CN114854155B - High-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer - Google Patents
High-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer Download PDFInfo
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- CN114854155B CN114854155B CN202210359243.9A CN202210359243A CN114854155B CN 114854155 B CN114854155 B CN 114854155B CN 202210359243 A CN202210359243 A CN 202210359243A CN 114854155 B CN114854155 B CN 114854155B
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- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
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Abstract
The invention discloses a high-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer. According to the invention, PVA/quaternary ammonium salt elastomer is prepared by a melt blending modification method and then by a volatile film forming method; the mass ratio of the quaternary ammonium salt to the polyvinyl alcohol is 15-30: 100. the invention is a polyvinyl alcohol conductive elastomer, which has excellent mechanical property, optical transparency and conductivity. Due to the melt ionization of quaternary ammonium salt uniformly distributed in the PVA composite matrix by hydrogen bond interaction, the PVA glass transition temperature (T g ) Melting temperature (T) m ) The crystallization performance is greatly changed, T g 、T m The PVA crystallization capability is reduced, and meanwhile, the composite material becomes soft due to the fact that the free volume of PVA molecular chains is increased, and the crystal area serves as a physical crosslinking point to provide restoring capability for the composite material, so that the conductive PVA/quaternary ammonium salt elastomer with high strength, freezing resistance and transparency can be obtained.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a high-strength, anti-freezing and transparent conductive PVA/quaternary ammonium salt elastomer and a preparation method thereof, and particularly relates to a preparation method of a polymer composite material which enables quaternary ammonium salt to be melt ionized through hydrogen bond interaction and to be uniformly distributed in the material.
Background
With the advent of flexible electronic devices such as flexible display screens, smart clothing, implantable medical devices, and the like, great changes are expected to be brought to the daily life of humans. The flexible wearable sensor is widely applied to the fields of health diagnosis, exercise monitoring, rehabilitation medical treatment, entertainment and the like due to the characteristics of stretchability, flexibility, thinness, portability, excellent electrical performance and the like. In recent years, there have been significant advances in flexible wearable stress sensors, and a variety of flexible stress sensors that can measure health information have been applied to pulse wave, motion, respiration, and Electrocardiogram (ECG) detection.
Conductive polymers are one of the most widely used sensing materials because of their easy processability, good environmental stability, excellent electrical conductivity, and good flame retardancy. However, materials with single properties have not been able to meet the demands of society, and conductive polymer composite materials capable of having various excellent properties after doping have been developed.
Polyvinyl alcohol (PVA), which is a water-soluble polymer, has excellent transparency, toughness, biocompatibility, barrier property, and biodegradability, and has been widely used in various fields such as biomedical science, packaging industry, and biosensors. PVA is not conductive, and thus it is necessary to modify PVA to impart conductivity to PVA. Dissolving PVA in water to introduce conductive ions or filling carbon-based/Mxene-based fillers and crosslinking to obtain conductive PVA hydrogels is a common practice for making PVA-based flexible sensors. But the sensor may lose performance due to freezing or volatilization of water at low or high temperatures.
Thus, it is a challenge to prepare antifreeze, transparent, high strength, electrically conductive PVA composites using simple methods.
First, there are two main methods for preparing freeze resistant flexible sensors. One is to introduce an antifreeze agent into the hydrogel sensor: for example, hydrogels are modified by the addition of glycerol. However, modification of the sensor by such a method may reduce the conductivity of the material, resulting in other performance losses. Another approach is to replace water with an ionic liquid that is still in a liquid state at low temperature as a solvent for the gel. This approach is mainly to use an ionic liquid capable of dissolving the polymer as a solvent, such as 1-ethyl-3-methylimidazole dinitrile amine salt/poly (2-acrylamido-2-methylpropanesulfonic acid) ([ EMIm ] [ DCA ]/PAMPS) ionogel. The strong electrostatic interaction between the [ EMim ] [ DCA ] and the PAMPS endows the material with excellent mechanical properties, and the ionic gel sensor has excellent sensing performance due to the high ionic conductivity of the [ EMim ] [ DCA ]; however, ionic liquids are expensive, so that gel sensors based on ionic liquids are difficult to mass produce. Therefore, the invention provides a simple, convenient, efficient and low-cost preparation method for the PVA flexible sensor which can be produced in a large scale.
