CN115558301B - High-flexibility high-ionic-conductivity anti-freezing hydrogel and preparation method thereof - Google Patents
High-flexibility high-ionic-conductivity anti-freezing hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-flexibility high-ionic-conductivity anti-freezing hydrogel and a preparation method thereof. The invention has simple process, raw materials are derived from natural products, the environment is protected, the safety is high, the prepared antifreeze hydrogel has good flexibility, high mechanical strength and excellent ion conductivity and antifreeze performance, and can be used as a flexible sensing material to meet the increasingly diversified application requirements.
Description
Technical Field
The invention belongs to the field of natural polymer materials, and particularly relates to an antifreeze hydrogel with high flexibility and high ion conductivity and a preparation method thereof.
Background
The flexible electronic product has the characteristics of excellent conductive performance, light texture, softness, skin friendliness, easiness in fitting with skin and the like, and is considered as a key for designing the next-generation wearable equipment. As typical rigid materials, traditional bioelectronic devices are mainly manufactured by conductors such as metal and silicon, and are not suitable for the requirements of wearable electronics, robots and artificial intelligence age on flexible devices. Hydrogel is used as an emerging polymer soft intelligent material and is widely applied to the fields of electronic skin, strain sensors and the like. Because the application environment of the hydrogel flexible sensor is complex and changeable, in order to prolong the service life of the device, the hydrogel flexible sensor must have good flexibility to respond to external changes, and can keep good mechanical performance and stable electrical performance at a lower temperature. Therefore, from the design of hydrogel materials, the construction of the antifreeze hydrogel sensor with high flexibility and high ionic conductivity is widely focused by combining the influence of the sensor structure on the sensing performance.
Disclosure of Invention
The invention aims to provide an antifreeze hydrogel with high flexibility and high ionic conductivity and a preparation method thereof, aiming at the defects of the existing hydrogel flexible material and the preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-flexibility high-ionic-conductivity antifreeze hydrogel is prepared by the following steps:
(1) Adding the thermally expanded vermiculite and the saturated sodium chloride solution into an ultrafine mill together for ultrafine grinding, then adding the ultrafine vermiculite and the saturated sodium chloride solution into a lithium chloride solution with the concentration of 2.5mol/L for microwave-hydrothermal reaction, and then filtering to obtain a vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding gelatin into the vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing until the gelatin is completely dissolved to form a uniform vermiculite nano sheet/gelatin mixed solution;
(3) Dissolving urushiol in glycerol to prepare urushiol solution; and (3) dripping the urushiol solution into the vermiculite nano sheet/gelatin mixed solution obtained in the step (2), uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to obtain the antifreeze hydrogel with high flexibility and high ionic conductivity.
Further, the ratio of the amount of the thermally expanded vermiculite to the saturated sodium chloride solution used in the step (1) is 1g to 50mL; the superfine grinding time is 24-36 h; the temperature of the microwave-hydrothermal reaction is 100-130 ℃, the time is 20-30 h, and the microwave power is 500W.
Further, the dosage of the gelatin in the step (2) is converted according to the solid content of the vermiculite nano sheet/gelatin mixed solution which is 6 to 9 weight percent; the temperature of the condensation reflux is 100 ℃ and the time is 3 hours.
Further, the concentration of the urushiol solution in the step (3) is 0.2g/mL-0.5g/mL, and the mass ratio of the using amount to the vermiculite nano sheet/gelatin mixed solution is 1:4-1:7.
According to the invention, vermiculite nano sheets are used as a rapid ion transmission channel, and the high ion conductivity of the hydrogel is provided by combining the ion regulation and control effect of a gelatin intercalation nano structure; the thermal polymerization of urushiol in the hydrogel system and the dense and strong Si-O-C crosslinking formed by the phenolic hydroxyl groups of the urushiol and the vermiculite nano sheets improve the flexibility and mechanical properties of the hydrogel; the glycerol, gelatin, urushiol and water molecules in the hydrogel system form hydrogen bond combination, so that the formation of ice crystals at low temperature is inhibited, and the hydrogel is endowed with good freezing resistance.
The invention has the remarkable advantages that:
(1) The method has simple process, the used gelatin and urushiol are natural biomass, and the method has rich resources, high safety and environmental protection;
(2) The hydrogel prepared by the method has good flexibility, high ionic conductivity and good freezing resistance, can be biodegradable, and can be used as a flexible sensing material to meet the increasingly diversified application requirements.
