CN117777360A - Preparation method of deep eutectic liquid gel, product and application thereof - Google Patents
Preparation method of deep eutectic liquid gel, product and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of ionic liquid gel, in particular to a preparation method of deep eutectic liquid gel, a product and application thereof, wherein the preparation method comprises the following steps: mixing and dissolving betaine and acrylic acid to obtain a deep eutectic solution; dissolving chitosan quaternary ammonium salt in a deep eutectic solution, adding a photoinitiator and a cross-linking agent, and continuing dissolving under a light-shielding condition to obtain a precursor solution; and (3) placing the precursor liquid under ultraviolet rays for curing reaction to obtain the deep eutectic liquid gel. Compared with the conventionally prepared deep eutectic liquid gel, the preparation method provided by the invention can form the deep eutectic liquid gel with a double-network structure, and the gel has the advantages of high antibacterial performance, high adhesion, low hysteresis rate, high stability and the like.
Description
Technical Field
The invention relates to the technical field of ionic liquid gel, in particular to a preparation method of deep eutectic liquid gel, a product and application thereof.
Background
At present, the requirements of the high and new technical field on the application of wearable sensors are continuously improved in the human society intelligence continuous upgrading. Compared with the traditional materials such as metal, plastic, silica gel and the like, the ionic liquid gel system not only has high strain capacity which is lack of rigid materials, but also has conductivity which is not possessed by the materials such as rubber, silica gel and the like. Meanwhile, in order to create a real-time application scene, low response time and fatigue resistance of a long-time application material are also indispensable, and as the ionic liquid can reduce the melting point of the gel material, the gel can adapt to the application of a considerable part of extreme climate areas, can be better close to the application scene of a sensor in life, and has very high potential market application value and prospect.
Among these, deep eutectic gels (eutec gels) are a special type of ionic liquid gels, anhydrous solvent gels, which are gel networks formed by two or more components having ionic liquid properties solidifying a solution or sol enhanced by a gelling agent by the force of ionic crosslinking. Deep eutectic gels, a special form of ionic liquid gel, have the characteristics of ionic liquid gels, but have unique properties and application potential due to their special deep eutectic phase change formation mechanism. Therefore, the deep eutectic gel has wide application prospect in the fields of electrochemistry, energy storage and conversion, sensors and the like.
However, the deep eutectic liquid gel used at present has the following problems in practical application:
1) A relatively complex preparation process: the preparation process of the deep eutectic gel is relatively complex, and the proportion of the deep eutectic substance and the choice of the solvent need to be accurately controlled to realize the formation of the gel. This increases the difficulty and cost of preparation. In addition, most of the gels are usually prepared by thermal polymerization, which is favorable for polymerization of the gel and formation of a network, but takes too long, usually takes several hours or even tens of hours to complete the polymerization process, and it is difficult to process the precise structure and microstructure.
2) Stability problem: the stability of deep eutectic gels may be affected by a variety of factors, such as temperature, humidity, and external environmental conditions; in particular, some deep eutectic gels may lose gel properties under certain conditions, resulting in limited applications.
In view of the foregoing, it is necessary to provide a solution to the above-mentioned problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the deep eutectic liquid gel is provided, the preparation method is simpler, and the obtained deep eutectic liquid gel has the advantages of high adhesiveness, high bacteriostasis, low hysteresis rate, high stability and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a deep eutectic liquid gel, comprising the steps of:
mixing and dissolving betaine and acrylic acid to obtain a deep eutectic solution;
dissolving chitosan quaternary ammonium salt in a deep eutectic solution, adding a photoinitiator and a cross-linking agent, and continuing dissolving under a light-shielding condition to obtain a precursor solution;
and (3) placing the precursor liquid under ultraviolet rays for curing reaction to obtain the deep eutectic liquid gel.
Preferably, betaine and acrylic acid are dissolved at 400-600 rpm, and the dissolution temperature is 35-50 ℃.
Preferably, the chitosan quaternary ammonium salt is dissolved in the deep eutectic solution at the speed of 400-600 rpm and the temperature of 35-50 ℃ for 6-10 hours.
Preferably, after the photoinitiator and the crosslinking agent are added, the solution is continued at 500-700 rpm.
