CN114736477A - Anti-freezing hydrogel, preparation method thereof and flexible temperature sensor suitable for extremely low temperature response - Google Patents
Anti-freezing hydrogel, preparation method thereof and flexible temperature sensor suitable for extremely low temperature response Download PDFInfo
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Abstract
The invention discloses an antifreeze hydrogel, a preparation method thereof and a flexible temperature sensor suitable for extremely low temperature response, wherein the hydrogel has stronger antifreeze performance, not only can keep the original mechanical property for a long time in the environment of 60 ℃ below zero, but also has a large temperature response range (60 ℃ below zero to 60℃)) High sensitivity (Delta R/R)010%/° c) and good recycling stability. The hydrogel consists of polyvinyl alcohol monomers, phytic acid molecules and glucose and/or fructose. The hydrogel can form a network structure formed by interweaving flexible chains and rigid chains through crosslinking in various modes such as hydrogen bonds, ester bonds and electrostatic adsorption. And directly arranging electrodes on the anti-freezing hydrogel to obtain the flexible temperature sensor. The temperature sensor is simple in preparation method, excellent in performance and has great application prospect.
Description
Technical Field
The invention belongs to the technical field of flexible sensing devices, and relates to a flexible temperature sensor with extremely low temperature response.
Background
In recent years, flexible sensors have attracted much attention from the industrial and academic industries as one of the important embodiments of flexible electronics. Due to the unique mechanical flexibility and extensibility, the flexible sensor can be conformally attached to the surface of a non-planar object to sense the body or external environment information in real time. The common flexible sensors are classified according to the physical quantity to be measured, and comprise a temperature sensor, a humidity sensor, a pressure sensor, a flow sensor and the like. The temperature sensor is used as a common temperature sensing device and is generally applied to detection of human body temperature or environmental physical temperature. However, limited by the inherent properties of the flexible/soft body matrix material, current flexible temperature sensors are generally applicable only for sensing in the conventional temperature range (10-110 ℃), limiting their application in extreme environments (e.g., extremely high or low temperatures).
The intelligent hydrogel can respond to physical and chemical signals of outside temperature, humidity, pH, light and the like. The hydrogel can undergo a volumetric change or a structural change upon stimulation with a different signal. Therefore, intelligent hydrogels with good mechanical properties are important materials for the construction of flexible sensors. For example, CN104961862A shows that a temperature-responsive smart hydrogel generally loses water when the temperature increases and the volume of the hydrogel decreases, while when the temperature decreases, the hydrogel slowly absorbs water in the environment, and then expands and gradually returns to its original volume, during which the electrical resistance of the hydrogel changes due to the change of water in the polymer chain.
Although the smart temperature-responsive hydrogel studied at present can achieve some functions, such as driving muscle modules, controlling drug release and water purification, the smart temperature-responsive hydrogel also has a plurality of defects, such as small detection range, slow response speed, poor signal repeatability and short service life, in terms of temperature detection. The reason for these defects is mainly that most of the hydrogel contains water, and most of the hydrogel with high water content cannot resist freezing at low temperature and loses water rapidly at high temperature. Thus, for a hydrogel to be relatively stable in properties, it is desirable to have certain freeze resistance and dry resistance over a wide temperature range. The literature "biomedical anti-freezing polymeric hydrogels active in cold environments" (Yukun Jian, Stephan Handschuh-Wang, Jianwei Zhang, Wei Lu, Xuechang ZHou and Tao Chen, Materials Horizons,8,2021.) lists the current methods of achieving anti-freeze and anti-drying properties of hydrogels, and indicates that these physical mixing/displacement methods are mainly based on salt addition, alcohol, ionic liquids, etc., and are not long-lasting, since these solutes may leak out of the hydrogel and the anti-freeze properties are also greatly affected. Another method is to modify the structure of the polymer material by introducing polar groups into the polymer chains, where strong hydrogen bonding interactions in the hydrogel structure hinder the formation of ice crystals.
Disclosure of Invention
Aiming at the defects of the performance of the existing hydrogel based on temperature response, the invention provides the antifreeze hydrogel, the preparation method thereof and the flexible temperature sensor suitable for extremely low temperature response, wherein the antifreeze hydrogel is a high-density strong hydrogen bond crosslinked polymer network and can keep lasting antifreeze property at the temperature of-60 ℃. The temperature sensor has the characteristics of large temperature response range, high sensitivity and good recycling stability.
The technical scheme adopted by the invention is as follows:
according to a specific embodiment of the invention, the antifreeze hydrogel is obtained by crosslinking a synthetic or semisynthetic polymer material, phytic acid and a substance containing glucose and/or fructose through hydrogen bonds, ester bonds and electrostatic adsorption, and can maintain mechanical properties and temperature responsiveness in an environment as low as-60 ℃.
