CN116426001A - Preparation method of metal complex hydrogel and organogel containing acylhydrazone hydrophobic monomer - Google Patents

Abstract

The invention discloses a preparation method of metal complex hydrogel containing acylhydrazone hydrophobic monomer, which comprises the steps of uniformly mixing (E) -N- (4- (2- ([ 1,1' -biphenyl ] -4-ylmethylene) hydrazine-1-carbonyl) phenyl) acrylamide, acrylic acid, polyethylene glycol diacrylate and an initiator in an organic solvent, carrying out free radical polymerization on a prepolymer solution to form organic gel, forming the hydrogel through a solvent replacement method, and then immersing the hydrogel into a metal ion solution to obtain the metal complex hydrogel. The invention also discloses a preparation method of the organogel, which comprises the steps of uniformly mixing the acylhydrazone structure monomer, the acrylic acid, the polyethylene glycol diacrylate and the initiator in an organic solvent to obtain a prepolymer solution, and carrying out free radical polymerization on the prepolymer solution to form the organogel. The organic gel disclosed by the invention does not need to wrap an acylhydrazone structure in the whole synthesis process, the synthesis method is simple and convenient, and the prepared hydrogel has excellent mechanical property and fluorescence property.

Description

Translated fromChinese

含酰腙疏水单体的金属络合水凝胶及有机凝胶的制备方法Preparation method of metal complex hydrogel and organogel containing acylhydrazone hydrophobic monomer

技术领域technical field

本发明涉及金属络合水凝胶，特别涉及一种含酰腙疏水单体的金属络合水凝胶的制备方法及有机凝胶的制备方法。The invention relates to a metal complex hydrogel, in particular to a preparation method of a metal complex hydrogel containing an acylhydrazone hydrophobic monomer and a preparation method of an organic gel.

背景技术Background technique

水凝胶具有通过共价键和/或物理相互作用所形成的三维网络结构，因其高度亲水性、良好的保水能力和无与伦比的生物相容性，水凝胶在生物医药、传感识别及电子器件等领域受到广泛关注。但是传统水凝胶存在力学性能差、功能性缺乏、刺激响应慢的问题，这限制了水凝胶的实际应用。Hydrogels have a three-dimensional network structure formed by covalent bonds and/or physical interactions. Because of their high hydrophilicity, good water retention capacity and unparalleled biocompatibility, hydrogels are used in biomedicine, sensing and recognition And electronic devices and other fields have received extensive attention. However, traditional hydrogels suffer from poor mechanical properties, lack of functionality, and slow response to stimuli, which limit the practical application of hydrogels.

为了解决水凝胶力学性能差的问题，常常改变成胶策略来提高水凝胶的力学性能，如双网络水凝胶、纳米复合、高分子微球复合和Tetra-PEG水凝胶等。这些策略利用共价和/或非共价键提高水凝胶交联密度和强度，从而提高水凝胶的力学强度。其中，非共价键作为一种可逆的物理交联，可赋予水凝胶能量耗散机制从而增强其延展性和抗疲劳能力。同时，由于非共价键的动态性和可配置性，可根据需求赋予水凝胶相应的功能，如刺激响应性、形状记忆和抗溶胀等。In order to solve the problem of poor mechanical properties of hydrogels, gel formation strategies are often changed to improve the mechanical properties of hydrogels, such as double network hydrogels, nanocomposites, polymer microspheres composites, and Tetra-PEG hydrogels. These strategies utilize covalent and/or non-covalent bonds to increase the crosslink density and strength of hydrogels, thereby enhancing the mechanical strength of hydrogels. Among them, the non-covalent bond, as a reversible physical cross-linking, can endow the hydrogel with an energy dissipation mechanism to enhance its ductility and fatigue resistance. At the same time, due to the dynamic and configurable nature of non-covalent bonds, hydrogels can be endowed with corresponding functions such as stimuli responsiveness, shape memory, and anti-swelling, etc.

为赋予水凝胶功能性，一般引入金属配位体与金属离子络合，通过离子对配位体的络合作用改变水凝胶的状态，使水凝胶在不同环境中发生可视化的荧光颜色或强度的变化。In order to endow the hydrogel with functionality, metal ligands are generally introduced to complex with metal ions, and the state of the hydrogel is changed through the complexation of the ion-to-ligand, so that the hydrogel can produce visible fluorescent colors in different environments. or changes in intensity.

因疏水单体与水分子不相容，疏水单体难以直接引入水凝胶体系中。常用且有效的方法有溶剂交换法、胶束共聚法和构建两亲性分子等方法。溶剂交换法制备疏水缔合水凝胶，通常先将疏水单体和亲水单体同时溶解在良溶剂中原位聚合形成有机凝胶，然后再将有机凝胶浸泡于对于疏水单体为不良溶剂的纯水中进行溶剂交换，从而得到疏水缔合水凝胶。Due to the incompatibility between hydrophobic monomers and water molecules, it is difficult to directly introduce hydrophobic monomers into hydrogel systems. Commonly used and effective methods include solvent exchange method, micellar copolymerization method and the construction of amphiphilic molecules and other methods. The solvent exchange method is used to prepare hydrophobic association hydrogels. Usually, the hydrophobic monomer and the hydrophilic monomer are dissolved in a good solvent at the same time to polymerize in situ to form an organic gel, and then the organic gel is soaked in a poor solvent for the hydrophobic monomer. Solvent exchange was carried out in pure water to obtain hydrophobically associated hydrogels.

