor with a multifunctional polymer dicationic hydrogel as a wire with an LED bulb and a 3 V external power supply to form a complete circuit. Test process: The LED bulb is lit when the double cation hydrogel is connected to the circuit (Figure 5a), which is due to the good conductivity of the double cation hydrogel. Cutting through the dicationic hydrogel breaks the circuit and the LED bulb turns off (Fig. 5b). This demonstrates the excellent electrical stability and sensitivity of the multifunctional polymer dicationic hydrogel for wearable sensors, and thus can be used as a wearable sensor for human motion monitoring.
②抗冻性能:② Antifreeze performance:
将可穿戴传感器用多功能聚合物双阳离子水凝胶在-10℃冷冻24 h后,其仍保持透明度和柔韧性,进一步进行拉伸实验,发现多功能聚合物双阳离子水凝胶仍可被拉伸至原长度的2倍(图6)。说明离子液体的加入使可穿戴传感器用多功能聚合物双阳离子水凝胶具有良好的抗冻性,扩大了水凝胶作为柔性可穿戴材料的应用范围。After freezing at -10°C for 24 h with multifunctional polymeric cation hydrogels for wearable sensors, it still maintained transparency and flexibility. Further stretching experiments revealed that the multifunctional polymeric dianionic hydrogels could still be Stretch to twice its original length (Figure 6). It shows that the addition of ionic liquids makes the multifunctional polymer dicationic hydrogels for wearable sensors have good freezing resistance, which expands the application range of hydrogels as flexible wearable materials.
③抗菌性能:③Antibacterial properties:
测试过程:金黄色葡萄球菌和大肠杆菌分别作为革兰氏阳性菌和革兰氏阴性菌的代表,用平板计数法对可穿戴传感器用多功能聚合物双阳离子水凝胶的抗菌性能进行了测试。首先,将材料切割成圆片,在进行抗菌实验前对待测圆片进行灭菌处理。其次,将灭菌后的材料圆片和活化好的菌悬液加入到磷酸盐缓冲液(PBS缓冲液)中,作为实验组;将含有细菌的PBS缓冲液作为对照组。实验组和对照组样品均在37℃恒温振荡器中培养4 h。最后,将获得的菌悬液涂布在营养琼脂平板上,在37℃恒温培养箱中培育48 h,观察菌落的生长情况,其实验结果如图7所示。Test process: Staphylococcus aureus and Escherichia coli were used as representatives of Gram-positive and Gram-negative bacteria, respectively, and the antibacterial properties of multifunctional polymer dicationic hydrogels for wearable sensors were tested by plate counting . First, the material is cut into discs, and the discs to be tested are sterilized before the antibacterial experiment. Secondly, the sterilized material disk and the activated bacterial suspension were added to phosphate buffered saline (PBS buffer) as the experimental group; the PBS buffer containing bacteria was used as the control group. The samples of the experimental group and the control group were incubated in a constant temperature shaker at 37°C for 4 h. Finally, the obtained bacterial suspension was spread on a nutrient agar plate and incubated in a constant temperature incubator at 37°C for 48 h to observe the growth of the colonies. The experimental results are shown in Figure 7.
从培养板的抗菌照片中可以清楚的看到细菌菌落的生存情况(平板上生长的小白点代表存活的细菌菌落)。在对照平板上,金黄色葡萄球菌(a)和大肠杆菌(c)均显示出相对密集的菌落,表明在没有多功能聚合物双阳离子水凝胶的情况下,金黄色葡萄球菌和大肠杆菌会无限制的生长。将细菌菌悬液与多功能聚合物双阳离子水凝胶接触一段时间后,培养板上金黄色葡萄球菌(b)和大肠杆菌(d)菌落的生长明显受到了限制,这表明可穿戴传感器用多功能聚合物双阳离子水凝胶对金黄色葡萄球菌和大肠杆菌均具有良好的抗菌活性。The survival of bacterial colonies can be clearly seen from the antibacterial photos of the culture plate (the small white spots growing on the plate represent surviving bacterial colonies). On the control plate, both S. aureus (a) and E. coli (c) showed relatively dense colonies, indicating that S. Unlimited growth. The growth of Staphylococcus aureus (b) and Escherichia coli (d) colonies on the culture plate was significantly restricted after the bacterial suspension was in contact with the multifunctional polymer dicationic hydrogel for a period of time, which indicated that the wearable sensor could be used The multifunctional polymer dicationic hydrogel exhibited good antibacterial activity against both Staphylococcus aureus and Escherichia coli.