According to a specific embodiment of the present invention, the method for preparing the freeze resistant hydrogel comprises the following steps:
1) mixing synthetic or semi-synthetic polymer material such as polyvinyl alcohol solution with phytic acid solution;
2) adding glucose and/or fructose-containing material such as Mel into the obtained solution, and stirring to mix well;
3) standing the obtained solution to remove bubbles, heating in water bath, observing the color of the solution to gradually change from white transparent to brown, stopping heating, and cooling at room temperature;
4) and after cooling to room temperature, respectively carrying out multiple freezing and unfreezing cycles on the prepared solution at-50 ℃ and room temperature to obtain the anti-freezing hydrogel.
According to a specific embodiment of the invention, the mass concentration of the synthetic or semi-synthetic polymer material solution in the step 1) is 5-30%, the mass concentration of the phytic acid solution is 10-50%, and the mass ratio of the synthetic or semi-synthetic polymer material solution to the phytic acid solution is 1: 1.
According to a specific embodiment of the invention, the mass of the glucose and/or fructose in the step 2) is 40-50% of that of the synthetic or semi-synthetic polymer material solution.
According to a particular embodiment of the invention, said step 2) is carried out with stirring at 50 ℃.
According to a specific embodiment of the invention, the water bath heating temperature in the step 3) is 80 ℃, and the heating time is 2 hours.
The synthetic or semi-synthetic polymer material can be selected from polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, and cellulose derivatives (such as carboxymethyl cellulose, hydroxypropyl cellulose, etc.).
The glucose and/or fructose containing material may be selected from one or more of the following macromolecules: mel (all varieties containing more than 20% of glucose in nature), glucose or saccharide containing glucose and its derivatives (such as sucrose, white sugar, brown sugar, caramel, crystal sugar, maltose, etc.), fructose or saccharide containing fructose (such as sucrose, fruit juice, etc.).
According to one embodiment of the present invention, the flexible temperature sensor suitable for very low temperature response uses the anti-freezing hydrogel as described above as a sensing material.
According to a specific embodiment of the invention, the flexible temperature sensor is obtained by directly arranging electrodes on the antifreeze hydrogel, and the temperature response range is-60 ℃ to 60 ℃.
According to one embodiment of the present invention, the hydrogel of the present invention is composed of polyvinyl alcohol monomers, phytic acid molecules, and glucose and/or fructose. As the three monomers can be crosslinked in various modes such as hydrogen bonds, ester bonds, electrostatic adsorption and the like, the hydrogel can form a network structure formed by interweaving flexible chains and rigid chains. Different from common anti-freezing hydrogel, the hydrogel does not need to realize anti-freezing through steps of solvent replacement, ionic liquid addition and the like, and the free moving space of water molecules is limited mainly by utilizing the compact network structure of the hydrogel, so that the process of forming ice nuclei by water is inhibited below zero, the water in the network structure is converted into supercooled water and still is in a liquid state, and the elasticity of the hydrogel is retained.
The invention has the beneficial effects that:
the hydrogel and the temperature sensor prepared by the invention have the temperature detection range of-60 ℃ to 60 ℃, and still keep good elasticity under the condition of freeze drying for 5 days (see figure 1). The main technical characteristics comprise: (1) the hydroxyl groups rich in polyvinyl alcohol and phytic acid in polymer chains and glucose and fructose in honey are utilized to ensure that the hydrogel after crosslinking has stronger hydrogen bond effect in the structure, and the infrared spectrogram in figure 2 shows that the molecular weight is 2933.67cm-1And 3291.96cm-1A wider hydrogen bond absorption peak (2) is generated by utilizing the abundant hydrogen bond donor and acceptor in the six polar phosphate radicals in the phytic acid moleculeGreatly improves the density of hydrogen bonds in the polymer chain. (3) The hydrogel has good mechanical properties due to ester bonds between phytic acid and polyvinyl alcohol, glucose and/or fructose and electrostatic adsorption.
Drawings
FIG. 1 is a graph showing the elasticity of the antifreeze hydrogel after being left for 1 month in a refrigerator (-50 ℃ C.)
FIG. 2 is an infrared spectrum of the temperature responsive hydrogel
FIG. 3 is a schematic structural view of the hydrogel temperature sensor
FIG. 4 is a temperature sensing curve of a hydrogel temperature sensor at-60 ℃ to 60 ℃
FIG. 5 is a cycle test curve of the hydrogel temperature sensor and a commercial temperature sensor in the range of-60 ℃ to 60 ℃
Detailed Description
The technical solution of the present invention is further described below with reference to the specific drawings and examples.