酰腙结构以其良好的配位能力、优异的生物相容性，酰腙结构引入水凝胶体系可以与金属离子络合产生荧光响应，但该类水凝胶成胶过程存在表面活性剂种类限制，不同酰腙结构需要选择相应的表面活性剂，否则无法包裹形成胶束，这限制了含酰腙疏水结构水凝胶的应用。The acylhydrazone structure is characterized by its good coordination ability and excellent biocompatibility. The introduction of the acylhydrazone structure into the hydrogel system can complex with metal ions to produce a fluorescent response, but there are surfactant types in the gelation process of this type of hydrogel. Restrictions, different acylhydrazone structures require the selection of corresponding surfactants, otherwise they cannot be encapsulated to form micelles, which limits the application of hydrogels containing acylhydrazone hydrophobic structures.

发明内容Contents of the invention

为了克服现有技术的上述缺点与不足，本发明的目的在于提供一种含酰腙疏水单体的金属络合水凝胶的制备方法，有机凝胶的合成全程不需要表面活性剂对酰腙结构进行包裹，合成方法简便。In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a method for preparing a metal-complexed hydrogel containing acylhydrazone hydrophobic monomers. The synthesis of the organic gel does not require surfactants to acylhydrazone. The structure is wrapped, and the synthesis method is simple.

本发明的另一目的在于提供一种有机凝胶的制备方法，全程不需要表面活性剂对酰腙结构进行包裹，合成方法简便。Another object of the present invention is to provide a method for preparing an organogel, which does not require surfactants to wrap the acylhydrazone structure in the whole process, and the synthesis method is simple.

本发明的目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:

含酰腙疏水单体的金属络合水凝胶的制备方法，包括以下步骤：The preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer comprises the following steps:

将有机凝胶浸泡于去离子水中2～4天，进行溶剂交换后得到水凝胶；再将水凝胶浸泡于金属离子溶液中6～12h，得到含酰腙疏水单体的金属络合水凝胶；Soak the organic gel in deionized water for 2 to 4 days, and perform solvent exchange to obtain a hydrogel; then soak the hydrogel in a metal ion solution for 6 to 12 hours to obtain metal complex water containing acylhydrazone hydrophobic monomers gel;

所述有机凝胶由以下步骤制备而成：The organogel is prepared by the following steps:

将(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、丙烯酸、聚乙二醇二丙烯酸酯与引发剂在有机溶剂中混合均匀，得到预聚液，预聚液发生自由基聚合形成有机凝胶。(E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide, acrylic acid, polyethylene glycol The diacrylate and the initiator are uniformly mixed in an organic solvent to obtain a pre-polymerization liquid, and the pre-polymerization liquid undergoes radical polymerization to form an organic gel.

优选的，所述有机凝胶的具体制备过程包括：Preferably, the specific preparation process of the organogel comprises:

1)将4-氨基苯甲酰肼和4-苯基苯甲醛加入到第一有机溶剂中，滴加催化剂冰醋酸，在氮气保护下65～85℃搅拌反应3～12h；反应结束后过滤得到粗产物，洗涤，干燥得(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼；1) Add 4-aminobenzoic hydrazide and 4-phenylbenzaldehyde to the first organic solvent, add the catalyst glacial acetic acid dropwise, and stir and react at 65-85°C for 3-12 hours under the protection of nitrogen; filter after the reaction to obtain The crude product was washed and dried to obtain (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzohydrazide;

2)将(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和三乙胺溶于第二有机溶剂中，搅拌均匀后滴加丙烯酰氯，在氮气氛围下50～70℃反应12～24h；反应结束后沉淀，过滤除去溶剂后，对粗产物进行重结晶，干燥得到(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺；2) Dissolve (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and triethylamine in the second organic solvent and stir well Then add acryloyl chloride dropwise, and react at 50-70°C for 12-24 hours under nitrogen atmosphere; precipitate after the reaction, remove the solvent by filtration, recrystallize the crude product, and dry to obtain (E)-N-(4-(2- ([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide;

3)将(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、丙烯酸、聚乙二醇二丙烯酸酯在第三有机溶剂中混合均匀，充入氮气后加入引发剂，在65～75℃下聚合4～8h，得到有机凝胶。3) Add (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide, acrylic acid, polyethylene The diol diacrylate is uniformly mixed in the third organic solvent, filled with nitrogen and then added with an initiator, and polymerized at 65-75° C. for 4-8 hours to obtain an organic gel.

优选的，所述金属离子溶液为Zn²⁺、Cd²⁺、Al³⁺、Pb²⁺或Mn²⁺溶液，浓度为0.0125～0.2M；每克水凝胶加入金属离子溶液1～3ml。Preferably, the metal ion solution is a Zn²⁺ , Cd²⁺ , Al³⁺ , Pb²⁺ or Mn²⁺ solution with a concentration of 0.0125-0.2M; 1-3ml of the metal ion solution is added per gram of hydrogel.

优选的，步骤1)中，4-氨基苯甲酰肼和4-苯基苯甲醛的摩尔比为1:(0.8～1.2)，每毫摩尔的4-氨基苯甲酰肼加入冰醋酸的量为0.1～0.2ml。Preferably, in step 1), the mol ratio of 4-aminobenzoic hydrazide and 4-phenylbenzaldehyde is 1:(0.8～1.2), the amount of glacial acetic acid added to every millimol of 4-aminobenzoic hydrazide 0.1-0.2ml.

优选的，步骤2)中，所述的(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和丙烯酰氯的摩尔比为1:2～1:4，丙烯酰氯与三乙胺的摩尔比为1:1.2～1:1.6。Preferably, in step 2), the molar ratio of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzohydrazide to acryloyl chloride The molar ratio of acryloyl chloride to triethylamine is 1:1.2 to 1:1.6.

