CN109777014B - High-strength anti-freezing conductive polypyrrole hydrogel and preparation method thereof - Google Patents
High-strength anti-freezing conductive polypyrrole hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength anti-freezing conductive polypyrrole hydrogel and a preparation method thereof, belonging to the field of high polymer materials. The method is characterized in that pyrrole monomers are subjected to in-situ chemical oxidative polymerization in a hydrogen bond enhanced polymer network, multiple freezing-unfreezing circulation processes are assisted, and a low freezing point medium is adopted to partially replace water in gel, so that the high-strength anti-freezing conductive polypyrrole hydrogel is obtained; the high-strength anti-freezing conductive polypyrrole hydrogel prepared by the method has good conductivity and mechanical property, can tolerate a wider temperature range, is not easy to lose water and collapse, and is not easy to freeze and freeze. The high-strength antifreeze conductive polypyrrole hydrogel can tolerate the temperature of minus 20 ℃ for 72 hours and is not frozen, the hydrogel can be placed at the temperature of 80 ℃ for 4 hours and cannot be dried or collapsed, the conductivity of the gel reaches 0.5-1.5S/m, the tensile strength reaches 0.5MPa, and the compression elastic modulus is 200 kPa.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a high-strength anti-freezing conductive polypyrrole hydrogel and a preparation method thereof, and particularly relates to a high-strength anti-freezing conductive hydrogel based on conductive polypyrrole and a hydrogen bond reinforced polymer network and a preparation method thereof.
Background
The hydrogel is a soft material containing a large amount of water by a high molecular three-dimensional network, has medium composition similar to an organism, good flexibility, unique performance and wide application prospect. The conductive polymer hydrogel built by the hydrogel matrix can conveniently convert stimuli such as strain, pressure, temperature and the like into electric signals and conduct the electric signals, and is an attractive flexible electronic material (patent CN108376618A, patent CN106009000A and the like). However, due to the contradiction between the conductivity and the mechanical properties of the hydrogel, the mechanical properties, especially the compression resistance, of the conductive polymer hydrogel obtained in the early stage are not satisfactory, and the conductive polymer hydrogel is difficult to meet the application requirements of flexible electronic materials required by electronic skin patches, wearable devices and the like. Although researchers have made extensive attempts to improve the mechanical properties of conductive gels (j. mater. chem. c,2014,2,736Scientific rep, 2014,4, 5792; adv. mater.2017,29,1700533; acsappl. mater. interfaces 2018,10, 36218. 36228; since the hydrogel contains a large amount of water (> 90%), conventional hydrogel materials inevitably collapse due to water evaporation under high temperature conditions, freeze and lose flexibility in low temperature environments, and the temperature window for operation is narrow, which greatly limits the application of such functional materials.
For example, patent publication No. CN 108794767 a discloses a method for preparing a strain-induced high-strength conductive hydrogel by first obtaining an insulating gel containing a conductive polymer monomer by ultraviolet-initiated polymerization, and then soaking the insulating gel in an oxidant solution. The method obtains the conductive polymer by diffusing and initiating polymerization of an oxidant solution into an acrylic gel, wherein the conductive polymer formed at the outer layer of the gel inevitably impedes further diffusion of the oxidant to the center of the gel, so that the conductive polymer monomer at the center of the gel cannot be fully reacted, and the gel composition is not uniform. For example, patent publication No. CN 108559022 a discloses a method for preparing a conductive gel by doping an acrylic polymer with lithium acetate. Such conductive gels rely essentially on ionic conductivity, which is often orders of magnitude less than electronic conductors. Liumingjie et al convert conductive poly 3, 4-ethylenedioxythiophene: polystyrene sulfonic acid solution (PEDOT: PSS) and PVA are jointly dissolved in a mixed medium of ethylene glycol and water, and the antifreezing conductive hydrogel is obtained by low-temperature cooling (Angew. chem. int. Ed.2017,56,14159). Although the method is simple and easy to mold, on one hand, the commercial PEDOT directly adopted by the method is easy to be expensive, and the material conductivity adjusting space is limited; on the other hand, the gel only depends on the molecular chain entanglement of the PVA with high concentration to form a three-dimensional network, PEDOT: the PSS and PVA have weaker interaction, so that the gel network is easy to scatter and deform at higher temperature, the geometrical shape can not be kept, and the mechanical property of the gel still has great promotion space from the practical application. The method comprises the steps of firstly carrying out dopamine oxidative polymerization in a carbon nanotube dispersion liquid to obtain a polydopamine modified carbon nanotube, then adding glycerol, further adding acrylamide, acrylic acid and a cross-linking agent, and finally carrying out ultraviolet light initiated polymerization to obtain the conductive antifreeze hydrogel (adv.funct.mater, 2018,28, 1704195). Although the hydrogel has good conductivity and mechanical properties, the preparation process is complicated, the price of the dopamine modifier is relatively high, and the hydrogel is not suitable for large-scale popularization and use in industry and life.