Example 1
A preparation method of a temperature sensor based on antifreeze hydrogel comprises the following steps:
1) preparing a polyvinyl alcohol solution with the content of 5-30%: adding polyvinyl alcohol solid particles with corresponding mass into deionized water, and heating and stirring for 24 hours at the constant temperature of 60 ℃ to obtain transparent and viscous polyvinyl alcohol solution.
2) Taking a certain amount of polyvinyl alcohol solution and phytic acid solution (10-50% (w/w) in H)2O) stirring and mixing at a mass ratio of 1: 1;
3) adding appropriate amount of Mel (glucose is 40-50% of polyvinyl alcohol solution), and mixing at 50 deg.C for half an hour until uniformly mixed;
4) the mixed solution was allowed to stand for 10 to 20 minutes to remove air bubbles therein, and then the solution was heated at a water bath temperature of 80 ℃ and after heating for about 2 hours, the color of the solution was observed to gradually turn from white transparent to brown, and then the heating was stopped and cooling was performed at room temperature.
5) After cooling to room temperature (25-30 ℃), the prepared solution was poured into molds and then subjected to 3 freeze-thaw cycles at-50 ℃ and room temperature, respectively.
6) The hydrogel sample cured in the mold was removed and cut into a size of 3cm in length and 1.5cm in width.
7) Two rectangles (long: 3 cm; width: 0.5cm), fixing the carbon cloth on two sides of the hydrogel by using a high-temperature resistant Teflon adhesive tape, and then placing the prepared hydrogel temperature sensor in a temperature and humidity oven for testing.
Example 2
Uniformly mixing a polyvinyl alcohol solution (with the mass concentration of 5%) with phytic acid (with the mass concentration of 50%) and honey (with the mass of glucose and/or fructose being 40% of the polyvinyl alcohol solution) at 50 ℃, then heating at the constant temperature of 80 ℃ for 2 hours (the other conditions are the same as in example 1), and finally performing freeze thawing on the obtained solution for 3 times to obtain hydrogel with good elasticity but poor mechanical strength.
Example 3
Uniformly mixing a polyvinyl alcohol solution (with the mass concentration of 10 percent) with phytic acid (with the mass concentration of 50 percent) and honey (the mass of glucose and/or fructose is 40 percent of that of the polyvinyl alcohol solution) at 50 ℃, then heating the mixture at a constant temperature of 80 ℃ for 2 hours, and finally freezing and unfreezing the obtained solution for 3 times to obtain the solidified hydrogel (the other conditions are the same as those in example 1). Compared with the hydrogel prepared in the example 2, the hydrogel prepared in the example has better elasticity and better mechanical strength, and it can be seen that when the content of the polyvinyl alcohol solution is increased, the mechanical strength of the prepared hydrogel is correspondingly increased.
Example 4
Uniformly mixing a polyvinyl alcohol solution (with the mass concentration of 10 percent) with phytic acid (with the mass concentration of 50 percent) and honey (with the mass of glucose and/or fructose being 50 percent of that of the polyvinyl alcohol solution) at 50 ℃, then heating the mixture at the constant temperature of 80 ℃ for 2 hours, and finally freezing and unfreezing the obtained solution for 3 times to obtain the hydrogel with good frost resistance and adhesiveness (the rest conditions are the same as those in example 1). In contrast to example 3, when the contents of the polyvinyl alcohol solution and the phytic acid solution were not changed, the viscosity and freezing resistance of the hydrogel were improved by increasing the content of glucose.
The hydrogel prepared by the invention has strong frost resistance, can keep the original mechanical property in the environment of 60 ℃ below zero for a long time, is directly provided with electrodes, the electrodes are conductive carbon cloth, the conductive carbon cloth is cut into strips according to the mode shown in figure 3, then the strips are adhered to two sides of the hydrogel, the two sides are fixed by a high-temperature resistant Teflon adhesive tape, then the hydrogel temperature sensor is placed in a temperature and humidity oven, the humidity of the oven is set to be 30%, the temperature is 60 ℃ below zero, and then the test is carried out, and the temperature sensing curve obtained by the test is shown in figure 4. The sensitivity of the hydrogel temperature sensor is about 10%/DEG C, and after logarithmic ordinate, the curve is linear, and the hydrogel temperature sensor shows better stability and cycle test performance in long-time test (see that the hydrogel temperature sensor prepared by the invention is basically consistent with a cycle test curve of a commercial temperature sensor in a range of-60 ℃ to 60 ℃). It can be seen that the temperature sensor prepared based on the antifreeze hydrogel of the invention has large temperature response range (-60 ℃ to 60 ℃), high sensitivity (delta R/R)010%/° c) and good recycling stability.