In user interactive displays, biomedical imaging, and touch screens, transparency is necessary because it facilitates the visual transfer of information. However, most electronic skin sensors (e-skin) are opaque because they are typically composed of opaque conductive elements (such as carbonaceous nanoparticles, liquid metals, and conductive polymers) and a polymer matrix. For example, PVA is modified by Mxene to obtain a PVA composite material of high conductivity. However, the composite material is black overall due to the optically opaque Mxene, thus limiting the application of PVA/Mxene composites. The invention mainly relates to a modification method of a solution blending quaternary ammonium salt. The reason for selecting the solution blend is as follows: 1. solution casting techniques have become established and are used in many ways. PVA melt temperature (T m ) Too close to degradation temperature for melt processing. 3. The water is selected as the solvent, no sewage and harmful gas are generated, the operation is simple, and the environment is protected. 4. The quaternary ammonium salt (QuaternaryAmmonium Salt) is a compound in which all four hydrogen atoms in the ammonium ion are substituted with hydrocarbon groups, and is a water-soluble salt itself, and can be well dispersed when blended with an aqueous PVA solution.
Firstly, adding PVA and quaternary ammonium salt into a reaction kettle according to a certain proportion for solution blending, wherein the mass ratio of the quaternary ammonium salt to the PVA is 15-30: 100; the PVA elastomer is then obtained by means of evaporation of the solvent. In detail, in this type of quaternary ammonium salt uniformly distributed in the PVA composite matrix by melt ionization due to hydrogen bond interaction, the PVA glass transition temperature (T g ) Melting temperature (T) m ) The crystallization performance is greatly changed, T g 、T m The PVA crystallization capability is reduced, and meanwhile, the composite material becomes soft due to the fact that the free volume of PVA molecular chains is increased, and the crystal area serves as a physical crosslinking point to provide restoring capability for the composite material, so that the conductive PVA/quaternary ammonium salt elastomer with high strength, freezing resistance and transparency can be obtained.
Disclosure of Invention
It is an object of the present invention to address the deficiencies of the prior art and to provide a high strength, freeze resistant and transparent electrically conductive PVA/quaternary ammonium salt elastomer.
The invention adopts the quaternary ammonium salt to modify PVA, and the hydrogen bond between the quaternary ammonium salt and the PVA leads the quaternary ammonium salt to melt ionization, and reduces T g 、T m The crystallization of PVA is inhibited, so that the material has better conductivity and toughness, and the quaternary ammonium salt is ionized without depending on water, so that the composite material can be used at subzero and high temperature; in addition, the high transparency of PVA is maintained, which is an advantage not possessed by carbon-based/Mxene-based fillers.
The high-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer is a blend, and comprises the following components in percentage by mass: 100 quaternary ammonium salt and PVA;
the quaternary ammonium salt has the following structural formula:
wherein R1-R4 are each independently a hydrocarbon group or a hydroxyhydrocarbon group and may be the same or different; x is X － Is halogen anion (F) － 、Cl － 、Br － 、I － )；
It is another object of the present invention to provide a process for the preparation of the above-described high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomers.
The method comprises the following steps:
step (1) adding PVA and quaternary ammonium salt into a reaction kettle according to a certain proportion for solution blending; wherein the mass ratio of the quaternary ammonium salt to the PVA is 15-30: 100. the solvent is water. The temperature was 80 ℃.
And (2) spreading the solution after solution blending, drying to remove the solvent to obtain the PVA/quaternary ammonium salt elastomer, and finally carrying out performance characterization.
It is a further object of the present invention to provide the use of the high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomers described above in freeze resistant flexible sensors.
It is a further object of the present invention to provide a freeze resistant flexible sensor comprising the high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer described above.
The beneficial effects of the invention are as follows:
1) The invention uniformly disperses the quaternary ammonium salt with large component proportion in the PVA matrix through solution blending, and the PVA/quaternary ammonium salt is a homogeneous blending system due to the hydrogen bond interaction between PVA and quaternary ammonium salt. Therefore, the PVA/quaternary ammonium salt elastomer has excellent optical transparency, has larger advantages compared with PVA/ionic liquid or PVA/Mxene blending systems, and has wider application prospects in the fields of user interaction displays, biomedical imaging, touch screens and the like. In addition, PVA and quaternary ammonium salt have hydrogen bonds, resulting in melting of quaternary ammonium salt, so that the composite material has excellent conductivity and transparency (transparency refers to transmittance of light and haze, and yellowing of the material is in two directions).
2) According to the PVA/quaternary ammonium salt elastomer, due to the fact that the free volume of PVA added with the quaternary ammonium salt with a large component proportion is enlarged, the composite material has excellent toughness, namely, the high-filling quaternary ammonium salt can effectively inhibit PVA from crystallizing, so that PVA becomes a tough material from brittleness, and a crystal area is used as a physical crosslinking point to provide certain restorability for the material. The PVA/quaternary ammonium salt elastomer of the invention shows excellent mechanical properties.