Therefore, obtaining a conductive hydrogel that has high strength and is resistant to freezing would be of great benefit to the development of new flexible electronic materials and to the broadening of hydrogel applications.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the high-strength anti-freezing conductive polypyrrole hydrogel and the preparation method thereof, and the method has wide raw material source, is simple to operate and is easy for industrial production; the high-strength anti-freezing conductive polypyrrole hydrogel prepared by the method has good conductivity and mechanical property, can tolerate a wider temperature range, is not easy to lose water and collapse, and is not easy to freeze and freeze.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a high-strength anti-freezing conductive polypyrrole hydrogel which comprises the following components in parts by mass:
preferably, the polymer stabilizer is polyvinyl alcohol with a molecular weight of 60000-210000 or polyacrylamide with a molecular weight of 100-200 ten thousand.
Preferably, the polyphenol substances are one or two of tannic acid, gallic acid and ellagic acid.
Preferably, the medium with low freezing point is one or two of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate ferric chloride salt, 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate and 1-butyl-3-methylimidazole tetrachloroferric salt.
Preferably, the high-strength antifreeze conductive polypyrrole hydrogel has the conductivity of 0.5-1.5S/m, the tensile strength of 0.5MPa and the compressive elastic modulus of 200 kPa.
The invention also discloses a preparation method of the high-strength antifreeze conductive polypyrrole hydrogel, which comprises the steps of carrying out in-situ chemical oxidative polymerization on pyrrole monomers in a hydrogen bond-enhanced polymer network, assisting in a multiple freezing-thawing cycle process, and partially replacing water in gel by using a low-freezing-point medium to obtain the high-strength antifreeze conductive polypyrrole hydrogel.
Preferably, the preparation method of the high-strength antifreeze conductive polypyrrole hydrogel comprises the following steps:
1) taking 5-10 parts by mass of a high-molecular stabilizer, 0.3-1.5 parts by mass of pyrrole, 0.08-0.4 part by mass of a sulfonic dye, 0.1-1 part by mass of a polyphenol substance, 2-15 parts by mass of a ferric salt and 90-95 parts by mass of deionized water;
2) dissolving a macromolecular stabilizer in deionized water to prepare a macromolecular stabilizer solution, and uniformly dividing the macromolecular stabilizer solution into two parts; adding pyrrole, sulfonic dye and polyphenol substances into 1 part of the macromolecular stabilizer solution, and fully and uniformly stirring to prepare a solution A; adding trivalent ferric salt into the other part of the macromolecular stabilizer solution, and stirring to dissolve the trivalent ferric salt to obtain a solution B;
3) quickly mixing the solution A and the solution B, fully stirring, injecting into a sealed mould, carrying out freezing treatment for 4-12 h at-30 ℃ to-70 ℃ together with the mould, and then carrying out freezing treatment for 24-72 h at-10 ℃ to-20 ℃;
4) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing according to the freezing condition of the step 2), repeating the freezing-unfreezing cycle process for 3-10 times, and dialyzing the obtained gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
5) and (3) placing the obtained high-strength conductive hydrogel in a low freezing point medium at room temperature for vibration treatment for 24 hours to obtain the high-strength antifreeze conductive antifreeze polypyrrole hydrogel.
Preferably, the sulfonic acid group dye is one or two of methyl orange, ethyl orange and acid blue 25.
Preferably, the ferric salt is one or two of ferric trichloride, ferric sulfate, ferric nitrate and ferric p-toluenesulfonate.