结果表明,该材料对革兰氏阳性菌(金黄色葡萄球菌)和革兰氏阴性菌(大肠杆菌)均有显著的抗菌性,并具有广谱的抗菌活性,这克服了柔性可穿戴传感器长期附着在人体皮肤或组织上容易引起的过敏和细菌感染的弊端。The results showed that the material showed remarkable antibacterial properties against both Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), and had a broad-spectrum antibacterial activity, which overcomes the long-term The disadvantages of allergies and bacterial infections easily caused by attachment to human skin or tissues.
④动作监测:④ Action monitoring:
将可穿戴传感器用多功能聚合物双阳离子水凝胶附着在人体各部位,并将其两端通过铜线连接到数字源表,通过数字源表记录可穿戴传感器用多功能聚合物双阳离子水凝胶的电阻随应变的变化,得到电阻-应变曲线,通过电阻-应变曲线形状和强度的变化可以实现对人体动作的准确监测。The wearable sensor is attached to various parts of the human body with multifunctional polymer dication hydrogel, and its two ends are connected to the digital source meter through copper wires, and the multifunctional polymer dication water gel used for the wearable sensor is recorded through the digital source meter. The resistance of the gel varies with strain to obtain a resistance-strain curve, and accurate monitoring of human body movements can be realized through changes in the shape and strength of the resistance-strain curve.
图8显示了可穿戴传感器用多功能聚合物双阳离子水凝胶在人体运动时其相对电阻(ΔR/R0)的变化。从图中可以看出,当人体关节开始运动时,多功能聚合物双阳离子水凝胶相对电阻的变化开始增大,关节运动幅度最大时达到最大值,随着关节动作的恢复,多功能聚合物双阳离子水凝胶的相对电阻变化开始减小,连续重复同一动作,信号也能连续重复输出,从而验证了可穿戴传感器用多功能聚合物双阳离子水凝胶的高应变敏感性、快动作响应性和可重复性。Figure 8 shows the relative resistance (ΔR/R 0 ) change of the multifunctional polymer dicative hydrogel for wearable sensors during human motion. It can be seen from the figure that when the human joints start to move, the change of the relative resistance of the multifunctional polymer dicationic hydrogel begins to increase, and reaches the maximum value when the joint movement range is the largest. The relative resistance change of the bication hydrogel begins to decrease, and the same action can be repeated continuously, and the signal can be continuously and repeatedly output, thus verifying the high strain sensitivity and fast action of the multifunctional polymer bication hydrogel for wearable sensors. Responsive and repeatable.