Preferably, the photoinitiator is diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide; the cross-linking agent is N, N-methylene bisacrylamide.
Preferably, the precursor solution is purged of gases prior to the curing reaction.
Preferably, the curing reaction time is 2-5 s.
Preferably, the mass ratio of betaine to chitosan quaternary ammonium salt is (10 g-15 g): (0.1 g to 1.1 g).
The second object of the present invention is: there is provided a deep eutectic liquid gel produced by the above-described method of producing a deep eutectic liquid gel.
The third object of the present invention is to: there is provided the use of a deep eutectic liquid gel made by the method of making a deep eutectic liquid gel described above in a flexible sensor.
The fourth object of the invention is that: the application of the deep eutectic liquid gel prepared by the preparation method of the deep eutectic liquid gel in the 3d printing technology is provided.
The invention has the beneficial effects that: according to the preparation method of the deep eutectic liquid gel, a solvent system formed by betaine and acrylic acid is adopted, wherein acrylic acid has a C=C double bond structure and can undergo polymerization reaction to form an acrylic acid network structure, so that the gel system is more stable; then adding chitosan quaternary ammonium salt as a second layer network structure of the gel to further strengthen the gel system, wherein the gel system contains a large number of-OH groups, so that the adhesive property of the gel is obviously improved, and the gel has no toxicity and excellent antibacterial property; then polymerizing the precursor liquid under ultraviolet rays by the added photoinitiator and crosslinking agent to convert the precursor liquid into a gel state, wherein the gel has excellent mechanical properties due to the self double-network structure and interaction among various chemical bonds, has low hysteresis rate after cyclic stretching, has strong fatigue resistance, and can quickly restore the connection of the chemical bonds in the gel after stretching.
Drawings
FIG. 1 is a schematic flow chart of the method for preparing deep eutectic liquid gel of the present invention.
FIG. 2 is a graph showing cyclic stretching of gels at different strains in a mechanical property test according to example 1 of the present invention.
FIG. 3 shows the first cycle hysteresis of the gel at various strains in the tensile property test of example 1 of the present invention.
FIG. 4 is a graph showing the response time of gel stretching and recovery in the self-healing test according to example 1 of the present invention.
FIG. 5 is a graph showing resistance change in 1000 cycles of stretching in electrochemical performance test according to example 1 of the present invention.
FIG. 6 shows the resistivity of the gel under cyclic stretching with small strain in electrochemical performance test in example 1 of the present invention.
FIG. 7 shows the resistivity of gels under large strain in electrochemical performance testing according to example 1 of the present invention.
FIG. 8 shows the rate of change of the electrical resistance of the gel at various rates in the electrochemical performance test of example 1 of the present invention.
Fig. 9 is a graph showing the comparison of cell voltages for different numbers of gels in series in a self-powered test according to example 1 of the present invention.
Fig. 10 shows the voltage change rate of the gel battery according to example 1 under 100 tensile strains in the self-powered test.
FIG. 11 is a graph showing the comparison of the adhesive strength of the gel on various materials in the adhesive property test according to example 1 of the present invention.
Fig. 12 is a model diagram of the invention in the 3D printing test of example 1.
FIG. 13 is a comparison of the CCK-8 assay gel extract of example 1 of the present invention with cell growth on normal growth medium in a biocompatibility test.
FIG. 14 is a graph showing the comparison of the zone of inhibition in a petri dish at various time points in the bacteriostasis test of example 1 of the present invention.
FIG. 15 is a graph showing comparison of the diameters of the inhibition zones at different time points in the inhibition test of example 1 of the present invention.
FIG. 16 is a plot of the change in resistance versus elongation in a sensitivity test for example 1 of the present invention.
FIG. 17 is a graph showing the comparison of the change rate of the resistance at different temperatures in example 1 of the present invention.
FIG. 18 is a graph showing the stable running ability of the gel of example 1 of the present invention.
FIG. 19 is a graph comparing anti-signal interference tests of the gel of example 1 of the present invention.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the specific embodiments, but the embodiments of the present invention are not limited thereto.