优选的，步骤2)中，步骤3)中，所述的丙烯酸在第三溶剂中摩尔浓度为3～6mM，(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺和丙烯酸的摩尔比为1:20～1:104，聚乙二醇二丙烯酸酯的摩尔浓度为丙烯酸摩尔浓度的0.5～2％，引发剂的用量为丙烯酸质量的1～3％。Preferably, in step 2), in step 3), the molar concentration of the acrylic acid in the third solvent is 3-6mM, (E)-N-(4-(2-([1,1'-biphenyl Base]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide and acrylic acid molar ratio is 1:20～1:104, the molar concentration of polyethylene glycol diacrylate is the molar concentration of acrylic acid 0.5-2%, the amount of the initiator is 1-3% of the mass of the acrylic acid.

优选的，所述的引发剂为偶氮二异丁腈、过硫酸钾或过硫酸铵。Preferably, the initiator is azobisisobutyronitrile, potassium persulfate or ammonium persulfate.

优选的，所述的聚乙二醇二丙烯酸酯的相对分子质量为400、600或1000的聚乙二醇二丙烯酸酯中的一种或多种。Preferably, the relative molecular weight of the polyethylene glycol diacrylate is one or more of polyethylene glycol diacrylates with a molecular mass of 400, 600 or 1000.

优选的，步骤1)中，所述的第一有机溶剂为甲醇、乙醇、乙腈中一种或多种；步骤2)中，所述的第二有机溶剂为N-甲基吡咯烷酮；步骤3)中，所述的第三有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜中的一种或两种。Preferably, in step 1), the first organic solvent is one or more of methanol, ethanol, acetonitrile; in step 2), the second organic solvent is N-methylpyrrolidone; step 3) Among them, the third organic solvent is one or both of N,N-dimethylformamide and dimethyl sulfoxide.

优选地，步骤1)中，所述的洗涤是用甲醇洗涤；步骤2)中，所述的沉淀是在水中沉淀，重结晶是粗产物溶解在吡啶后，于正己烷中进行重结晶；步骤4)中，每克有机凝胶浸泡于100～200ml去离子水中。Preferably, in step 1), the washing is washing with methanol; in step 2), the precipitation is precipitation in water, and recrystallization is carried out after the crude product is dissolved in pyridine, and then recrystallized in n-hexane; step 4), soak each gram of organogel in 100-200ml deionized water.

优选地，步骤5)中，所述的金属离子溶液为Zn²⁺、Cd²⁺、Al³⁺、Pb²⁺或Mn²⁺溶液，分别由二水合乙酸锌、氯化镉、九水合硝酸铝、无水乙酸铅或四水合硝酸锰溶解于去离子水中配制而成，浓度为0.0125～0.2M，每克水凝胶加入金属溶液的用量为1～3ml。Preferably, in step 5), the metal ion solution is Zn²⁺ , Cd²⁺ , Al³⁺ , Pb²⁺ or Mn²⁺ solution, which are prepared from zinc acetate dihydrate, cadmium chloride, nitric acid nonahydrate Aluminum, anhydrous lead acetate or manganese nitrate tetrahydrate are dissolved in deionized water, the concentration is 0.0125-0.2M, and the amount of adding metal solution per gram of hydrogel is 1-3ml.

一种有机凝胶的制备方法，包括以下步骤：A preparation method of organogel, comprising the following steps:

将酰腙结构单体、丙烯酸、聚乙二醇二丙烯酸酯与引发剂在有机溶剂中混合均匀，得到预聚液，预聚液发生自由基聚合形成有机凝胶。The acylhydrazone structural monomer, acrylic acid, polyethylene glycol diacrylate and initiator are uniformly mixed in an organic solvent to obtain a pre-polymerization liquid, and the pre-polymerization liquid undergoes radical polymerization to form an organic gel.

与现有技术相比，本发明具有以下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1)本发明的含酰腙疏水单体的金属络合水凝胶的制备方法，有机凝胶的合成全程不需要表面活性剂对酰腙结构进行包裹，合成方法简便。(1) The preparation method of the metal complexed hydrogel containing acylhydrazone hydrophobic monomers of the present invention, the synthesis of the organic gel does not require surfactants to wrap the acylhydrazone structure, and the synthesis method is simple.

(2)本发明的含酰腙疏水单体的金属络合水凝胶的制备方法，通过溶剂交换法将其作为疏水部分引入以丙烯酸为亲水单体的水凝胶体系中，酰腙配体间的疏水缔合作用以及Zn²⁺离子与配体间的金属络合作用都可以提高水凝胶的力学强度。此外，引入含酰腙疏水单体也赋予了水凝胶荧光性能和离子响应性，与金属络合前后存在明显的荧光性能变化。(2) The preparation method of the metal complexed hydrogel containing acylhydrazone hydrophobic monomer of the present invention is introduced as a hydrophobic part into a hydrogel system using acrylic acid as a hydrophilic monomer by a solvent exchange method, and the acylhydrazone complex The hydrophobic association between bodies and the metal complexation between Zn²⁺ ions and ligands can improve the mechanical strength of hydrogels. In addition, the introduction of acylhydrazone-containing hydrophobic monomers also endowed the hydrogel with fluorescent properties and ion responsiveness, and there were obvious changes in fluorescent properties before and after complexing with metals.

(3)本发明的含酰腙疏水单体的金属络合水凝胶的制备方法，可针对不同力学性能需求通过改变酰腙疏水单体比例以及金属离子浓度进行调节。(3) The preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomers of the present invention can be adjusted by changing the ratio of acylhydrazone hydrophobic monomers and the concentration of metal ions according to different mechanical property requirements.

(4)本发明的含酰腙疏水单体的金属络合水凝胶的制备方法，成胶方法简单，制备条件温和，可适用于大部分含酰腙疏水单体引入水凝胶体系中，且种类和浓度均不受限制。(4) The preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomers of the present invention has a simple gelation method and mild preparation conditions, and is applicable to the introduction of most acylhydrazone hydrophobic monomers into hydrogel systems, And the type and concentration are not limited.