Preferably, in the step 5), vibration treatment is performed according to the proportion that 1 part of the high-strength conductive hydrogel is placed in 0.5-0.8 part of the low freezing point medium in parts by mass.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-strength antifreeze conductive polypyrrole hydrogel, firstly, polypyrrole which is low in cost and convenient to synthesize is used as a conductive component, and the conductivity of the polypyrrole used as a filler is up to 10000S/m; secondly, by introducing polyphenol-based biomass components with wide sources, abundant hydrogen bond sites are provided, and a non-covalent network with enhanced multiple hydrogen bonds is formed with a high polymer stabilizer forming a gel network, so that the gel can be endowed with good deformability and high toughness; and thirdly, the ionic liquid with a low freezing point is used as a medium to replace part of water in the commonly used glycerin and glycol anti-freezing medium to replace the water in the gel, so that the conductive gel can be effectively protected from being frozen in the environment with the temperature lower than 0 ℃, the conductive gel can not be greatly evaporated and collapsed due to the water in the environment with the temperature higher than room temperature, certain ionic conductivity can be provided for the gel, the ion and electron transmission can be simultaneously carried out, and the excellent conductivity is shown. Therefore, the high-strength antifreeze conductive polypyrrole hydrogel can resist freezing for 72 hours at the temperature of-20 ℃ and cannot be frozen, the hydrogel can be placed for 4 hours at the temperature of 80 ℃ and cannot be dried or collapsed, the conductivity of the gel reaches 0.5-1.5S/m, the tensile strength reaches 0.5MPa, and the compression elastic modulus is 200 kPa.
The invention discloses a preparation method of high-strength antifreeze conductive polypyrrole hydrogel, which adopts pyrrole monomers to carry out in-situ chemical oxidative polymerization in a hydrogen bond enhanced polymer network, assists in multiple freezing-thawing circulation processes, and adopts a low freezing point medium to partially replace water in gel to prepare the high-strength antifreeze conductive polypyrrole hydrogel. The method has the advantages of cheap and easily-obtained raw materials, simple and feasible preparation method, and wide application prospect, and the obtained gel material has good mechanical property, ionic and electronic conductivity and wide temperature tolerance range.
Drawings
FIG. 1 is a SEM image of the network structure of the high-strength antifreeze conductive polypyrrole hydrogel prepared in example 3 of the invention;
FIG. 2 is a photograph showing the conductivity of the high strength antifreeze conductive polypyrrole hydrogel prepared by the present invention;
FIG. 3 is a graph showing tensile (a) and compressive (b) stress-strain curves of a freeze-resistant conductive polypyrrole hydrogel containing polyphenols (represented by tannic acid TA).
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
The preparation method of the high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps
1) 10 parts of PVA having a molecular weight of 67000 were dissolved in 90 parts of deionized water, and the resulting solution was divided into two parts (about 50ml each); to 1 part of the PVA solution, 0.670 parts of pyrrole, 0.164 parts of methyl orange, 0.5 parts of tannic acid and 0.3 parts of gallic acid were added, and ultrasonic waves were applied to dissolve and uniformly disperse the above substances in the polymer stabilizer solution. Adding 5.4 parts of ferric trichloride into the other part of PVA solution, fully stirring to dissolve and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-50 deg.C ice bath for 8 hr, and standing at-15 deg.C for 72 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing cycle process for 10 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (3) placing 1 part of the obtained hydrogel in 0.5 part of 1-butyl sulfonic acid-3-methylimidazole bisulfate at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 2
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 7.5 parts of PVA with a molecular weight of 145000 are dissolved in 92.5 parts of deionized water and the resulting solution is divided into two portions (about 50ml each); to 1 part of the PVA solution, 0.67 parts of pyrrole, 0.1 parts of methyl orange, 0.64 parts of ethyl orange and 0.5 parts of gallic acid were added, and ultrasonic waves were applied to dissolve and uniformly disperse the above substances in the PVA solution. Adding 2.7 parts of ferric trichloride hexahydrate and 2.0 parts of ferric nitrate into the other part of PVA solution, and fully stirring to dissolve and uniformly mix the ferric trichloride hexahydrate and the ferric nitrate;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-50 deg.C ice bath for 8 hr, and placing in-10 deg.C environment for 24 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 8 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (3) placing 1 part of the obtained hydrogel in 0.6 part of 1-butyl sulfonic acid-3-methylimidazol hydrogen sulfate trichloroferric salt at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 3
