CN109749441B - A kind of preparation method of conductive hydrogel based on one-dimensional nano-polypyrrole - Google Patents

Abstract

Translated fromChinese

一种基于一维纳米聚吡咯导电水凝胶的制备方法,其步骤为，将结构引导组分加入去离子水中,施加超声波，再向此溶液中加入吡咯；称取三价铁盐溶解去离子水中；将步骤一和步骤三得到的溶液快速混合均匀静置减压抽滤同时用酸溶液淋洗滤饼至滤液接近无色、滤饼经抽气凝缩至多孔的类海绵结构，得到一维纳米聚吡咯；减压抽真空条件下，按照质量份，取1份一维纳米聚吡咯和1～5份能形成物理交联的高分子溶液或者能形成化学交联的高分子溶液及其相应的交联剂渗入至多孔的一维纳米聚吡咯中，待混合均匀后灌装至模具中，通过凝胶化过程即得到一维纳米聚吡咯的导电水凝胶；本发明具有能够充分发挥廉价导电高分子的应用优势，更适合于大规模推广的优点。

A preparation method based on one-dimensional nano-polypyrrole conductive hydrogel, the steps are: adding a structure guiding component into deionized water, applying ultrasonic waves, and then adding pyrrole to the solution; weighing a ferric salt to dissolve deionized water In water; the solutions obtained in steps 1 and 3 are quickly mixed and evenly left to stand under reduced pressure and suction filtration, while the filter cake is rinsed with an acid solution until the filtrate is nearly colorless, and the filter cake is condensed into a porous sponge-like structure by suction to obtain a One-dimensional nano-polypyrrole; under reduced pressure and vacuum conditions, take 1 part of one-dimensional nano-polypyrrole and 1-5 parts of polymer solution capable of forming physical cross-linking or polymer solution capable of forming chemical cross-linking and its The corresponding cross-linking agent penetrates into the porous one-dimensional nano-polypyrrole, and after being mixed evenly, it is filled into the mold, and the conductive hydrogel of the one-dimensional nano-polypyrrole is obtained through the gelation process; The application advantages of cheap conductive polymers are more suitable for large-scale promotion.

Description

Preparation method of conductive hydrogel based on one-dimensional nano polypyrrole

Technical Field

The invention belongs to the field of preparation of conductive hydrogel, and particularly relates to a preparation method of conductive hydrogel based on one-dimensional nano polypyrrole.

Background

The conductive hydrogel has good flexibility and conductivity, can conveniently reflect information such as stress, strain and temperature through the change of an electric signal, and is a multifunctional flexible electronic material which is expected to be used for artificial intelligence, wearable equipment, energy storage devices and the like. Electrolyte salt, nano carbon material and conductive polymer can be used for constructing conductive hydrogel. Compared with electrolyte salts, the conductive polymer has the dual characteristics of an electronic conductor and an ion conductor, and the conductivity is more outstanding; compared with nano carbon materials such as graphene, carbon nano tubes and the like, the conductive polymer is convenient to synthesize and strong in modifiability, and the characteristic of the polymer has excellent compatibility with a gel network supporting material which is the polymer. In addition, by means of the hydrogen bond action, the electrostatic action and the like between the specific chemical groups of the conductive polymer and the water-soluble polymers forming the gel network, the composition, the structure and the performance of the hydrogel can be effectively regulated and controlled, and the application range of the flexible electronic material is remarkably widened.

However, since polyaniline, polypyrrole and other conductive polymer materials are often not melted and dissolved, there are multiple technical difficulties in preparing conductive hydrogel by compounding conductive polymer and water-soluble polymer. Various methods for preparing conductive polymer-based hydrogels have been reported in the literature, and these methods can be mainly classified into two types according to the preparation process: the first method, also the most commonly used method, is to prepare insulating hydrogel in advance by using polymers such as polyvinyl alcohol (PVA), polyacrylic acid (PAA) or Polyacrylamide (PAM) (j.mater.chem.b., 2016,4,8016), and then to immerse the insulating hydrogel in solutions of conductive polymer monomers and oxidants in sequence for polymerization to obtain conductive hydrogel (CN 108794767A; chem.pap. (2017)71: 269-291). However, due to the three-dimensional block structure of the gel, when the conductive polymer is formed on the outer layer of the gel, the monomer or oxidant is prevented from further diffusing into the gel, so that the inner and outer conductive components of the gel are unevenly distributed to form a skin-core structure, and the conductivity and mechanical properties of the gel are affected; in addition, the synthesis of conductive polymers often produces multiple oligomeric products and by-products simultaneously, and after the gel is formed, a lengthy and time-consuming dialysis purification process is required to remove impurities remaining in the gel (Macromolecules,2017,50, 972).