The first aspect of the present invention aims to provide a method for preparing deep eutectic liquid gel, as shown in fig. 1, comprising the following steps:
mixing and dissolving betaine and acrylic acid to obtain a deep eutectic solution;
dissolving chitosan quaternary ammonium salt in a deep eutectic solution, adding a photoinitiator and a cross-linking agent, and continuing dissolving under a light-shielding condition to obtain a precursor solution;
and (3) placing the precursor liquid under ultraviolet rays for curing reaction to obtain the deep eutectic liquid gel.
Compared with the traditional thermal polymerization method, the preparation method provided by the invention has the advantages that the photoinitiator is utilized, all components in the precursor liquid can be quickly connected under ultraviolet rays, and the solution can be polymerized to form gel within a few seconds, so that the preparation time is greatly shortened.
In addition, betaine, acrylic acid, chitosan quaternary ammonium salt and a cross-linking agent are adopted as reaction raw materials in the precursor liquid, so that deep eutectic liquid gel with a double-network structure can be formed, and compared with the deep eutectic liquid gel prepared conventionally, the deep eutectic liquid gel has the advantages of high antibacterial property, high adhesion, good biocompatibility, low hysteresis rate, high stability and the like, and the electric signal response of the deep eutectic liquid gel is tested, so that the deep eutectic liquid gel has excellent consistency and high sensitivity, has a larger strain response range, and can keep the stability of signals in a more extreme environment.
In addition, compared with the conventionally prepared deep eutectic liquid gel, the ionic liquid or organic substances contained in the deep eutectic liquid gel can have toxicity or environmental influence on human bodies and the environment, and the material components of the deep eutectic liquid gel are nontoxic, safer and more environment-friendly.
Wherein, the acrylic acid and the betaine can be produced in large scale, and the cost price is low in the existing mature industrial production system; in addition, in the gel preparation process, the materials are almost lossless, can be completely converted into gel for use, and the industrial production cost is reduced.
Betaine and acrylic acid are mixed to form deep eutectic solution, and the solution is clear, transparent, strong in fluidity, and more antibacterial and biocompatible, wherein the acrylic acid not only can be used as a hydrogen bond donor, but also can be subjected to polymerization reaction by self because the acrylic acid has a C=C double bond structure, and an acrylic acid network structure is formed, so that a gel system is more stable.
In addition, acrylic acid is used as a raw material, and a large amount of freely movable hydrogen ions are contained, and the hydrogen ions can perform autonomous power generation in a circuit which is constructed in a imitated mode, so that the gel has characteristics similar to a fruit battery, and a new function of the deep eutectic liquid gel is provided. Moreover, the self-powered intensity is also very considerable, a gel with the length of 25mm, the width of 10mm and the height of 2mm has about 0.8V voltage, the voltage of a serial circuit consisting of two gels can be comparable to the voltage of a standard No. seven battery, the LED lamp can normally emit light, and most of electric appliances which can be driven by the No. seven battery can be driven.
Meanwhile, the gel can still maintain stable voltage in an environment of-40 ℃ so that the LED lamp emits light, and the gel has stable self-power supply characteristic. The gel also exhibited excellent stability to electrical signal changes in 1000 repeated tensile or compressive cycles. This also benefits from the use of anhydrous solvents in the reaction feed, so that the gel can maintain stability of the conducted signals for a long period of time.
Similarly, the chitosan quaternary ammonium salt is extracted from marine crustaceans, the cost is low, the chitosan quaternary ammonium salt is nontoxic, and more importantly, the chitosan quaternary ammonium salt in the gel is used as a second network structure, so that dissipation energy generated during deformation can be greatly reduced, and the gel has a good hysteresis rate.
Compared with deep eutectic liquid gel prepared by adding no chitosan quaternary ammonium salt, the adhesive of the gel can be obviously improved after the addition, the gel can be easily adhered to common living scene substances such as paper, glass, copper sheets, oily skin, plastic products and the like, even if the gel is carried and sheared with inorganic materials, the viscosity strength is higher than 20kPa as a whole, and the adhesive is higher than that of common adhesive tapes on the market. This is mainly because quaternary ammonium molecules contain a large number of-OH groups, which can lead to a significant increase in the adhesion of the gel.