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 5 parts of PVA with molecular weight of 205000 were dissolved in 95 parts of deionized water, and the resulting solution was divided into two parts (about 50ml each); to 1 part of the PVA solution, 0.3 part of pyrrole, 0.08 part of methyl orange and 0.3 part of ellagic acid were added, and ultrasonic waves were applied to dissolve and uniformly disperse the above substances in the PVA solution. Adding 3.00 parts of ferric sulfate into the other part of the high polymer PVA solution, fully stirring to dissolve and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-40 deg.C ice bath for 10 hr, and standing at-15 deg.C for 24 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 5 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (3) placing 1 part of the obtained hydrogel in 0.7 part of 1-butyl-3-methyl ferric tetrachlorosalt at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 4
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 6 parts of Polyacrylamide (PAM) having a molecular weight of 100 ten thousand are dissolved in 94 parts of deionized water, and the resulting solution is divided into two parts (about 50ml each); to 1 part of the PAM solution, 0.503 parts of pyrrole, 0.133 parts of ethyl orange, and 0.2g of tannic acid were added, and ultrasonic waves were applied to dissolve and uniformly disperse the above substances in the PAM solution. Adding 2.03 parts of ferric trichloride into the other part of the PAM solution, fully stirring to dissolve and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-30 deg.C ice bath for 12h, and standing at-18 deg.C for 48 h;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 5 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (3) placing 1 part of the obtained hydrogel in 0.6 part of 1-butyl-3-methyl iron tetrachlorosalt at room temperature, and oscillating for 12 hours to obtain the high-strength conductive anti-freezing hydrogel.
Example 5
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 5 parts of PAM having a molecular weight of 200 ten thousand was dissolved in 95 parts of deionized water, and the resulting solution was divided into two parts (about 50ml each); 1 part of pyrrole, 0.245 part of methyl orange and 0.1 part of gallic acid are added into 1 part of the macromolecular stabilizer solution, and ultrasonic waves are applied to dissolve and uniformly disperse the substances in the PAM solution. Adding 11.3 parts of ferric p-toluenesulfonate and 2.7 parts of ferric trichloride into the other part of the PAM solution, fully stirring to dissolve the ferric p-toluenesulfonate and the ferric trichloride, and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-40 deg.C ice bath for 10 hr, and standing at-20 deg.C for 48 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 10 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (2) placing 1 part of the obtained hydrogel in 0.4 part of 1-butyl-3-methyl tetrachloroferric salt and 0.1 part of 1-butyl sulfonic acid-3-methylimidazole bisulfate at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 6
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 8 parts of PVA with a molecular weight of 145000 are dissolved in 92 parts of deionized water and the resulting solution is divided into two portions (about 50ml each); 1.3 parts of pyrrole, 0.4 part of acid blue 25, 0.5 part of ellagic acid and 0.3 part of tannic acid are added to 1 part of the PVA solution, and ultrasonic waves are applied to dissolve and disperse uniformly. Adding 5.4 parts of ferric trichloride and 2.0 parts of ferric sulfate into the other part of PVA solution, and fully stirring to dissolve and uniformly mix the ferric trichloride and the ferric sulfate;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-60 deg.C ice bath for 6 hr, and placing in-18 deg.C environment for 24 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 8 times, and dialyzing the gel in 0.2M acid solution to obtain high-strength conductive hydrogel;
4) and (2) placing 1 part of the obtained hydrogel in 0.4 part of 1-butyl sulfonic acid-3-methylimidazole bisulfate and 0.3 part of 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate trichloroferric salt at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 7
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 9 parts of PVA with a molecular weight of 145000 were dissolved in 91 parts of deionized water and the resulting solution was divided into two portions (about 50ml each); to 1 part of the PVA solution, 0.9 parts of pyrrole, 0.245 parts of methyl orange and 1 part of tannic acid were added, and ultrasonic waves were applied so that pyrrole, methyl orange and tannic acid were dissolved and uniformly dispersed in the PVA solution. Adding 12 parts of ferric nitrate into the other part of PVA solution, fully stirring to dissolve the ferric nitrate and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-70 deg.C ice bath for 4 hr, and standing at-10 deg.C for 24 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 8 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (2) placing 1 part of the obtained hydrogel in 0.6 part of 1-butyl-3-methyl tetrachloroferric salt and 0.2 part of 1-butyl sulfonic acid-3-methylimidazole bisulfate at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 8