3) The PVA/quaternary ammonium salt elastomer sensor obtained by the invention can work in a wide temperature range (-20-150 ℃) because the quaternary ammonium salt is completely melted and ionized under the action of hydrogen bonds, which is difficult to realize by the traditional PVA hydrogel sensor. The PVA/quaternary ammonium salt elastomer of the present invention exhibits excellent electrical conductivity.
4) The PVA/quaternary ammonium salt elastomer sensor has a wider market prospect compared with the PVA composite material modified by expensive ionic liquid due to a plurality of quaternary ammonium salt types and low price.
Drawings
FIG. 1 (a) is an external view of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer) and example 4 (30 wt% ChCl-PVA modified elastomer), respectively; FIG. 1 (b) is a graph of clarity versus haze for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 2 is an SEM image of comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer), respectively;
FIG. 3 (a) is an IR chart for comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer); FIG. 3 (b) is an IR chart showing the temperature rise (40 to 90 ℃) of example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 4 is an x-ray diffraction pattern of comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 5 is a DSC graph of comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 6 (a) is a TGA graph of comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer); FIG. 6 (b) is a dTMA plot of comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer)
FIG. 7 is a stress-strain plot for comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 8 is a graph of electrical conductivity for comparative example 1 (PVA film), example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 9 is a graph of the visible light transmittance spectrum of example 4 (30 wt% ChCl-PVA modified elastomer);
FIG. 10 (a) is a stress-strain (stretch-recovery) curve for example 4 (30 wt% ChCl-PVA modified elastomer); FIG. 10 (b) is a plot of the resistivity sense signal for example 4 (30 wt% ChCl-PVA modified elastomer) as a sensor;
FIG. 11 is a graph of the resistance sensing signal for example 4 (30 wt% ChCl-PVA modified elastomer) as a sensor to monitor finger deformation.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and practiced in a large number of ways, and have proposed the technical solution of the present invention, which is based on at least: 1) The invention uniformly disperses the quaternary ammonium salt with large component proportion in the PVA matrix through solution blending, and the PVA/quaternary ammonium salt is a homogeneous blending system due to the hydrogen bond interaction between PVA and quaternary ammonium salt. In addition, the PVA and the quaternary ammonium salt have hydrogen bonds, so that the quaternary ammonium salt is molten, and the composite material has excellent conductivity and transparency. 2) According to the PVA/quaternary ammonium salt elastomer, due to the fact that the free volume of PVA added with the quaternary ammonium salt with a large component proportion is enlarged, the composite material has excellent toughness, namely, the high-filling quaternary ammonium salt can effectively inhibit PVA from crystallizing, so that PVA becomes a tough material from brittleness, and a crystal area is used as a physical crosslinking point to provide certain restorability for the material. The PVA/quaternary ammonium salt elastomer of the invention shows excellent mechanical properties. 3) The PVA/quaternary ammonium salt elastomer sensor obtained by the invention can work in a wide temperature range (-20-150 ℃) because the quaternary ammonium salt is completely melted and ionized under the action of hydrogen bonds.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In one aspect, the high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer is a blend comprising by mass 15 to 30:100 quaternary ammonium salt and PVA;
the quaternary ammonium salt has the following structural formula:
wherein R1-R4 are each independently a hydrocarbon group or a hydroxyhydrocarbon group and may be the same or different; x is X － Is halogen anion (F) － 、Cl － 、Br － 、I － )；
In another aspect, a method for preparing a high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer comprises the steps of:
step (1) adding PVA and quaternary ammonium salt into a reaction kettle according to a certain proportion for solution blending; wherein the mass ratio of the quaternary ammonium salt to the PVA is 15-30: 100. the solvent is water. The temperature was 80 ℃.
And (2) spreading the solution after solution blending, drying to remove the solvent to obtain the PVA/quaternary ammonium salt elastomer, and finally carrying out performance characterization.
The following description of the present invention is further provided with reference to several preferred embodiments, but the experimental conditions and setting parameters should not be construed as limiting the basic technical scheme of the present invention. And the scope of the present invention is not limited to the following examples.
In this example and its comparative example, a polymer PVA, manufactured by Allatin, model 1799 was used as the matrix.
The quaternary ammonium salts used in this example were: choline chloride (ChCl).
Example 1
Firstly, adding 10g of PVA and 1g of ChCl into a reaction kettle, and blending the solution for 6 hours at the temperature of 80 ℃;
and (2) cooling the solution to room temperature, pouring the solution into a PTFE mold for film laying, volatilizing the solvent of the obtained film, and drying in vacuum for 24 hours. 15wt% to PVA elastomer is noted.