(5)本发明制备的含酰腙疏水单体的金属络合水凝胶，拉伸应力可达410～865kPa，最大拉伸应变可达324～559％。(5) The metal complex hydrogel containing acylhydrazone hydrophobic monomer prepared by the present invention has a tensile stress of 410-865kPa and a maximum tensile strain of 324-559%.

(6)本发明制备的有机凝胶，与金属离子络合前后荧光变化明显且具有可视化的特点，具有较好的识别能力。(6) The organogel prepared by the present invention has obvious fluorescence changes before and after complexing with metal ions and has the characteristics of visualization, and has better recognition ability.

(7)本发明的含酰腙疏水单体的金属络合水凝胶，其荧光强度具有可调性，可对各类信息进行保存与加密，可应用于智能光学器件、离子检测、传感器等领域的应用。(7) The metal complex hydrogel containing acylhydrazone hydrophobic monomer of the present invention has adjustable fluorescence intensity, can store and encrypt various information, and can be applied to intelligent optical devices, ion detection, sensors, etc. field applications.

附图说明Description of drawings

图1为本发明制备的水凝胶的金属离子响应原理图。Fig. 1 is a schematic diagram of the metal ion response of the hydrogel prepared in the present invention.

图2为本发明的实施例1所得(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图。Fig. 2 is the result of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzohydrazide obtained in Example 1 of the present invention using d6-DMSO as solvent¹ H NMR spectrum.

图3为本发明的实施例1所得(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图。Figure 3 is (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl) obtained in Example 1 of the present invention¹ H NMR spectrum of acrylamide with d6-DMSO as solvent.

图4为本发明的实施例1、实施例2、实施例3所得原始水凝胶的拉伸应力应变图。Fig. 4 is a tensile stress-strain diagram of the original hydrogel obtained in Example 1, Example 2, and Example 3 of the present invention.

图5为本发明的实施例1、实施例6、实施例7所得金属络合水凝胶的拉伸应力应变图。Fig. 5 is a tensile stress-strain diagram of the metal complex hydrogel obtained in Example 1, Example 6, and Example 7 of the present invention.

图6为本发明的实施例1、实施例4、实施例5、实施例6、实施例7所得水凝胶金属离子络合前后的荧光发射谱图。Fig. 6 is the fluorescence emission spectrum before and after metal ion complexation of the hydrogel obtained in Example 1, Example 4, Example 5, Example 6, and Example 7 of the present invention.

图7为本发明的实施例1所得原始水凝胶用Zn²⁺进行多次荧光印刷的效果图。Fig. 7 is an effect diagram of multiple times of fluorescent printing of the original hydrogel obtained in Example 1 of the present invention with Zn²⁺ .

具体实施方式Detailed ways

下面结合实施例，对本发明作进一步地详细说明，但本发明的实施方式不限于此。The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

下面实施例中，除特别说明，水凝胶的性能采用以下方法检测：In the following examples, unless otherwise specified, the performance of the hydrogel is detected by the following methods:

(1)拉伸性能测试：室温下将长方形水凝胶样品在KJ-1065A-T拉伸强度试验机上进行测试，样品实际测量长度为10mm，厚度1mm，宽度4mm，拉伸速率为100mm/min。(1) Tensile performance test: At room temperature, the rectangular hydrogel sample is tested on a KJ-1065A-T tensile strength testing machine. The actual measured length of the sample is 10mm, the thickness is 1mm, the width is 4mm, and the tensile rate is 100mm/min .

(2)荧光性能测试：水凝胶的荧光测试在Hitachi F-4500荧光分光光度计中进行。测试的水凝胶样品尺寸为15mm×7.5mm×1mm，将其置于两片玻璃片之间固定进行测试。激发波长为377nm，激发及发射狭缝为10nm。(2) Fluorescence performance test: The fluorescence test of the hydrogel was carried out in a Hitachi F-4500 fluorescence spectrophotometer. The tested hydrogel sample has a size of 15mm×7.5mm×1mm, which is placed between two glass slides and fixed for testing. The excitation wavelength is 377nm, and the excitation and emission slits are 10nm.

(3)水凝胶的荧光印刷性能测试：将刻有“SCUT”字样的模具浸泡在0.3mol/L的Zn2+溶液中5s，把模具置于水凝胶上方5s，取下模具，在365nm的UV光照射下观察水凝胶表面是否有带强烈黄色荧光的“SCUT”字样，判断所制备的水凝胶能否用于荧光印刷。(3) Fluorescence printing performance test of hydrogel: Soak the mold engraved with "SCUT" in 0.3mol/L Zn2+ solution for 5s, place the mold on top of the hydrogel for 5s, remove the mold, and test at 365nm Under UV light irradiation, observe whether there is a word "SCUT" with strong yellow fluorescence on the surface of the hydrogel, and judge whether the prepared hydrogel can be used for fluorescent printing.

实施例1Example 1

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将10mg(5wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶。(3) Preparation of organogel: 10 mg (5 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.05M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal-complex hydrogel: soak the hydrogel in 1 ml of 0.05M Zn²⁺ solution for 6 hours at room temperature to obtain metal-complex hydrogel.

图1为本发明制备的水凝胶的金属离子响应原理，图中虚线部分为含酰腙结构与Zn²⁺所形成的动态金属配位键，改善了水凝胶的力学性能。在水凝胶受到应力时可作为水凝胶中的能力耗散机制，从而提高其延展性。Fig. 1 is the metal ion response principle of the hydrogel prepared by the present invention. The dotted line in the figure is the dynamic metal coordination bond formed by the acylhydrazone structure and Zn²⁺ , which improves the mechanical properties of the hydrogel. It can serve as an energy dissipation mechanism in the hydrogel when the hydrogel is stressed, thereby enhancing its ductility.