In addition, the deep eutectic liquid gel also has a strong antibacterial function. Wherein, the positively charged sites of chitosan quaternary ammonium salt can be combined with cell walls of negatively charged bacteria, thereby distorting the structure of the original cell walls, leading the original cell walls to be cracked and destroying the permeability of the cell walls, leading the proteins to be denatured and leading low molecular weight substances in the bacteria to leak, thus having good growth inhibition effect on escherichia coli and staphylococcus aureus. Acrylic acid, however, also has a certain killing power to bacteria due to the large number of-COOH structures carried by the acrylic acid itself. Meanwhile, betaine also has a bacteriostatic mechanism similar to quaternary ammonium salt substances, compared with other raw materials, the betaine can interfere the normal life process of bacteria by being adsorbed on the surface of bacteria with negative charges, so that a bacteriostatic effect is generated, and the integral bacteriostatic effect of the gel is greatly improved by being matched with chitosan quaternary ammonium salt and acrylic acid. Through the combined application of the three, the antibacterial performance of the gel is greatly improved.
In addition, the gel provided by the invention has high-efficiency self-healing capacity. Crosslinking between gels is typically due to interactions between chemical bonds, including covalent and hydrogen bonds, and the like. After gel breakage, irreversible damage to the covalent bond occurs, but other interactions such as hydrogen bonding and ionic bonding remain. The deep eutectic liquid gel contains a large number of anions and cations and hydrogen bond groups, and after gel fracture, the sections are spliced together, so that new chemical bond connection can be generated to maintain the complete state. Experiments show that the gel shows stronger self-repairing capability from the 3 rd hour in the environment of 70 ℃, and chemical bonds gradually recover connection; and the repair degree and time of the gel are positively correlated, the healing degree of the gel is increased continuously along with the time extension, the gel is stable in the 24 th hour, the healing degree is about 60%, and the service life of the deep eutectic liquid gel is greatly prolonged.
Moreover, the gel provided by the invention has excellent mechanical properties, and the gel has excellent mechanical properties through the self double-network structure of the gel and the interaction among various chemical bonds. Experiments have shown that the gel can extend to 1800% of its own length under stable stretching conditions. Meanwhile, in the aspect of hysteresis rate, the hysteresis rate of 10 times of cyclic stretching is below 10%, and the gel has excellent anti-fatigue capability, can quickly restore the connection of chemical bonds in the gel, and effectively ensures the service life of the gel by matching with the high-efficiency self-healing capability of the gel.
In some embodiments, betaine and acrylic acid are dissolved at 400 to 600rpm, and the dissolution temperature is 35 to 50 ℃. Specifically, the stirring speed of dissolution may be 400 to 450rpm, 450 to 500rpm, 500 to 550rpm or 550 to 600rpm; the dissolution temperature may be 35 to 40 ℃, 40 to 45 ℃ or 45 to 50 ℃. Preferably, the stirring speed of the dissolution is 500rpm and the dissolution temperature is 40 ℃.
In some embodiments, the chitosan quaternary ammonium salt is dissolved in the deep eutectic solution at 400-600 rpm and 35-50 ℃ for 6-10 hours. Preferably, the chitosan quaternary ammonium salt is uniformly stirred and dissolved in the deep eutectic solution while maintaining the same dissolution speed and temperature as those of betaine and acrylic acid, and the corresponding dissolution time can be 6-7 h, 7-8 h, 8-9 h or 9-10 h, and the preferred dissolution time is 8h.
In some embodiments, after adding the photoinitiator and the crosslinker, dissolution continues at 500 to 700rpm. After the photoinitiator and the cross-linking agent are added, the stirring speed is preferably increased to 500-700 rpm, so that the photoinitiator and the cross-linking agent are easier to dissolve in the solution.
In some embodiments, the reaction bottle bearing the reaction raw material can be subjected to light-shielding treatment in a manner of wrapping tin foil, so that the polymerization degree of gel is prevented from being influenced by indoor light or sunlight, and the normal operation of the curing reaction is ensured.
In some embodiments, the photoinitiator is diphenyl- (2, 4, 6-Trimethylbenzoyl) Phosphorus Oxide (TPO); the cross-linking agent is N, N-Methylene Bisacrylamide (MBA). Wherein, the photoinitiator can rapidly complete polymerization reaction under the irradiation of ultraviolet rays, so that the precursor solution is converted into a gel state. The cross-linking agent can increase the interaction force between the gels, so that the chemical bond linkage among the components of a gel system is enhanced, the mechanical property of the gel is further enhanced, and various three-dimensional structures and complex microstructures can be easily printed by using the gel through a commercial 3D printer.