Drawings
FIG. 1 is a graph showing macroscopic tensile properties of the antifreeze hydrogel obtained in example 2 (200 g weight lifted);
FIG. 2 is a graph showing the resistance change of the antifreeze hydrogel obtained in example 2 when used as a strain sensor for testing movement of a laryngeal junction (acoustic "self-standing and self-strength").
Detailed Description
A high-flexibility high-ionic-conductivity antifreeze hydrogel is prepared by the following steps:
(1) Adding the heat-expanded vermiculite and the saturated sodium chloride solution into an ultrafine mill according to the dosage ratio of 1g to 50mL, ultrafine grinding for 24-36 h, adding the mixture into a lithium chloride solution with the concentration of 2.5mol/L, performing microwave-hydrothermal reaction for 20-30 h at the temperature of 100-130 ℃ and under the condition of 500W, and filtering to obtain a vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding gelatin into the vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved to form a uniform vermiculite nano sheet/gelatin mixed solution with the solid content of 6-9 wt%;
(3) Dissolving urushiol in glycerol to prepare urushiol solution with the concentration of 0.2g/mL-0.5 g/mL; dripping the urushiol solution into the vermiculite nano sheet/gelatin mixed solution obtained in the step (2) according to the mass ratio of 1:4-1:7, uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to obtain the antifreeze hydrogel with high flexibility and high ionic conductivity.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Adding 10g of heat-expanded vermiculite and 500mL of saturated sodium chloride solution into an ultrafine mill for ultrafine grinding for 28 hours, then adding the ultrafine vermiculite into 200mL of lithium chloride solution with the concentration of 2.5mol/L, carrying out microwave-hydrothermal reaction for 20 hours at the temperature of 100 ℃ and under the condition of 500W, and filtering to obtain vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding 7g of gelatin into 93g of vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved, so as to prepare a vermiculite nano sheet/gelatin mixed solution with 7.1 weight percent of solid content;
(3) And (3) dissolving urushiol in glycerol to prepare a urushiol solution with the concentration of 0.3g/mL, then dripping 1.2g of urushiol solution into an 8g vermiculite nano sheet/gelatin mixed solution, uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to form the antifreeze hydrogel with high flexibility and high ionic conductivity.
Example 2
(1) Adding 10g of heat-expanded vermiculite and 500mL of saturated sodium chloride solution into an ultrafine mill for ultrafine grinding for 36 hours, then adding the mixture into 200mL of lithium chloride solution with the concentration of 2.5mol/L, carrying out microwave-hydrothermal reaction for 24 hours at the temperature of 120 ℃ and under the condition of 500W, and filtering to obtain vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding 8g of gelatin into 92g of vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved, so as to prepare a vermiculite nano sheet/gelatin mixed solution with the solid content of 8.1 wt%;
(3) And (3) dissolving urushiol in glycerol to prepare a urushiol solution with the concentration of 0.4g/mL, then dripping 1.4g of urushiol solution into an 8g vermiculite nano sheet/gelatin mixed solution, uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to form the antifreeze hydrogel with high flexibility and high ionic conductivity.
Example 3
(1) Adding 10g of heat-expanded vermiculite and 500mL of saturated sodium chloride solution into an ultrafine mill for ultrafine grinding for 24 hours, then adding the mixture into 200mL of 2.5mol/L lithium chloride solution, carrying out microwave-hydrothermal reaction for 30 hours at 110 ℃ and 500W, and filtering to obtain vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding 12g of gelatin into 188g of vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved, so as to prepare a vermiculite nano sheet/gelatin mixed solution with 6.1 weight percent of solid content;
(3) And (3) dissolving urushiol in glycerol to prepare a urushiol solution with the concentration of 0.5g/mL, then dripping 2g of urushiol solution into an 8g vermiculite nano sheet/gelatin mixed solution, uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to form the antifreeze hydrogel with high flexibility and high ionic conductivity.
Comparative example 1
(1) Adding 8g of gelatin into 92g of deionized water, and condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved, so as to prepare gelatin solution with the solid content of 8 wt%;
(2) Urushiol is dissolved in glycerol to prepare 0.4g/mL urushiol solution, then 1.4g urushiol solution is dripped into 8g gelatin solution, and after being stirred uniformly, the urushiol solution is transferred into a cylindrical mold and is placed at 50 ℃ for 4 hours to form gel.