The second method is to synthesize a conductive polymer in advance, and then introduce a polymer forming a gel network or a prepolymer thereof into the conductive polymer to prepare hydrogel. The disadvantage of this type of method is that, on the one hand, in addition to commercially available electrically conductive polythiophenes (PEDOT: PSS) which are formed directly in aqueous dispersion (angelw. chem. int. ed.2017,56,14159), the disadvantage of their insolubility and non-melting of inexpensive electrically conductive polyaniline and polypyrrole fillers leads to poor dispersibility of the electrically conductive fillers in highly viscous water-soluble polymers or their prepolymer systems, making it difficult to obtain a uniform electrically conductive network. For example, in the literature (adv. mater.2017,29,1700533), a hydrogel is constructed by modifying PPy with chitosan to improve the dispersibility of PPy in the PAA system. On the other hand, in a system in which a gel network polymer is formed by radical-initiated polymerization, a peroxide initiator generally used, for example, ammonium persulfate, potassium persulfate, or the like, also changes the oxidation-reduction state of the conductive polymer, and deteriorates the conductivity of the latter. Patent CN 107137765A ball-milling and pulverizing electrochemically polymerized PPy, mixing with lyophilized carboxymethyl chitosan, stirring, and injecting water to prepare hydrogel. In such a process, PPy incorporated into the hydrogel will not retain its in situ formed micro/nano-structure, and the non-covalent interaction between PPy in the form of ball-milled micro-particles and the chitosan network will be difficult to perform adequately.

Stejskal et al have proposed a method for obtaining a conductive polyaniline hydrogel having a uniform composition and good mechanical properties and conductivity by performing dispersion polymerization of aniline in a solution of a water-soluble polymer (e.g., PVA) and causing the PVA solution to gel by low-temperature freezing (Macromolecules 2017,50, 972; ColloidPolym. Sci.,2018,296,989). Similarly, pyrrole polymerization is carried out in agarose solution at high temperature as in Park et al, and cryogenically cooled to obtain conductive polypyrrole-containing sepharose (j. mater.chem.c,2014,2, 736). Although the method overcomes the defects of the two methods to a certain extent, a dispersion polymerization system can interfere the formation of a self-assembled micro/nano structure of the conductive polymer, and the conductive polymer hydrogel obtained by the method is difficult to have a micro/nano-scale woven structure. Especially for PPy whose conductivity strongly depends on nanoscale morphology, it is important to ensure good conductivity of the gel that one-dimensional nanostructures are maintained during the formation of the hydrogel.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a one-dimensional nano polypyrrole-based conductive hydrogel, which enables polypyrrole to keep a nano structure formed by in-situ assembly of the polypyrrole and a high doping degree to be uniformly and effectively compounded with gel network macromolecules according to the characteristic that a pyrrole chemical oxidation polymerization system is easy to form a loose and porous sponge-like product, so that the polypyrrole hydrogel with uniform composition and high conductivity can be obtained without complex post-treatment procedures.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.1 to 0.6 part of structure-directing component into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the structure-directing component, and then adding 1 to 3 parts of pyrrole into the solution;

weighing trivalent ferric salt, wherein the molar ratio of the trivalent ferric salt to the pyrrole in the step one is (1-3):1, and dissolving the trivalent ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing at room temperature, carrying out vacuum filtration on the obtained product to obtain a filter cake, simultaneously leaching the filter cake with 0.2-1 mol/L acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain one-dimensional nano polypyrrole;

step four: and (2) under the condition of vacuum pumping, according to the mass part, infiltrating 1 part of one-dimensional nano polypyrrole and 1-5 parts of polymer solution capable of forming physical crosslinking or polymer solution capable of forming chemical crosslinking and a corresponding crosslinking agent into porous one-dimensional nano polypyrrole, uniformly mixing, filling into a mold, and obtaining the conductive hydrogel of the one-dimensional nano polypyrrole through a gelation process.