由图4可知，水凝胶的拉伸应力为185.8kPa，拉伸应变为129％。结合图4中实施例2、实施例3中的水凝胶应力应变曲线可知，疏水单体之间产生的疏水缔合作用明显增强了水凝胶的力学性能，这是因为水凝胶体系中存在的疏水缔合点，不仅增加了交联密度，同时在受到应力时可以作为水凝胶中的能量耗散机制，从而提高其延展性。因此，可以通过改变含酰腙疏水单体比例从而调节力学性能以满足不同应用场景下的需求。It can be seen from Figure 4 that the tensile stress of the hydrogel is 185.8kPa, and the tensile strain is 129%. Combined with the hydrogel stress-strain curves in Example 2 and Example 3 in Figure 4, it can be seen that the hydrophobic association between hydrophobic monomers significantly enhances the mechanical properties of the hydrogel, because the hydrogel system The presence of hydrophobic association points not only increases the crosslink density, but also acts as an energy dissipation mechanism in the hydrogel under stress, thereby enhancing its ductility. Therefore, the mechanical properties can be adjusted to meet the needs of different application scenarios by changing the proportion of hydrophobic monomers containing acylhydrazone.

水凝胶在不同金属离子浓度溶液中浸泡得到不同力学性能的金属络合水凝胶，如图5所示，金属离子浓度为0.05M时，拉伸应力为242.6kPa，拉伸应变为203％，随着金属离子浓度增大，金属络合水凝胶的拉伸应力与拉伸应变均逐渐增大，金属离子浓度为0.2M时，拉伸应力为865kPa，拉伸应变为559％。因此，也可以通过改变金属离子浓度从而调节力学性能以满足不同应用场景下的需求。The hydrogel is soaked in solutions with different metal ion concentrations to obtain metal complex hydrogels with different mechanical properties. As shown in Figure 5, when the metal ion concentration is 0.05M, the tensile stress is 242.6kPa and the tensile strain is 203%. , as the metal ion concentration increases, the tensile stress and tensile strain of the metal complex hydrogel increase gradually. When the metal ion concentration is 0.2M, the tensile stress is 865kPa and the tensile strain is 559%. Therefore, the mechanical properties can also be adjusted by changing the concentration of metal ions to meet the needs of different application scenarios.

由图6可知，水凝胶在金属离子络合后呈现明显的荧光变化，随着Zn²⁺浓度的增加，金属络合水凝胶的荧光强度逐渐增大。当Zn²⁺浓度从从0.0125M增加到0.2M时，水凝胶的荧光强度提升了448％。说明该水凝胶对Zn²⁺具有较好的选择响应性，并且其荧光强度具有较好的可调性，在离子检测传感器中具有潜在的应用前景。It can be seen from Figure 6 that the hydrogel exhibits obvious fluorescence changes after metal ion complexation, and the fluorescence intensity of the metal complex hydrogel increases gradually with the increase of Zn²⁺ concentration. When the concentration of Zn²⁺ increased from 0.0125M to 0.2M, the fluorescence intensity of the hydrogel increased by 448%. It shows that the hydrogel has a good selective response to Zn²⁺ , and its fluorescence intensity is well tunable, and has potential application prospects in ion detection sensors.

由图7可知，基于水凝胶的荧光调控性能，该水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from Figure 7 that based on the fluorescence regulation properties of the hydrogel, the hydrogel can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例2Example 2

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred and reacted at 65°C for 6h under the protection of nitrogen; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将20mg(10wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 20 mg (10 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.0125M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal complex hydrogel: soak the hydrogel in 1 ml of 0.0125M Zn²⁺ solution for 6 hours at room temperature to obtain metal complex hydrogel.

由图4可知，实施例2水凝胶的拉伸应力为290.8kPa，拉伸应变为215％；结合图4中实施例1、实施例3中的水凝胶应力应变曲线可知，疏水单体之间产生的疏水缔合作用明显增强了水凝胶的力学性能，这是因为水凝胶体系中存在的疏水缔合点，不仅增加了交联密度，同时在受到应力时可以作为水凝胶中的能量耗散机制，从而提高其延展性。因此，可以通过改变含酰腙疏水单体比例从而调节力学性能以满足不同应用场景下的需求。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from Figure 4 that the tensile stress of the hydrogel in Example 2 is 290.8kPa, and the tensile strain is 215%; combined with the hydrogel stress-strain curves in Example 1 and Example 3 in Figure 4, it can be known that the hydrophobic monomer The hydrophobic association generated between them significantly enhances the mechanical properties of the hydrogel, because the hydrophobic association points in the hydrogel system not only increase the crosslink density, but also act as The energy dissipation mechanism, thereby improving its ductility. Therefore, the mechanical properties can be adjusted to meet the needs of different application scenarios by changing the proportion of hydrophobic monomers containing acylhydrazone. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例3Example 3

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将30mg(15wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 30 mg (15 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.0125M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal complex hydrogel: soak the hydrogel in 1 ml of 0.0125M Zn²⁺ solution for 6 hours at room temperature to obtain metal complex hydrogel.

由图4可知，实施例3水凝胶的拉伸应力为410.2kPa，拉伸应变为324％；结合图4中实施例1、实施例2中的水凝胶应力应变曲线可知，疏水单体之间产生的疏水缔合作用明显增强了水凝胶的力学性能，这是因为水凝胶体系中存在的疏水缔合点，不仅增加了交联密度，同时在受到应力时可以作为水凝胶中的能量耗散机制，从而提高其延展性。因此，可以通过改变含酰腙疏水单体比例从而调节力学性能以满足不同应用场景下的需求。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from Figure 4 that the tensile stress of the hydrogel in Example 3 is 410.2kPa, and the tensile strain is 324%; combined with the hydrogel stress-strain curves in Example 1 and Example 2 in Figure 4, it can be known that the hydrophobic monomer The hydrophobic association generated between them significantly enhances the mechanical properties of the hydrogel, because the hydrophobic association points in the hydrogel system not only increase the crosslink density, but also act as The energy dissipation mechanism, thereby improving its ductility. Therefore, the mechanical properties can be adjusted to meet the needs of different application scenarios by changing the proportion of hydrophobic monomers containing acylhydrazone. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例4Example 4

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将10mg(5wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 10 mg (5 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.0125M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal complex hydrogel: soak the hydrogel in 1 ml of 0.0125M Zn²⁺ solution for 6 hours at room temperature to obtain metal complex hydrogel.