Comparative example 2
(1) Adding 10g of heat-expanded vermiculite and 500mL of saturated sodium chloride solution into an ultrafine mill, ultrafine grinding for 36 hours, adding the mixture into 200mL of lithium chloride solution with the concentration of 2.5mol/L, carrying out microwave-hydrothermal reaction at 120 ℃ and 500W for 24 hours, and filtering to obtain vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding 8g of gelatin into 92g of vermiculite nano sheet solution obtained in the step (1), condensing and refluxing for 3 hours at 100 ℃ until the gelatin is completely dissolved, preparing a vermiculite nano sheet/gelatin mixed solution with the solid content of 8.1wt%, transferring the mixed solution into a cylindrical mold, and standing for 4 hours at 50 ℃ to form gel.
The hydrogel samples obtained in examples and comparative examples were subjected to performance test, and the results are shown in Table 1.
TABLE 1 results of Performance test of different hydrogels
As can be seen from table 1, the mechanical properties and conductivity of the hydrogel obtained in the example are significantly better than those of the comparative example, and the hydrogel obtained in the example can still maintain better conductivity and mechanical properties at a low temperature of-40 ℃, in contrast, the hydrogel obtained in the comparative example is not conductive, and the mechanical properties are severely reduced, because the vermiculite nano-sheets in the hydrogel of the example provide a rapid ion transmission channel, and the ion conductivity of the hydrogel is improved; the thermal polymerization of urushiol itself and the dense and strong Si-O-C crosslinking formed by phenolic hydroxyl groups and vermiculite nano sheets improve the flexibility and mechanical property of the hydrogel; the glycerol, gelatin, urushiol and water molecules form hydrogen bond combination, so that the formation of ice crystals at low temperature is inhibited, and the freezing resistance of the hydrogel is enhanced. In contrast to the example, the absence of vermiculite nanoplatelets in comparative example 1 does not allow the formation of ion transport channels in the hydrogel, and therefore the conductivity of the hydrogel is poor; in comparative example 2, the urushiol solution is absent, and the thermal polymerization of urushiol and coordination with vermiculite nano sheets cannot be performed in the hydrogel system, so that the gel network structure is loose, the mechanical property is reduced, and the frost resistance of the hydrogel is poor due to the absence of glycerol, so that the mechanical property is obviously reduced under the low-temperature condition.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. A preparation method of a high-flexibility high-ionic-conductivity antifreeze hydrogel is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding the thermally expanded vermiculite and the saturated sodium chloride solution into an ultrafine mill together for ultrafine grinding, then adding the ultrafine vermiculite and the saturated sodium chloride solution into a lithium chloride solution with the concentration of 2.5mol/L for microwave-hydrothermal reaction, and then filtering to obtain a vermiculite nano sheet solution with the solid content of 0.15 wt%;
(2) Adding gelatin into the vermiculite nano sheet solution obtained in the step (1), and condensing and refluxing until the gelatin is completely dissolved to form a uniform vermiculite nano sheet/gelatin mixed solution;
(3) Dissolving urushiol in glycerol to prepare urushiol solution; dripping the urushiol solution into the vermiculite nano sheet/gelatin mixed solution obtained in the step (2), uniformly stirring, transferring into a cylindrical mold, and standing at 50 ℃ for 4 hours to obtain the antifreeze hydrogel with high flexibility and high ionic conductivity;
and (3) converting the dosage of the gelatin in the step (2) according to the solid content of the vermiculite nano sheet/gelatin mixed solution of 6-9 wt%.
2. The method for preparing the high-flexibility high-ionic-conductivity antifreeze hydrogel according to claim 1, wherein the method comprises the following steps: the ratio of thermally expanded vermiculite to saturated sodium chloride solution used in step (1) was 1g:50mL.
3. The method for preparing the high-flexibility high-ionic-conductivity antifreeze hydrogel according to claim 1, wherein the method comprises the following steps: the superfine grinding time in the step (1) is 24-36 h.
4. The method for preparing the high-flexibility high-ionic-conductivity antifreeze hydrogel according to claim 1, wherein the method comprises the following steps: the temperature of the microwave-hydrothermal reaction in the step (1) is 100-130 ℃, the time is 20-30 h, and the microwave power is 500W.
5. The method for preparing the high-flexibility high-ionic-conductivity antifreeze hydrogel according to claim 1, wherein the method comprises the following steps: the temperature of the condensed reflux in the step (2) is 100 ℃ and the time is 3 hours.
6. The method for preparing the high-flexibility high-ionic-conductivity antifreeze hydrogel according to claim 1, wherein the method comprises the following steps: the concentration of the urushiol solution in the step (3) is 0.2g/mL-0.5g/mL, and the mass ratio of the using amount to the vermiculite nano sheet/gelatin mixed solution is 1:4-1:7.
7. A highly flexible, highly ionic conductive freeze resistant hydrogel made by the method of any one of claims 1-6.
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