And further, standing for 6-24 hours at room temperature.

Further, the pressure reduction condition of the product obtained in the third step is 0.4-0.7 atm.

Further, the structure guiding component is methyl orange or orange I;

further, the ferric iron salt is one or more of ferric trichloride, ferric sulfate and ferric nitrate;

further, the acid solution is one of a hydrochloric acid solution, a sulfuric acid solution and a p-toluenesulfonic acid solution;

further, the vacuum pumping condition is 0.1-0.5 atm.

Further, the water-soluble polymer solution for forming physical crosslinking is a polyvinyl alcohol solution with the molecular weight of 6-20 ten thousand and the concentration of 5-20 wt%, and a polyacrylamide solution with the molecular weight of 100-200 ten thousand and the concentration of 3-8%; the water-soluble polymer capable of forming chemical crosslinking and the corresponding crosslinking agent system thereof are that 0.5 part of 0.02-0.05 mol/L Fe is adopted corresponding to 1 part of polyacrylic acid (PAA) aqueous solution with the concentration of 10-40 percent³⁺、Zn²⁺Or Al³⁺One of the ionic solutions is crosslinked.

Compared with the prior art, the invention has the following beneficial technical effects:

(1) the doped polypyrrole directly and uniformly enters the gel network in a form of a one-dimensional nanostructure, so that the self-assembly characteristic of a PPy in-situ polymerization system is retained, the PPy is in contact with a gel network polymer to the maximum extent, and the conductive performance advantage of the one-dimensional polypyrrole can be fully exerted;

(2) the processes of reduced pressure suction filtration and leaching can not only remove oligomers and byproducts of a polymerization system, but also carry out acid doping on PPy, and the polymer solution permeates into a PPy filter cake to prepare hydrogel, so that a time-consuming dialysis purification procedure on the hydrogel is not needed, swelling of the hydrogel in the purification process by dialysis is avoided, and the quality and the size stability of a product can be effectively ensured;

(3) the gel network is constructed by directly using the prefabricated polymer solution, the method for preparing the composite gel can be conveniently popularized to various polymer hydrogel systems, the applicability of the process method is strong, and the method is very suitable for regulating and controlling the gel composition and the mechanical property.

The conductivity of the polypyrrole hydrogel obtained by the method is 1-5S/m, the tensile elastic modulus of the hydrogel is 80kPa, the tensile strength is 40kPa, the compressive elastic modulus is 350kPa, and the conductivity and the strength of the polypyrrole hydrogel are superior to those of conductive polymer hydrogels (Macromolecules 2017,50,972) obtained in the literature through in-situ polymerization and the like. Compared with the existing method for preparing the conductive hydrogel, the method has the advantages of simple operation and strong universality, can fully exert the application advantages of cheap conductive macromolecules, and is more suitable for large-scale popularization.

Drawings

FIG. 1 shows a large number of nano-cores (left) rapidly formed by mixing a sulfonic dye and a ferric salt and one-dimensional nano-polypyrrole (right) obtained by guiding pyrrole polymerization.

FIG. 2 polymerization product (a) obtained in step three of the present invention, polypyrrole "sponge" (b, c) after washing with suction.

FIG. 3 shows the conductive hydrogel obtained by pouring the water-soluble polymer solution obtained in step four of the present invention.

FIG. 4 tensile (a) and compressive (b) performance test curves for a conductive hydrogel obtained by the present invention.

Detailed Description

The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.