Claims (9)
1. An anti-freezing hydrogel is characterized in that the anti-freezing hydrogel is obtained by crosslinking a synthetic or semi-synthetic polymer material, phytic acid and a substance containing glucose and/or fructose through hydrogen bonds, ester bonds and electrostatic adsorption, and can keep mechanical properties and temperature responsiveness in an environment as low as minus 60 ℃.
2. The antifreeze hydrogel of claim 1, wherein said synthetic or semi-synthetic polymeric material is one or more of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, and cellulose derivatives.
3. A process for the preparation of a freeze-resistant hydrogel according to claim 1, comprising the steps of:
1) mixing synthetic or semi-synthetic polymer material solution and phytic acid solution;
2) adding substances containing glucose and/or fructose into the obtained solution, and stirring until the substances are uniformly mixed;
3) standing the obtained solution to remove bubbles, heating in water bath, observing the color of the solution to gradually change from white transparent to brown, stopping heating, and cooling at room temperature;
4) and after cooling to room temperature, respectively carrying out multiple freezing and unfreezing cycles on the prepared solution at-50 ℃ and room temperature to obtain the anti-freezing hydrogel.
4. The method of claim 3, wherein the mass concentration of the synthetic or semi-synthetic polymer material solution in step 1) is 5-30%, the mass concentration of the phytic acid solution is 10-50%, and the mass ratio of the synthetic or semi-synthetic polymer material solution to the phytic acid solution is 1: 1.
5. The method for preparing antifreeze hydrogel according to claim 3, wherein the mass of the glucose and/or fructose in step 2) is 40-50% of that of the synthetic or semisynthetic polymer material solution.
6. Process for the preparation of antifreeze hydrogels according to claim 3, characterized in that in step 2) the mixing is carried out with stirring at 50 ℃.
7. Process for the preparation of antifreeze hydrogels of claim 3, characterized by the fact that in step 3) the water bath is heated at 80 ℃ for 2 hours.
8. A flexible temperature sensor suitable for very low temperature response, characterized in that a deicing hydrogel according to claim 1 or 2 or a deicing hydrogel produced by a process according to one of claims 3 to 7 is used as the sensor material.
9. The flexible temperature sensor suitable for very low temperature response of claim 8, wherein the flexible temperature sensor is obtained by directly arranging electrodes on the anti-freezing hydrogel, and the temperature response range is-60 ℃ to 60 ℃.
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| JP2023079003A JP7397542B2 (en) | 2022-05-18 | 2023-05-12 | Method for manufacturing freeze-resistant hydrogel and flexible temperature sensor suitable for cryogenic response |
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| CN110467735A (en) * | 2019-06-20 | 2019-11-19 | 哈尔滨工程大学 | A kind of product of hydrogel and preparation method thereof and aqueous gel |
| CN111372551A (en) * | 2017-12-27 | 2020-07-03 | 株式会社高丝 | Gel sheet for skin adhesion |
| CN112521630A (en) * | 2020-08-28 | 2021-03-19 | 同济大学 | Preparation method and application of green flexible conductive anti-freezing hydrogel |
| CN113943427A (en) * | 2021-09-30 | 2022-01-18 | 天津理工大学 | Preparation method of low-temperature-resistant and dehydration-resistant conductive hydrogel and strain sensor thereof |
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| US20190381469A1 (en) * | 2017-03-09 | 2019-12-19 | Nissan Chemical Corporation | Temperature-responsive hydrogel and method for producing the same |
| JP2021161415A (en) * | 2020-03-31 | 2021-10-11 | 学校法人東京理科大学 | Composition for the production of temperature sensor, temperature sensor, and method for producing temperature sensor |
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| CN111372551A (en) * | 2017-12-27 | 2020-07-03 | 株式会社高丝 | Gel sheet for skin adhesion |
| CN110467735A (en) * | 2019-06-20 | 2019-11-19 | 哈尔滨工程大学 | A kind of product of hydrogel and preparation method thereof and aqueous gel |
| CN112521630A (en) * | 2020-08-28 | 2021-03-19 | 同济大学 | Preparation method and application of green flexible conductive anti-freezing hydrogel |
| CN113943427A (en) * | 2021-09-30 | 2022-01-18 | 天津理工大学 | Preparation method of low-temperature-resistant and dehydration-resistant conductive hydrogel and strain sensor thereof |
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