实施例2 可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、2.54 g 1-丙基-3-乙烯基咪唑磺酸盐、3.56 gN,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵,搅拌直至形成250 g/L的均相溶液;然后迅速加入0.22 g N,N′-亚甲基双丙烯酰胺、0.32 g 2,4,6-三甲基苯甲酰基苯基膦酸乙酯,搅拌30 min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至具有模具中,采用254 nm的紫外光光照下反应6 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。Example 2 Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, 2.54 g 1-propyl-3- Vinylimidazole sulfonate, 3.56 g N,N,N-trimethyl-3-(2-methacrylamido)-1-propylammonium chloride, stirred until a homogeneous solution of 250 g/L was formed; Then, 0.22 g of N,N′-methylenebisacrylamide and 0.32 g of
实施例3 可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、1.32 g 1-乙基-3-(1-乙烯基咪唑-3-己基)咪唑溴盐、4.05 g γ-(异丁烯酰胺)丙基三甲基氯化铵,搅拌直至形成115 g/L的均相溶液;然后迅速加入0.15 g乙二醇二丙烯酸酯、0.17 g 2-羟基-4′-(2-羟乙氧基)-2-甲基苯丙酮,搅拌25 min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至所需模具中,采用365 nm的紫外光在光照下反应10 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。Example 3 Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, 1.32 g 1-ethyl-3- (1-vinylimidazol-3-hexyl) imidazolium bromide, 4.05 g γ-(methacrylamide) propyltrimethylammonium chloride, stirred until a homogeneous solution of 115 g/L was formed; then quickly added 0.15 g ethyl alcohol Diol diacrylate, 0.17 g 2-hydroxyl-4'-(2-hydroxyethoxy)-2-methylpropiophenone, stirred for 25 min to obtain a monomer mixture containing the initiator; the monomer containing the initiator The mixture was transferred to the desired mold, and reacted with 365 nm ultraviolet light for 10 h under light to obtain a multifunctional polymer dicationic hydrogel for wearable sensors.
实施例4 可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、0.98 g 1-丁基-3-乙烯基咪唑溴盐、1.89 gγ-(异丁烯酰胺)丙基三甲基氯化铵,搅拌直至形成180 g/ L的均相溶液;然后迅速加入0.18 g 乙二醇二丙烯酸酯、0.33 g 2-羟基-2-甲基-1-苯基丙酮,搅拌50 min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至所需模具中,采用254 nm的紫外光光照下反应10 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。Example 4 Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, 0.98 g 1-butyl-3- Vinylimidazolium bromide, 1.89 g γ-(methacrylamide) propyltrimethylammonium chloride, stirred until a homogeneous solution of 180 g/L was formed; then quickly added 0.18 g ethylene glycol diacrylate, 0.33 g 2- Hydroxy-2-methyl-1-phenylacetone was stirred for 50 min to obtain a monomer mixture containing an initiator; the monomer mixture containing an initiator was transferred to the required mold and reacted under ultraviolet light at 254 nm for 10 h, The obtained multifunctional polymer dicationic hydrogel for wearable sensors.
实施例5 可穿戴传感器用多功能聚合物双阳离子水凝胶的制备方法:在-4℃~0℃冰水浴条件下,于容器中依次加入去离子水、3.01 g 1-乙基-3-(1-乙烯基咪唑-3-己基)咪唑溴盐、2.88 g N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵,搅拌直至形成70 g/L的均相溶液;然后迅速加入0.29 g N,N′-亚甲基双丙烯酰胺、0.55 g 2-羟基-2-甲基-1-苯基丙酮,搅拌40 min,得到含有引发剂的单体混合物;含有引发剂的单体混合物转移至所需模具中,采用365 nm的紫外光光照下反应12 h,即得到可穿戴传感器用多功能聚合物双阳离子水凝胶。Example 5 Preparation method of multifunctional polymer dicationic hydrogel for wearable sensors: Add deionized water, 3.01 g 1-ethyl-3- (1-vinylimidazol-3-hexyl)imidazolium bromide, 2.88 g N,N,N-trimethyl-3-(2-methacrylamido)-1-propylammonium chloride, stirred until 70 g/L homogeneous solution; then quickly added 0.29 g N,N′-methylenebisacrylamide, 0.55 g 2-hydroxy-2-methyl-1-phenylacetone, stirred for 40 min, and obtained The monomer mixture containing the initiator; the monomer mixture containing the initiator was transferred to the required mold, and reacted under 365 nm ultraviolet light for 12 h to obtain a multifunctional polymer dicationic hydrogel for wearable sensors.
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