Example 1

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.1 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 2 parts of pyrrole into the solution;

weighing ferric trichloride, wherein the molar ratio of the ferric trichloride to the pyrrole in the step one is 1:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 6 hours at room temperature, decompressing the obtained product by 0.7atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.2mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: under the condition of reducing pressure and pumping air to 0.5atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 1 part of solution with the molecular weight of 65000 of PVA to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, and freezing and then thawing to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 2

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.2 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 1.5 parts of pyrrole into the solution

Weighing ferric sulfate, wherein the molar ratio of the ferric sulfate to the pyrrole in the step one is 2:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 12 hours at room temperature, decompressing the obtained product by 0.6atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.2mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: under the condition of reducing pressure and pumping air to 0.3atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 2 parts of 3% PVA and solution with the molecular weight of 200 ten thousand to permeate into the one-dimensional nano polypyrrole and uniformly mix, filling the mixture into a mold, and freezing and then thawing to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 3

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.3 part of orange I into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the orange I, and adding 1.5 parts of pyrrole into the solution

Weighing ferric nitrate, wherein the molar ratio of ferric nitrate to the pyrrole in the step one is 2:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 24 hours at room temperature, decompressing the obtained product by 0.5atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.5mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: under the condition of reducing pressure and pumping air to 0.2atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 1 part of 5% PAM solution with the molecular weight of 100 ten thousand to permeate into the one-dimensional nano polypyrrole and uniformly mix, filling the mixture into a mold, and cooling to room temperature to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 4

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.4 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 2 parts of pyrrole into the solution

Weighing ferric sulfate, wherein the molar ratio of the ferric sulfate to the pyrrole in the step one is 1.5:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 8 hours at room temperature, decompressing the obtained product by 0.4atm, carrying out suction filtration to obtain a filter cake, leaching the filter cake by using 1mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain one-dimensional nano polypyrrole;

step four: under the condition of reducing pressure and pumping air to 0.2atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 4 parts of 10% PVA solution and 14500 molecular weight solution to permeate into the one-dimensional nano polypyrrole and uniformly mix, filling the mixture into a mold, freezing and then thawing to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 5

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.5 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 3 parts of pyrrole into the solution

Weighing ferric sulfate, wherein the molar ratio of the ferric sulfate to the pyrrole in the step one is 1.8:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 12 hours at room temperature, decompressing the obtained product by 0.5atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.5mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: at 60 ℃, decompressing and pumping to 0.3atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 5 parts of 5% PVA and 205000 molecular weight solution to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, freezing and then thawing to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 6

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.6 part of orange I into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the orange I, and adding 3 parts of pyrrole into the solution;

weighing ferric sulfate, wherein the molar ratio of the ferric sulfate to the pyrrole in the step one is 2.5:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 18 hours at room temperature, decompressing the obtained product by 0.5atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.75mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: at room temperature, decompressing and pumping to 0.2atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 1 part of 30% PAA solution and 0.5 part of 0.03mol/L ferric trichloride solution to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, and standing at room temperature for 12 hours to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 7

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.2 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 1 part of pyrrole into the solution;

weighing ferric trichloride, wherein the molar ratio of the ferric trichloride to the pyrrole in the step one is 1:1, and dissolving ferric salt in 50 parts of deionized water;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 24 hours at room temperature, decompressing the obtained product by 0.5atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.75mol/L hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: at room temperature, decompressing and pumping to 0.4atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 2 parts of 10% PAA solution and 0.5 part of 0.02mol/L zinc acetate solution to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, and standing at room temperature for 12 hours to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 8

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.5 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 3 parts of pyrrole into the solution;

weighing ferric nitrate and ferric sulfate, wherein the molar ratio of the total molar amount of the ferric nitrate and the ferric sulfate to the pyrrole in the step one is 1.5:1, and dissolving the ferric nitrate and the ferric sulfate in 50 parts of deionized water, wherein the molar ratio of the ferric nitrate to the ferric sulfate is 2: 1;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 6 hours at room temperature, decompressing the obtained product by 0.4atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.2mol of hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain one-dimensional nano polypyrrole;

step four: at room temperature, decompressing and pumping to 0.1atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 1 part of 40% PAA solution and 0.5 part of 0.05mol/L aluminum sulfate solution to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, and standing at room temperature for 12 hours to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 9