由图4可知，实施例4水凝胶的拉伸应力为185.8kPa，拉伸应变为129％。由图6可知，水凝胶在金属离子络合后呈现明显的荧光变化，随着Zn²⁺浓度的增加，金属络合水凝胶的荧光强度逐渐增大。说明该水凝胶对Zn²⁺具有较好的选择响应性，并且其荧光强度具有较好的可调性，在离子检测传感器中具有潜在的应用前景。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from FIG. 4 that the tensile stress of the hydrogel in Example 4 is 185.8 kPa, and the tensile strain is 129%. It can be seen from Figure 6 that the hydrogel exhibits obvious fluorescence changes after metal ion complexation, and the fluorescence intensity of the metal complex hydrogel increases gradually with the increase of Zn²⁺ concentration. It shows that the hydrogel has a good selective response to Zn²⁺ , and its fluorescence intensity is well tunable, and has potential application prospects in ion detection sensors. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例5Example 5

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将10mg(5wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 10 mg (5 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.025M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal-complex hydrogel: soak the hydrogel in 1 ml of 0.025M Zn²⁺ solution for 6 hours at room temperature to obtain metal-complex hydrogel.

由图4可知，实施例5水凝胶的拉伸应力为185.8kPa，拉伸应变为129％。由图6可知，水凝胶在金属离子络合后呈现明显的荧光变化，随着Zn²⁺浓度的增加，金属络合水凝胶的荧光强度逐渐增大。说明该水凝胶对Zn²⁺具有较好的选择响应性，并且其荧光强度具有较好的可调性，在离子检测传感器中具有潜在的应用前景。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from FIG. 4 that the tensile stress of the hydrogel in Example 5 is 185.8 kPa, and the tensile strain is 129%. It can be seen from Figure 6 that the hydrogel exhibits obvious fluorescence changes after metal ion complexation, and the fluorescence intensity of the metal complex hydrogel increases gradually with the increase of Zn²⁺ concentration. It shows that the hydrogel has a good selective response to Zn²⁺ , and its fluorescence intensity is well tunable, and has potential application prospects in ion detection sensors. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例6Example 6

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将10mg(5wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 10 mg (5 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.1M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal-complex hydrogel: soak the hydrogel in 1 ml of 0.1M Zn²⁺ solution for 6 hours at room temperature to obtain metal-complex hydrogel.

由图4和图5可知，实施例6水凝胶的拉伸应力为185.8kPa，拉伸应变为129％；金属络合水凝胶的拉伸应力为437.3kPa，拉伸应变为517％。由图6可知，水凝胶在金属离子络合后呈现明显的荧光变化，随着Zn²⁺浓度的增加，金属络合水凝胶的荧光强度逐渐增大。说明该水凝胶对Zn²⁺具有较好的选择响应性，并且其荧光强度具有较好的可调性，在离子检测传感器中具有潜在的应用前景。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from Figure 4 and Figure 5 that the tensile stress of the hydrogel in Example 6 is 185.8kPa, and the tensile strain is 129%; the tensile stress of the metal complex hydrogel is 437.3kPa, and the tensile strain is 517%. It can be seen from Figure 6 that the hydrogel exhibits obvious fluorescence changes after metal ion complexation, and the fluorescence intensity of the metal complex hydrogel increases gradually with the increase of Zn²⁺ concentration. It shows that the hydrogel has a good selective response to Zn²⁺ , and its fluorescence intensity is well adjustable, and has potential application prospects in ion detection sensors. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

实施例7Example 7

(1)制备(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼：将10mmol 4-氨基苯甲酰肼和10mmol 4-苯基苯甲醛加入到甲醇中，滴加1ml冰醋酸作为催化剂，在氮气保护下65℃搅拌反应6h；反应结束后过滤得到粗产物，在甲醇中洗涤，过滤，干燥。(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼以d6-DMSO为溶剂的¹H NMR谱图如图2所示。(1) Preparation of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide: mix 10mmol 4-aminobenzoic hydrazide and 10mmol 4 -Phenylbenzaldehyde was added to methanol, 1ml of glacial acetic acid was added dropwise as a catalyst, and the reaction was stirred at 65°C for 6h under nitrogen protection; after the reaction was completed, the crude product was obtained by filtration, washed in methanol, filtered, and dried. The¹ H NMR spectrum of (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide using d6-DMSO as solvent is shown in Figure 2 .

(2)制备(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺：将2mmol(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和4.8mmol三乙胺溶于N-甲基吡咯烷酮中，搅拌均匀后滴加4mmol丙烯酰氯，在氮气氛围下65℃反应12h；反应结束后在水中沉淀，过滤得到粗产物，将其溶解在吡啶后，于正己烷中重结晶，干燥。(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺以d6-DMSO为溶剂的¹H NMR谱图如图3所示。(2) Preparation of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide: 2mmol ( E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and 4.8mmol triethylamine were dissolved in N-methylpyrrolidone, after stirring 4mmol of acryloyl chloride was added dropwise, and reacted at 65°C for 12h under a nitrogen atmosphere; after the reaction, it precipitated in water and was filtered to obtain a crude product, which was dissolved in pyridine, recrystallized in n-hexane, and dried. (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide¹ The H NMR spectrum is shown in FIG. 3 .