A preparation method of a high-strength anti-freezing conductive polypyrrole hydrogel comprises the following steps:
1) 5 parts of PVA with molecular weight of 205000 were dissolved in 95 parts of deionized water, and the resulting solution was divided into two parts (about 50ml each); 1.2 parts of pyrrole, 0.25 parts of methyl orange, 0.05 parts of acid blue 25 and 0.3 parts of ellagic acid are added to 1 part of the PVA solution, and ultrasonic waves are applied to dissolve and uniformly disperse the pyrrole, the methyl orange and the ellagic acid in the PVA solution. Adding 7 parts of ferric p-toluenesulfonate and 8 parts of ferric nitrate into the other part of the PVA solution, and fully stirring to dissolve and uniformly mix the ferric p-toluenesulfonate and the ferric nitrate;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, rapidly freezing together with the mold in-60 deg.C ice bath for 6h, and standing at-20 deg.C for 72 h;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing cycle process for 8 times, and dialyzing the gel in 0.2M acid solution to obtain high-strength conductive hydrogel;
4) and (3) placing 1 part of the obtained hydrogel in 0.6 part of 1-butyl sulfonic acid-3-methylimidazole tetrachloroferric salt at room temperature, and oscillating for 12 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Example 9
1) 8 parts of Polyacrylamide (PAM) having a molecular weight of 100 ten thousand are dissolved in 92 parts of deionized water, and the resulting solution is divided into two parts (about 50ml each); 1.5 parts of pyrrole, 0.36 parts of ethyl orange, 0.04 parts of acid blue 25 and 0.1 part of gallic acid are added into 1 part of the polymer stabilizer solution, and ultrasonic waves are applied to dissolve and uniformly disperse the substances in the PAM solution. Adding 6.5 parts of ferric trichloride into the other part of the PAM solution, fully stirring to dissolve and uniformly mixing;
2) mixing the two solutions quickly, stirring thoroughly, injecting into sealed plastic mold, freezing together with the mold in-40 deg.C ice bath for 12 hr, and standing at-20 deg.C for 48 hr;
3) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing, repeating the freezing-unfreezing process for 10 times, and dialyzing the gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
4) and (2) placing 1 part of the obtained hydrogel in 0.4 part of 1-butyl-3-methyl tetrachloroferric salt and 0.1 part of 1-butyl sulfonic acid-3-methylimidazole bisulfate at room temperature, and oscillating for 24 hours to obtain the high-strength anti-freezing conductive polypyrrole hydrogel.
Referring to fig. 1, there is shown an electron micrograph of the network structure of the polypyrrole hydrogel obtained in this example. As can be seen from FIG. 1, the conductive component polypyrrole and the gel network support material are effectively compounded, and fine one-dimensional structures are distributed on the walls of gel channels, indicating the formation of conductive nano polypyrrole. The porous structure is very beneficial to the formation of a conductive path in the hydrogel, and the good combination of the polypyrrole and the gel support material is also beneficial to the gel to show excellent mechanical properties.
Referring to fig. 2, 5 hydrogel samples were randomly selected from the above examples, and 5 LED small bulbs were connected in parallel to both ends of the dry cell by wires, and the connected small bulbs all emitted light, indicating that the resulting gel had good electrical conductivity. And the obtained polypyrrole hydrogel still has good conductivity after being frozen for 72 hours at the temperature of-20 ℃.
The tensile (a) and compressive (b) properties of the high strength, freeze resistant, electrically conductive polypyrrole hydrogels made by the present invention are shown in fig. 3. It can be seen that by adding the polyphenol substances (taking tannic acid as an example), the tensile strength and the compressive strength of the gel are both remarkably improved, which indicates that the hydrogen bonding effect between the added polyphenol substances and the gel support network material greatly enhances the mechanical property of the hydrogel.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. The high-strength anti-freezing conductive polypyrrole hydrogel is characterized by comprising the following components in parts by mass:
5-10 parts of a high-molecular stabilizer,
0.5 to 3 parts of high-conductivity polypyrrole,
0.1 to 1 part of polyphenol substances,
2-15 parts of a trivalent ferric salt,
40-60 parts of low freezing point medium,
90-95 parts of water;
the medium with low freezing point is one or two of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate ferric chloride salt, 1-butyl sulfonic acid-3-methylimidazole bisulfate and 1-butyl-3-methylimidazole tetrachloroferric salt.