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.55 part of methyl orange into 50 parts of deionized water according to the mass part, applying ultrasonic waves to dissolve and uniformly disperse the methyl orange, and adding 3 parts of pyrrole into the solution;

weighing ferric trichloride, ferric nitrate and ferric sulfate, wherein the ratio of the total mole of the ferric trichloride, the ferric nitrate and the ferric sulfate to the mole of the pyrrole in the step one is 1:1, and the ferric trichloride, the ferric nitrate and the ferric sulfate are dissolved in 50 parts of deionized water, wherein the mole ratio of the three ferric salts is 5:3: 2;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 6 hours at room temperature, decompressing the obtained product by 0.4atm, carrying out suction filtration to obtain a filter cake, simultaneously leaching the filter cake by 0.2mol of hydrochloric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain one-dimensional nano polypyrrole;

step four: at room temperature, decompressing and pumping to 0.3atm, taking 1 part of one-dimensional nano polypyrrole according to the mass part, enabling 4 parts of 15% PVA solution with the molecular weight of 145000 to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, freezing and then thawing to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

Example 10

A preparation method of conductive hydrogel based on one-dimensional nano polypyrrole comprises the following steps:

step one, adding 0.2 part of methyl orange and 0.1 part of orange I into 50 parts of deionized water according to the mass parts, applying ultrasonic waves to dissolve and disperse the methyl orange and the orange I uniformly, and adding 3 parts of pyrrole into the solution;

weighing ferric trichloride, ferric nitrate and ferric sulfate, wherein the ratio of the total mole of the ferric trichloride, the ferric nitrate and the ferric sulfate to the mole of the pyrrole in the step one is 1.5: dissolving ferric trichloride, ferric nitrate and ferric sulfate in 50 parts of deionized water, wherein the molar ratio of the three ferric salts is 3:2: 1;

step three, quickly and uniformly mixing the solutions obtained in the step one and the step two, standing for 20 hours at room temperature, decompressing the obtained product by 0.5atm, filtering to obtain a filter cake, leaching the filter cake by using 0.4mol/L sulfuric acid solution until the filtrate is nearly colorless, and condensing the filter cake to a porous sponge-like structure by pumping to obtain the one-dimensional nano polypyrrole;

step four: at room temperature, decompressing and pumping to 0.2atm, taking 1 part of one-dimensional nano polypyrrole, 1 part of 8% PAM and 100 ten thousand of solution with molecular weight to permeate into the one-dimensional nano polypyrrole and uniformly mixing, filling the mixture into a mold, and cooling to room temperature to obtain the conductive hydrogel of the one-dimensional nano polypyrrole.

The method makes full use of the characteristic of pyrrole chemical oxidative polymerization in a system containing sulfonic acid group dye, namely, polypyrrole obtained by polymerization grows into a one-dimensional nano structure (figure 1) with a large length-diameter ratio by attaching to a nano core which is formed in a large amount at the beginning of reaction, a loose and porous sponge-like structure (figure 2) is formed by lapping, and high molecular aqueous solution forming a gel network uniformly enters pores of the polypyrrole-like sponge structure by decompressing and vacuumizing. Acid doping is carried out on the polypyrrole in the process of suction filtration and leaching (the conductivity of the obtained polypyrrole is up to 14000S/m), and the polypyrrole hydrogel with good mechanical property and conductivity is obtained after a water-soluble polymer network is reinforced in a freezing-thawing or crosslinking mode and the like. The conductivity of the polypyrrole hydrogel obtained by the method is 1-5S/m, the tensile elastic modulus of the hydrogel is 80kPa, the tensile strength is 40kPa, the compressive elastic modulus is 350kPa, and the conductivity and the strength of the polypyrrole hydrogel are superior to those of conductive polymer hydrogels (Macromolecules 2017,50,972) obtained in the literature through in-situ polymerization and the like. Compared with the existing method for preparing the conductive hydrogel, the method has the advantages of simple operation and strong universality, can fully exert the application advantages of cheap conductive macromolecules, and is more suitable for large-scale popularization.