In some embodiments, the precursor solution is purged of gases prior to the curing reaction. The removal of the gases from the gel prior to the curing reaction can avoid affecting the structural integrity of the gel. Specifically, the precursor liquid can be vibrated in the ultrasonic cleaning instrument, and meanwhile, the gas in the precursor liquid is pumped through the vacuum pump in an auxiliary mode, so that tiny bubbles in the solution are removed sufficiently, the integrity of a gel structure is guaranteed, and the ultrasonic vibration time can be 30-60 min.
In some embodiments, the curing reaction time is 2-5 s. The gel prepared by the method can be cured in a few seconds, and the gel preparation time is greatly shortened.
In some embodiments, the mass ratio of betaine to chitosan quaternary ammonium salt is (10 g-15 g): (0.1 g to 1.1 g). The quality of betaine and chitosan quaternary ammonium salt is controlled within the above range, wherein a deep eutectic solution formed by betaine and acrylic acid is used as a substrate, which is more favorable for dissolving the chitosan quaternary ammonium salt, so that the gel provided by the invention has a stable double-layer network structure. Preferably, the mass ratio of betaine to chitosan quaternary ammonium salt is (10 g-15 g): (0.1 g to 0.5 g).
The second aspect of the invention aims to provide the deep eutectic liquid gel prepared by the preparation method of the deep eutectic liquid gel, and each performance of the gel is effectively improved, so that the application range of the deep eutectic liquid gel is greatly widened.
A third aspect of the present invention is directed to the use of a deep eutectic liquid gel made by the method of making a deep eutectic liquid gel described above in a flexible sensor. The sensor is used in a flexible sensor, has excellent consistency and high sensitivity, has a large strain response range, and can maintain the stability of signals in a more extreme environment.
A fourth aspect of the present invention is directed to the use of a deep eutectic liquid gel made by the method of making a deep eutectic liquid gel described above in 3d printing technology. The gel is mainly used as a printing raw material in a 3D printing technology, and before preparation, a gel precursor liquid can be used as printing ink, and then ultraviolet light is utilized to rapidly carry out photo-curing, so that a micro and precise structure is printed, and the application range of the deep eutectic liquid gel is further widened.
In order to make the technical scheme and advantages of the present invention more clear, the present invention and its advantageous effects will be described in further detail below with reference to the detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A method for preparing a deep eutectic liquid gel, comprising the steps of:
1) Taking a clean eggplant-shaped bottle, and putting the clean eggplant-shaped bottle into a magnetic stirrer; precisely weighing 12.50g of betaine by using an electronic balance, placing in an eggplant-shaped bottle, precisely measuring 23.00mL of acrylic acid by using a 50mL graduated cylinder, pouring into the eggplant-shaped bottle, and starting a magnetic stirrer to maintain until the betaine is completely dissolved at 40 ℃ and 500rpm to obtain a deep eutectic solution;
2) Continuously using an electronic balance, precisely weighing 0.3305g of chitosan quaternary ammonium salt, uniformly and slowly adding the chitosan quaternary ammonium salt into the transparent deep eutectic solution, and continuously stirring for 8 hours while maintaining the rotation speed and the temperature unchanged until the chitosan quaternary ammonium salt is completely dissolved in the solution; precisely weighing 0.0231g of photo-initiator TPO and 0.0495g of cross-linking agent MBA again, adding into the completely dissolved solution, regulating the rotating speed to 600rpm, wrapping a layer of tinfoil on the eggplant-shaped bottle to perform light-shielding treatment, and uniformly dissolving to obtain a precursor solution;
3) Placing the eggplant-shaped bottle containing the precursor liquid in an ultrasonic cleaning instrument, vibrating for 40min, and simultaneously pumping gas in the bottle by a vacuum pump to remove tiny bubbles in the solution so as not to influence the structural integrity of the gel;
4) And finally, injecting the obtained precursor liquid into corresponding moulds for testing by using a dropper, and curing for a plurality of seconds under UV rays by using an ultraviolet curing box to complete gel polymerization so as to obtain deep eutectic liquid gel.