Example 2
Firstly, adding 10g of PVA and 1g of ChCl into a reaction kettle, and blending the solution for 6 hours at the temperature of 80 ℃;
and (2) cooling the solution to room temperature, pouring the solution into a PTFE mold for film laying, volatilizing the solvent of the obtained film, and drying in vacuum for 24 hours. 20wt% -PVA elastomer is recorded.
Example 3
Firstly, adding 10g of PVA and 1g of ChCl into a reaction kettle, and blending the solution for 6 hours at the temperature of 80 ℃;
and (2) cooling the solution to room temperature, pouring the solution into a PTFE mold for film laying, volatilizing the solvent of the obtained film, and drying in vacuum for 24 hours. 25wt% to PVA elastomer is noted.
Example 4
Firstly, adding 10g of PVA and 1g of ChCl into a reaction kettle, and blending the solution for 6 hours at the temperature of 80 ℃;
and (2) cooling the solution to room temperature, pouring the solution into a PTFE mold for film laying, volatilizing the solvent of the obtained film, and drying in vacuum for 24 hours. 30wt% -PVA elastomer is recorded.
Comparative example 1
Firstly, adding 10g of PVA into a reaction kettle, wherein the temperature is 80 ℃, and blending the solution for 6 hours;
and (2) cooling the solution to room temperature, pouring the solution into a PTFE mold for film laying, volatilizing the solvent of the obtained film, and drying in vacuum for 24 hours. The PVA elastomer was designated as pure.
The samples obtained in example 1, example 2, example 3, example 4 and comparative example 1 were subjected to characterization of elastomer structure and performance testing.
As shown in FIG. 1, examples 1 (15 wt% ChCl-PVA modified elastomer), 2 (20 wt% ChCl-PVA modified elastomer), 3 (25 wt% ChCl-PVA modified elastomer) and 4 (30 wt% ChCl-PVA modified elastomer) were all transparent samples, and the addition of ChCl did not significantly affect the optical clarity of PVA.
As shown in FIG. 2, SEM analysis of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer) and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film) showed that ChCl was not dispersed in the form of crystals, but uniformly dispersed in the PVA matrix in the molten state and no phase domains were present, demonstrating that the products of examples 1 to 5 were macroscopically transparent.
As shown in FIG. 3 (a), it can be seen from the analysis of the Fourier infrared spectra of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film) that as the ChCl ratio increases, the-CH of ChCl 3 The stretching vibration peak appears in 3020cm -1 A place; the hydroxyl group peak (-OH) of PVA is 3270cm -1 Blue shift to 3260cm- 1 While the-CH-stretching vibration peak of PVA is always 2905cm -1 Where it is located. As shown in FIG. 3 (b), it can be seen that the-CH of ChCl increases from 40℃to 90℃as the temperature increases, for the analysis of the Fourier infrared spectrum at varying temperatures (40-90 ℃) of example 4 (30 wt% ChCl-PVA-modified elastomer) 3 The stretching vibration peak always appears in 3020cm -1 A place; while the hydroxyl group peak of PVA is 3274cm -1 Red shifted to 3291cm -1 . Taken together, fourier infrared spectroscopy confirmed the presence of hydrogen bonds between ChCl and PVA, demonstrating that the reduction in ChCl melting point was dispersed in PVA in the molten state.
As shown in FIG. 4, there are X-ray diffraction analyses of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film). As the ChCl addition increases, PVA crystallinity decreases; the peak area of the amorphous area at 31 degrees and 41 degrees is greatly increased along with the increase of the ChCl addition amount. The addition of ChCl resulted in a small angular shift of the plane diffraction peak at the 2θ=20° PVA101 face, to 19 °, indicating that the addition of ChCl resulted in a larger PVA cell parameter and a wider interplanar spacing.
Table 1 shows the crystallinity and amorphous region measurements for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film).
As shown in FIG. 5, DSC analysis was performed for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film). With increasing ChCl addition, PVA T m And T is g And decrease in crystallization ability. This is because hydrogen bonding between ChCl and PVA inhibits the generation of hydrogen bonds between PVA molecular chains, thereby inhibiting PVA crystallization; t of PVA due to the addition of ChCl increases the free volume of PVA chain m And T is g Descending. This not only renders the PVA flexible, but also imparts processability characteristics to the PVA.
Table 2 shows examples of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film) T m 、T g Measurement of melting enthalpy and melt recrystallization crystallinity.