(3)制备有机凝胶：将10mg(5wt％)(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、200mg丙烯酸、60mg聚乙二醇二丙烯酸酯(相对分子质量为400)在1ml二甲基亚砜中混合均匀，充入氮气后加入3mg偶氮二异丁腈，在65℃下聚合6h，得到有机凝胶.(3) Preparation of organogel: 10 mg (5 wt%) of (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl ) phenyl) acrylamide, 200mg acrylic acid, 60mg polyethylene glycol diacrylate (relative molecular mass is 400) are mixed uniformly in 1ml dimethyl sulfoxide, add 3mg azobisisobutyronitrile after being filled with nitrogen, in Polymerized at 65°C for 6 h to obtain an organogel.

(4)制备水凝胶：室温下将有机凝胶浸泡于100ml去离子水中2天进行溶剂交换，每12h换一次水，得到水凝胶。(4) Preparation of hydrogel: Soak the organogel in 100 ml of deionized water for 2 days at room temperature for solvent exchange, and change the water every 12 hours to obtain a hydrogel.

(5)制备金属络合水凝胶：室温下将水凝胶浸泡于1ml的0.2M Zn²⁺溶液中6h，得到金属络合水凝胶。(5) Preparation of metal complex hydrogel: soak the hydrogel in 1 ml of 0.2M Zn²⁺ solution for 6 hours at room temperature to obtain metal complex hydrogel.

由图4和图5可知，实施例7水凝胶的拉伸应力为185.8kPa，拉伸应变为129％；金属络合水凝胶的拉伸应力为865kPa，拉伸应变为559％。由图6可知，水凝胶在金属离子络合后呈现明显的荧光变化，随着Zn²⁺浓度的增加，金属络合水凝胶的荧光强度逐渐增大。说明该水凝胶对Zn²⁺具有较好的选择响应性，并且其荧光强度具有较好的可调性，在离子检测传感器中具有潜在的应用前景。此外，水凝胶可用于可擦拭的荧光书写以及信息加密与储存。将蘸满Zn²⁺溶液的棉签作为笔，在水凝胶上可以在1s内快速且清晰地画出字母“H”。然后，利用EDTA溶液可在30s内擦除该荧光信息，并且可再次利用相同方法书写字母“N”。由此可知，水凝胶的荧光书写功能具有较好的对比度和可逆性。It can be seen from Figure 4 and Figure 5 that the tensile stress of the hydrogel in Example 7 is 185.8kPa, and the tensile strain is 129%; the tensile stress of the metal complex hydrogel is 865kPa, and the tensile strain is 559%. It can be seen from Figure 6 that the hydrogel exhibits obvious fluorescence changes after metal ion complexation, and the fluorescence intensity of the metal complex hydrogel increases gradually with the increase of Zn²⁺ concentration. It shows that the hydrogel has a good selective response to Zn²⁺ , and its fluorescence intensity is well adjustable, and has potential application prospects in ion detection sensors. In addition, hydrogels can be used for erasable fluorescent writing and information encryption and storage. Using a cotton swab dipped in Zn²⁺ solution as a pen, the letter "H" can be drawn quickly and clearly on the hydrogel within 1 s. Then, the fluorescent information can be erased within 30 seconds using EDTA solution, and the letter "N" can be written again using the same method. It can be seen that the fluorescent writing function of the hydrogel has good contrast and reversibility.

本发明利用溶剂交换法将酰腙疏水单体引入水凝胶体系中，提高其力学性能，通过金属离子与酰腙疏水单体的络合作用赋予水凝胶以荧光性能，同时能够实现荧光书写及信息加密与储存等功能，使其在离子检测、柔性传感器、光学器件等领域具有巨大的应用价值。The present invention introduces the acylhydrazone hydrophobic monomer into the hydrogel system by using a solvent exchange method to improve its mechanical properties, endows the hydrogel with fluorescent properties through the complexation of metal ions and the acylhydrazone hydrophobic monomer, and can realize fluorescent writing at the same time And information encryption and storage functions, so that it has great application value in ion detection, flexible sensors, optical devices and other fields.

上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, substitutions and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims (10)