Example 2
Unlike example 1, step 2) differs in that the rotational speed at which the photoinitiator TPO and the crosslinker MBA are dissolved is 500rpm.
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 1, step 2) differs in that the rotational speed at which the photoinitiator TPO and the crosslinker MBA are dissolved is 700rpm.
The remainder is the same as embodiment 1 and will not be described here again.
Example 4
The mass of the quaternary ammonium salt of chitosan added in step 2) was 0.1832g, which is different from example 1.
The remainder is the same as embodiment 1 and will not be described here again.
Example 5
The mass of the quaternary ammonium salt of chitosan added in step 2) was 1.0995g, which is different from example 1.
The remainder is the same as embodiment 1 and will not be described here again.
Example 6
The difference from example 1 is that the mass of betaine added in step 1) is 10g.
The remainder is the same as embodiment 1 and will not be described here again.
Example 7
The difference from example 1 is that the mass of betaine added in step 1) is 15g.
The remainder is the same as embodiment 1 and will not be described here again.
Example 8
Unlike example 1, step 3), the time of the ultrasonic vibration was 5min.
The remainder is the same as embodiment 1 and will not be described here again.
Comparative example 1
Step 2) is different from example 1 in that the comparative example does not contain chitosan quaternary ammonium salt.
The rest refers to embodiment 1, and will not be described here again.
Comparative example 2
Unlike example 1, step 1), this comparative example does not contain betaine.
The rest refers to embodiment 1, and will not be described here again.
Comparative example 3
Step 2) is different from example 1 in that the comparative example is directly dissolved uniformly without light-shielding treatment after adding the photoinitiator TPO and the crosslinking agent MBA, and a precursor liquid is obtained.
The remainder is the same as embodiment 1 and will not be described here again.
The following is a performance test of a deep eutectic liquid gel based primarily on example 1 to demonstrate the advantages of the present gel.
The test methods are as follows:
1) Mechanical property test: a dumbbell-shaped gel sample was prepared for testing using a UTM2102 electromechanical tester and tested at room temperature, and the test results are shown in fig. 2.
2) Tensile property test: in the experiment, the sensors are 200N load cells; the uniaxial stretching and the cyclic stretching tests are all carried out at the speed of 50 mm/min; tensile stress (σ) is defined as the loading force (F) divided by the cross-sectional area (A) of the original sample 0 ）（σ=F/A 0 ) The method comprises the steps of carrying out a first treatment on the surface of the Tensile strain (ε) is defined as the deformation length divided by the original length (ε= (L-L) 0 ）/L 0 ) The method comprises the steps of carrying out a first treatment on the surface of the The hysteresis rate delta refers to the energy dissipation efficiency of the material, and is calculated by the following steps: delta= U i /U i The test results are shown in fig. 3. As can be seen from fig. 3, the gel of the present invention has a lower hysteresis rate and a higher rebound ability than the gel of the prior art.
3) Self-healing test: dumbbell-shaped materials are also used; the dumbbell-shaped gel is cut off from the middle, the sections are spliced in an anastomotic manner, then the gel is sealed and placed in a 70 ℃ oven, hydrogen bonds are generated by heating for different times, the stretching length of the gel is tested by using a UTM2102 electromechanical tester and is compared with that of the gel which is not cut off, and the test result is shown in figure 4. As can be seen from fig. 4, the gel of the present invention can be recovered in a short time.
4) Electrochemical performance test: the test was performed using a combination of both UTM2102162 type electromechanical tester (Shenzhen SANS tester, shenzhen) and LCR163 type meter (VC 4091C, victory instruments, china). Wherein, the bridge instrument records the real-time resistance change value of the gel in the stretching or compressing state; the relative change value of the resistor is calculated by the initial resistor and the real-time resistor value recorded in the test process, and the formula is as follows: deltaR/R 0 =R-R 0 /R 0 The method comprises the steps of carrying out a first treatment on the surface of the R represents the resistance value at various strains measured in real time, representing the initial resistance value. Wherein the change coefficient of the resistance is GF= [ (R-R) 0 )/R 0 ]Epsilon is the degree of deformation applied. In addition, in the construction of the sensor, 25mm long-strip gel is adopted as a test object; on both sides of the gelCopper wires are respectively fixed and connected with an LCR163 type measuring instrument to form a sensor; the data generated by the method are all collected through an LCR163 type measuring instrument and are converted into visual information in a computer. The sensors are fixed on the surface of the human joint skin to collect human motion information, including large-amplitude motions (such as finger, elbow, shoulder and knee motions), fine motions (such as pulse, swallowing and chest motions) and conventional writing activities (such as different resistance changes written by WFMU and different volunteers W). The test results are shown in fig. 5-8.