2. The high-strength antifreeze conductive polypyrrole hydrogel according to claim 1, wherein the high molecular stabilizer is polyvinyl alcohol with a molecular weight of 60000-210000 or polyacrylamide with a molecular weight of 100-200 ten thousand.
3. The high strength antifreeze conductive polypyrrole hydrogel according to claim 1, wherein said polyphenols are one or two of tannic acid, gallic acid and ellagic acid.
4. The high-strength antifreeze conductive polypyrrole hydrogel according to claim 1, wherein the conductivity of the high-strength antifreeze conductive polypyrrole hydrogel is 0.5 to 1.5S/m, the tensile strength is 0.5MPa, and the modulus of elasticity under compression is 200 kPa.
5. The preparation method of the high-strength antifreeze conductive polypyrrole hydrogel according to any one of claims 1 to 4, characterized in that pyrrole monomers are subjected to in-situ chemical oxidative polymerization in a hydrogen bond-enhanced polymer network, a plurality of freezing-thawing cycles are assisted, and a low freezing point medium is used to partially displace water in the gel to obtain the high-strength antifreeze conductive polypyrrole hydrogel, wherein the specific preparation process comprises the following steps:
1) taking 5-10 parts by mass of a high-molecular stabilizer, 0.3-1.5 parts by mass of pyrrole, 0.08-0.4 part by mass of a sulfonic dye, 0.1-1 part by mass of a polyphenol substance, 2-15 parts by mass of a ferric salt and 90-95 parts by mass of deionized water;
2) dissolving a macromolecular stabilizer in deionized water to prepare a macromolecular stabilizer solution, and uniformly dividing the macromolecular stabilizer solution into two parts; adding pyrrole, sulfonic dye and polyphenol substances into 1 part of the macromolecular stabilizer solution, and fully and uniformly stirring to prepare a solution A; adding trivalent ferric salt into the other part of the macromolecular stabilizer solution, and stirring to dissolve the trivalent ferric salt to obtain a solution B;
3) quickly mixing the solution A and the solution B, fully stirring, injecting into a sealed mould, carrying out freezing treatment for 4-12 h at-30 ℃ to-70 ℃ together with the mould, and then carrying out freezing treatment for 24-72 h at-10 ℃ to-20 ℃;
4) taking out the frozen sample, unfreezing at room temperature, freezing and unfreezing according to the freezing condition of the step 2), repeating the freezing-unfreezing cycle process for 3-10 times, and dialyzing the obtained gel in 0.2M hydrochloric acid solution to obtain high-strength conductive hydrogel;
5) and (3) placing the obtained high-strength conductive hydrogel in a low freezing point medium for vibration treatment at room temperature to obtain the high-strength antifreeze conductive antifreeze polypyrrole hydrogel.
6. The method for preparing a high-strength antifreeze conductive polypyrrole hydrogel according to claim 5, wherein the sulfonic dye is one or two of methyl orange, ethyl orange and acid blue 25.
7. The method for preparing the high-strength antifreeze conductive polypyrrole hydrogel according to claim 5, wherein the ferric salt is one or two of ferric trichloride, ferric sulfate, ferric nitrate and ferric p-toluenesulfonate.
8. The preparation method of the high-strength antifreeze conductive polypyrrole hydrogel according to claim 5, wherein in the step 5), the high-strength conductive hydrogel is placed in the low freezing point medium in an amount of 0.5-0.8 part by mass according to the proportion of 1 part by mass.
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| CN111849367B (en) * | 2020-07-22 | 2022-07-01 | 三峡大学 | High-molecular strip-shaped sheet material for improving sealing and fitting performance of mask and preparation method thereof |
| CN111875960B (en) * | 2020-07-28 | 2022-05-10 | 华北科技学院 | Anti-freezing viscous flame-retardant conductive polymer gel and preparation method and application thereof |
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| CN112708148B (en) * | 2020-12-24 | 2022-08-23 | 江西科技师范大学 | Preparation method of conductive polymer hydrogel applied to solar water purification |
| CN113995889A (en) * | 2021-11-10 | 2022-02-01 | 中新国际联合研究院 | Preparation method and application of exosome-loaded electric signal and chemical signal double-conduction hydrogel scaffold |
| CN113831556A (en) * | 2021-11-10 | 2021-12-24 | 中新国际联合研究院 | Preparation method and application of tannin crosslinked polypyrrole conductive polymer hydrogel |
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