Translated fromChinese

1.含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，包括以下步骤：1. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer, is characterized in that, comprises the following steps:将有机凝胶浸泡于去离子水中2～4天，进行溶剂交换后得到水凝胶；再将水凝胶浸泡于金属离子溶液中6～12h，得到含酰腙疏水单体的金属络合水凝胶；Soak the organic gel in deionized water for 2 to 4 days, and perform solvent exchange to obtain a hydrogel; then soak the hydrogel in a metal ion solution for 6 to 12 hours to obtain metal complex water containing acylhydrazone hydrophobic monomers gel;所述有机凝胶由以下步骤制备而成：The organogel is prepared by the following steps:将(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、丙烯酸、聚乙二醇二丙烯酸酯与引发剂在有机溶剂中混合均匀，得到预聚液，预聚液发生自由基聚合形成有机凝胶。(E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide, acrylic acid, polyethylene glycol The diacrylate and the initiator are uniformly mixed in an organic solvent to obtain a pre-polymerization liquid, and the pre-polymerization liquid undergoes radical polymerization to form an organic gel.2.根据权利要求1所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，所述有机凝胶的具体制备过程包括：2. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 1, is characterized in that, the concrete preparation process of described organogel comprises:1)将4-氨基苯甲酰肼和4-苯基苯甲醛加入到第一有机溶剂中，滴加催化剂冰醋酸，在氮气保护下65～85℃搅拌反应3～12h；反应结束后过滤得到粗产物，洗涤，干燥得(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼；1) Add 4-aminobenzoic hydrazide and 4-phenylbenzaldehyde to the first organic solvent, add the catalyst glacial acetic acid dropwise, and stir and react at 65-85°C for 3-12 hours under the protection of nitrogen; filter after the reaction to obtain The crude product was washed and dried to obtain (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzohydrazide;2)将(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和三乙胺溶于第二有机溶剂中，搅拌均匀后滴加丙烯酰氯，在氮气氛围下50～70℃反应12～24h；反应结束后沉淀，过滤除去溶剂后，对粗产物进行重结晶，干燥得到(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺；2) Dissolve (E)-N'-([1,1'-biphenyl]-4-ylmethylene)-4-aminobenzoic hydrazide and triethylamine in the second organic solvent and stir well Then add acryloyl chloride dropwise, and react at 50-70°C for 12-24 hours under nitrogen atmosphere; precipitate after the reaction, remove the solvent by filtration, recrystallize the crude product, and dry to obtain (E)-N-(4-(2- ([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide;3)将(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺、丙烯酸、聚乙二醇二丙烯酸酯在第三有机溶剂中混合均匀，充入氮气后加入引发剂，在65～75℃下聚合4～8h，得到有机凝胶。3) Add (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide, acrylic acid, polyethylene The diol diacrylate is uniformly mixed in the third organic solvent, filled with nitrogen and then added with an initiator, and polymerized at 65-75° C. for 4-8 hours to obtain an organic gel.3.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，所述金属离子溶液为Zn²⁺、Cd²⁺、Al³⁺、Pb²⁺或Mn²⁺溶液，浓度为0.0125～0.2M；每克水凝胶加入金属离子溶液1～3ml。3. The preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, characterized in that, the metal ion solution is Zn²⁺ , Cd²⁺ , Al³⁺ , Pb^{2 +} or Mn²⁺ solution, the concentration is 0.0125 ~ 0.2M; add 1 ~ 3ml of metal ion solution per gram of hydrogel.4.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，步骤1)中，4-氨基苯甲酰肼和4-苯基苯甲醛的摩尔比为1:(0.8～1.2)，每毫摩尔的4-氨基苯甲酰肼加入冰醋酸的量为0.1～0.2ml。4. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, is characterized in that, in step 1), 4-aminobenzohydrazide and 4-phenylbenzaldehyde The molar ratio is 1:(0.8-1.2), and the amount of glacial acetic acid added to every mmol of 4-aminobenzoic hydrazide is 0.1-0.2ml.5.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，步骤2)中，所述的(E)-N'-([1,1'-联苯]-4-基亚甲基)-4-氨基苯甲酰肼和丙烯酰氯的摩尔比为1:2～1:4，丙烯酰氯与三乙胺的摩尔比为1:1.2～1:1.6。5. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, is characterized in that, in step 2), described (E)-N'-([1,1 The molar ratio of '-biphenyl]-4-ylmethylene)-4-aminobenzohydrazide and acryloyl chloride is 1:2～1:4, and the molar ratio of acryloyl chloride and triethylamine is 1:1.2～ 1:1.6.6.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，步骤2)中，步骤3)中，所述的丙烯酸在第三溶剂中摩尔浓度为3～6mM，(E)-N-(4-(2-([1,1'-联苯基]-4-基亚甲基)肼-1-羰基)苯基)丙烯酰胺和丙烯酸的摩尔比为1:20～1:104，聚乙二醇二丙烯酸酯的摩尔浓度为丙烯酸摩尔浓度的0.5～2％，引发剂的用量为丙烯酸质量的1～3％。6. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, is characterized in that, in step 2), in step 3), described acrylic acid is molar in the third solvent The concentration is 3~6mM, (E)-N-(4-(2-([1,1'-biphenyl]-4-ylmethylene)hydrazine-1-carbonyl)phenyl)acrylamide and acrylic acid The molar ratio is 1:20-1:104, the molar concentration of polyethylene glycol diacrylate is 0.5-2% of the molar concentration of acrylic acid, and the amount of initiator is 1-3% of the mass of acrylic acid.7.根据权利要求1或2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，所述的引发剂为偶氮二异丁腈、过硫酸钾或过硫酸铵。7. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 1 or 2, is characterized in that, described initiator is azobisisobutyronitrile, potassium persulfate or persulfate ammonium sulfate.8.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，所述的聚乙二醇二丙烯酸酯为相对分子质量为400、600或1000的聚乙二醇二丙烯酸酯中的一种或多种。8. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, is characterized in that, described polyethylene glycol diacrylate is that relative molecular mass is 400,600 or 1000 One or more of polyethylene glycol diacrylates.9.根据权利要求2所述的含酰腙疏水单体的金属络合水凝胶的制备方法，其特征在于，步骤1)中，所述的第一有机溶剂为甲醇、乙醇、乙腈中一种或多种；步骤2)中，所述的第二有机溶剂为N-甲基吡咯烷酮；步骤3)中，所述的第三有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜中的一种或两种。9. the preparation method of the metal complex hydrogel containing acylhydrazone hydrophobic monomer according to claim 2, is characterized in that, in step 1), described first organic solvent is one of methyl alcohol, ethanol, acetonitrile one or more; in step 2), the second organic solvent is N-methylpyrrolidone; in step 3), the third organic solvent is N,N-dimethylformamide, dimethyl One or both of the sulfoxides.10.一种有机凝胶的制备方法，其特征在于，包括以下步骤：10. A method for preparing an organogel, comprising the following steps:将酰腙结构单体、丙烯酸、聚乙二醇二丙烯酸酯与引发剂在有机溶剂中混合均匀，得到预聚液，预聚液发生自由基聚合形成有机凝胶。The acylhydrazone structural monomer, acrylic acid, polyethylene glycol diacrylate and initiator are uniformly mixed in an organic solvent to obtain a pre-polymerization liquid, and the pre-polymerization liquid undergoes radical polymerization to form an organic gel.

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