5) Self-powered testing: copper and zinc sheets are arranged and fixed on two sides of the prepared cuboid gel (25 mm long, 10mm wide and 2mm high) to form a battery. The voltage of gel batteries with different numbers, voltage change values under different degrees of bending and voltage conditions under the gel compression recovery state are measured by using a universal meter, and the test results are shown in figures 9-10. Wherein, the coefficient of variation of the voltage:
GF=[(V-V 0 )/V 0 ]/ε
in the formula, V represents the real-time voltage value in the measuring process, V0 is the initial value of the voltage at the beginning of the measurement, and epsilon is the applied deformation degree.
6) Adhesion performance test: the adhesive strength of the DES gel was measured by the carrying shear test, two sides of the cuboid gel were placed between five different materials and fixed for 3 hours, and then the maximum adhesive strength was measured by a UTM2102 electromechanical tester and tested 5 times in cycles. The running speed of the tester during the test was 5mm/min. The test results are shown in fig. 11.
7) 3D printing test: a suitable amount of lemon yellow was added to the prepared precursor and the yellow gel was poured into a projector (15 mW/m -2 ) A commercial DLP 3D printer (suzhou Yongqing intelligent equipment limited) in stock. The light scattering is prevented by adding the lemon yellow dye, so that the printing resolution is improved. The print thickness of each layer was set to 0.1 mm and the exposure time of each layer was about 2s. The printing temperature was kept at room temperature 25 ℃. The 3d printed product may be as shown in fig. 12.
8) Biocompatibility testing: the mouse fibroblast line L929 was selected as the evaluation cell. First, the ion gel is treated by ultraviolet raysSterilizing, and soaking in eagle medium at 37deg.C for 24 hr. After soaking, the gel was washed with PBS buffer and placed in eagle complete medium supplemented with 10% bovine serum and 1% penicillin-streptomycin for 24 hours. The extract was obtained, sterilized and filtered (S2635 sterile syringe filter, 13 mm). The cells were then lysed with trypsin and concentrated by centrifugation. The cell concentration was adjusted to 1X 10 4 cells/mL, cells were seeded with 200 μl of medium per well in 96-well plates, placed at 37 ℃ and 5% co 2 Culturing for 1, 4 and 7 days under the humidifying condition, and ensuring that the culture medium is replaced once for 24 hours. Cell viability and cytotoxicity were assessed on days 1, 4, and 7 using the CCK8 assay, which was repeated 5 times to reduce errors, and the control group selected cells cultured in medium without gel extract. The test results are shown in fig. 13.
9) The bacteriostasis test adopts a disc diffusion method. The gel is inoculated on a culture dish fully coated with escherichia coli and staphylococcus aureus, the bacteriostasis capacity of the gel is reflected by observing and measuring the size of a bacteriostasis zone, and the test result is shown in figures 14-15. The calculation formula of the width (H) of the inhibition zone is as follows: h= (D-D)/2;
wherein D is the outer diameter value of the inhibition zone, and D is the diameter of the gel.
10 Sensitivity test): the test was performed using a combination of both a UTM 2102162-type electromechanical tester and an LCR 163-type meter, and the test method can be referred to as the electrochemical performance test method described above.
As shown in FIG. 16, the sensitivity coefficient (GF) of the deep eutectic liquid gel of the present invention is divided into 3 linear response regions, wherein GF is 1.05 when the elongation is 0-200%, GF is 2.40 when the elongation is 200-700%, GF is 7.02 when the elongation is 700-900%, and the resistance change rate value is increased along with the increase of strain, so that the deep eutectic liquid gel of the present invention has high strain sensitivity and good tensile property.