As shown in FIGS. 6 (a) and 6 (b), TGA and dTMA analyses were performed for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer) and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film). The hydrogen bond between the ChCl and the PVA inhibits the degradation of the first step of dehydroxylation of the PVA, so that the thermal stability of the PVA is improved.
Table 3 shows the 5% degradation temperature (T) for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film) 5％ ) And degradation rate maximum temperature (T) max ) Is measured.
As shown in FIG. 7, stress-strain graphs of example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer), and example 4 (30 wt% ChCl-PVA modified elastomer) and comparative example 1 (PVA film) are shown. With the ChCl addition reaching 10%, the stress yield and cold drawing occur in the example 1, and the brittle-ductile transition occurs; as the ChCl addition amount is increased, the toughness of the material is improved, and the elongation at break of the example 4 can reach 450%.
As shown in FIG. 8, conductivity tests were performed for example 1 (15 wt% ChCl-PVA modified elastomer), example 2 (20 wt% ChCl-PVA modified elastomer), example 3 (25 wt% ChCl-PVA modified elastomer) and example 4 (30 wt% ChCl-PVA modified elastomer). Examples 1 to 6 all have good conductivity, and the conductivity increases as the amount of ChCl added increases and the number of ions which can move freely increases. Wherein the conductivity of example 4 is 3.5X10 -6 S·m -1 。
As shown in FIG. 9, a spectrum of visible light transmittance of example 4 (30 wt% ChCl-PVA modified elastomer) was obtained. The sample has a high transmittance (91.5%) in the visible wavelength range.
As shown in FIG. 10 (a), the stress-strain (stretch-recovery) curve of example 4 (30 wt% ChCl-PVA modified elastomer). The samples exhibited excellent stretch recovery at 5 to 40% strain. As shown in fig. 10 (b), the measurement of the resistance was performed on the sample while the stretch-recovery test was performed in example 4, and the rate of change in resistance was used as the sensor output signal, which revealed that example 4 had excellent stability as a sensor, and the sensor signal outputting the rate of change in resistance increased as the deformation increased, and the degree of deformation of the sensor could be determined from the magnitude of the rate of change in resistance.
As shown in FIG. 11, example 4 (30 wt% ChCl-PVA modified elastomer) was used as a resistance sensor signal plot for the sensor to monitor finger deformation. The sensor can monitor the minute deformation of the finger, and the magnitude of the resistance change increases as the degree of bending of the finger increases.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (9)
1. A high-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer is characterized in that the mass ratio is 15-30: 100 is prepared by adopting solution blending of quaternary ammonium salt and PVA;
the quaternary ammonium salt has the following structural formula:
wherein R1-R4 are each independently hydrocarbyl or hydroxyalkyl; x is X － Is halogen anion.
2. A high strength, freeze resistant and transparent electrically conductive PVA/quaternary ammonium salt elastomer according to claim 1, wherein X in the quaternary ammonium salt － In particular F － 、Cl － 、Br － Or I － 。
3. A high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer according to claim 1, wherein said quaternary ammonium salt is choline chloride.
4. A process for the preparation of a high strength, freeze resistant and transparent electrically conductive PVA/quaternary ammonium salt elastomer according to any of claims 1 to 3, characterized by the steps of:
step (1), adding PVA and quaternary ammonium salt into a reaction kettle according to a certain proportion for solution blending; wherein the mass ratio of the quaternary ammonium salt to the PVA is 15-30: 100;
and (2) spreading the solution after solution blending, drying to remove the solvent to obtain the PVA/quaternary ammonium salt elastomer, and finally carrying out performance characterization.
5. The method of producing a high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer according to claim 4, wherein the solvent in step (1) is water.
6. The method of producing a high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer according to claim 4, wherein the temperature in step (1) is 80 ℃.
7. Use of a high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer according to any of claims 1-3 in freeze resistant flexible sensors.
8. The use according to claim 7, wherein the PVA has hydrogen bonds with the quaternary ammonium salt, and the melting ionization of the quaternary ammonium salt in the PVA composite matrix due to the hydrogen bond interactions results in a PVA glass transition temperature T g Melting temperature T m The crystallization performance changes, T g 、T m The crystallization capacity of PVA is reduced, and meanwhile, the composite material becomes soft due to the increase of the free volume of PVA molecular chains, and the crystal region serves as a physical crosslinking point to provide the composite material with the recovery capacity.
9. A freeze resistant flexible sensor comprising a high strength, freeze resistant and transparent conductive PVA/quaternary ammonium salt elastomer as claimed in any of claims 1 to 3.
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