11 In addition, based on the sensitivity test, the inventors have studied the strain sensing performance thereof at different temperatures (-20 ℃, 10 ℃ and 50 ℃), and as shown in fig. 17, the gel can monitor a distinct and stable electrical signal at 100% tensile strain at different temperature conditions.
In addition, it should be noted that most strain sensing systems generally have excellent sensitivity, but there is a large deviation in the rate of change of resistance of the strain signal measurement due to poor mechanical properties of the material, which makes it challenging to obtain a stable signal in a complex environment. Therefore, in order to evaluate the mechanical interference factors common in practical use, a series of anti-interference experiments are also carried out, but the deep eutectic liquid gel still shows excellent performance, and on one hand, as shown in fig. 18, the strain sensor shows the capability of keeping stable operation even if a gap exists, shows the minimum signal drift or fluctuation and shows the anti-damage capability; on the other hand, as shown in fig. 19, signal interference caused by off-axis deformation such as manual torsion is negligible compared to the original state. The reliability of the data obtained from the use of the deep eutectic liquid gel of the present invention as a flexible sensor for testing was also demonstrated.
As can be seen from the test results of fig. 2 to 19, the deep eutectic liquid gel provided by the invention has excellent mechanical properties, self-healing properties, adhesion properties, low hysteresis rate, biocompatibility and antibacterial properties, also has self-powered properties, and shows good electrochemical properties, and can be used not only in flexible sensors, but also as a 3D printing material, and certainly can also be used in the fields of energy storage and the like.
In addition, the deep eutectic liquid gels obtained in examples 1 to 8 and comparative examples 1 to 3 were also subjected to mechanical properties, adhesiveness, and first cycle hysteresis rate test, and the test methods were referred to above.
The test results are shown in table 1 below,
TABLE 1
In summary, the deep eutectic liquid gel prepared by the method is simpler in preparation method, has better performance than the conventional deep eutectic liquid gel at present, effectively solves the problems of long preparation time, complex preparation process, poor gel stability and the like of the conventional deep eutectic liquid gel at present, and has the advantages of higher adhesiveness, high antibacterial property, low hysteresis rate, high stability and the like.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A method for preparing a deep eutectic liquid gel, comprising the steps of:
mixing and dissolving betaine and acrylic acid to obtain a deep eutectic solution;
dissolving chitosan quaternary ammonium salt in a deep eutectic solution, adding a photoinitiator and a cross-linking agent, and continuing dissolving under a light-shielding condition to obtain a precursor solution;
and (3) placing the precursor liquid under ultraviolet rays for curing reaction to obtain the deep eutectic liquid gel.
2. The method for preparing a deep eutectic liquid gel according to claim 1, wherein betaine and acrylic acid are dissolved at 400-600 rpm, and the dissolution temperature is 35-50 ℃.
3. The method for preparing the deep eutectic liquid gel according to claim 1 or 2, wherein chitosan quaternary ammonium salt is dissolved in the deep eutectic solution at 400-600 rpm and 35-50 ℃ for 6-10 hours.
4. The method for preparing deep eutectic liquid gel according to claim 1, wherein the photoinitiator and the cross-linking agent are added and then dissolved continuously at 500-700 rpm.
5. The method of preparing a deep eutectic liquid gel according to claim 1 or 4, wherein the photoinitiator is diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide; the cross-linking agent is N, N-methylene bisacrylamide.
6. The method of preparing a deep eutectic liquid gel according to claim 1, wherein the precursor liquid is degassed prior to the solidification reaction; the curing reaction time is 2-5 s.
7. The preparation method of the deep eutectic liquid gel according to claim 1, wherein the mass ratio of betaine to chitosan quaternary ammonium salt is (10 g-15 g): (0.1 g to 1.1 g).
8. A deep eutectic liquid gel produced by the method for producing a deep eutectic liquid gel according to any one of claims 1 to 7.
9. Use of a deep eutectic liquid gel prepared by the method of preparing a deep eutectic liquid gel according to any one of claims 1 to 7 in a flexible sensor.
10. Use of a deep eutectic liquid gel prepared by the method of preparing a deep eutectic liquid gel according to any one of claims 1 to 7 in a 3d printing technique.
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