Claims (7)

Translated fromChinese

1.一种基于一维纳米聚吡咯导电水凝胶的制备方法，其特征在于，其步骤为:1. a preparation method based on one-dimensional nano-polypyrrole conductive hydrogel, is characterized in that, its steps are:步骤一：按照质量份，将0.1份~0.6 份的甲基橙或橙黄I加入至50份去离子水中，施加超声波使得甲基橙或橙黄I溶解、分散均匀，再向此溶液中加入1份~3份的吡咯；Step 1: According to mass parts, add 0.1 to 0.6 parts of methyl orange or orange yellow I to 50 parts of deionized water, apply ultrasonic waves to make methyl orange or orange yellow I dissolve and disperse uniformly, and then add 1 part to this solution. ~3 parts pyrrole;步骤二：称取三价铁盐，三价铁盐与步骤一中的吡咯的摩尔比为（1-3）:1，将三价铁盐溶解于50 份去离子水中；Step 2: Weigh the ferric salt, the molar ratio of the ferric salt to the pyrrole in step 1 is (1-3): 1, and dissolve the ferric salt in 50 parts of deionized water;步骤三：将步骤一和步骤二得到的溶液快速混合均匀，于室温下静置，将所得产物减压抽滤，得到滤饼，同时用0.2 mol/L~1mol/L的酸溶液淋洗滤饼至滤液接近无色、滤饼经抽气凝缩至多孔的类海绵结构，得到一维纳米聚吡咯；Step 3: Quickly mix the solutions obtained in steps 1 and 2, let stand at room temperature, and filter the obtained product under reduced pressure to obtain a filter cake, and at the same time, use 0.2 mol/L to 1 mol/L acid solution to wash and filter The cake is nearly colorless to the filtrate, and the filter cake is condensed into a porous sponge-like structure by suction to obtain one-dimensional nano-polypyrrole;步骤四：减压抽真空条件下，按照质量份，取1份一维纳米聚吡咯和1~5份能形成物理交联的高分子溶液或者能形成化学交联的高分子溶液及其相应的交联剂渗入至多孔的一维纳米聚吡咯中，待混合均匀后灌装至模具中，通过凝胶化过程即得到一维纳米聚吡咯的导电水凝胶。Step 4: Under the condition of reduced pressure and vacuum, take 1 part of one-dimensional nano-polypyrrole and 1 to 5 parts of the polymer solution that can form physical cross-linking or the polymer solution that can form chemical cross-linking and its corresponding The cross-linking agent penetrates into the porous one-dimensional nano-polypyrrole, and after mixing uniformly, it is filled into the mold, and the conductive hydrogel of the one-dimensional nano-polypyrrole is obtained through the gelation process.2.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法,其特征在于，所述的室温下静置的时间为6 ~24 h。2. a kind of preparation method based on one-dimensional nano polypyrrole conductive hydrogel according to claim 1, is characterized in that, the time of standing at room temperature is 6～24 h.3.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法,其特征在于，所述的步骤三中的所得产物减压的条件为0.4~0.7 atm。3. a kind of preparation method based on one-dimensional nano polypyrrole conductive hydrogel according to claim 1, is characterized in that, the condition that the obtained product in described step 3 is decompressed is 0.4～0.7 atm.4.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法,其特征在于，所述的三价铁盐为三氯化铁、硫酸铁、硝酸铁中的一种或几种。4. a kind of preparation method based on one-dimensional nano-polypyrrole conductive hydrogel according to claim 1, is characterized in that, described ferric salt is one of ferric chloride, ferric sulfate, ferric nitrate species or several.5.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法,其特征在于，所述的酸溶液为盐酸溶液、硫酸溶液、对甲苯磺酸溶液中的一种。5. a kind of preparation method based on one-dimensional nano polypyrrole conductive hydrogel according to claim 1, is characterized in that, described acid solution is a kind of in hydrochloric acid solution, sulfuric acid solution, p-toluenesulfonic acid solution .6.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法,其特征在于，所述的减压抽真空条件为0.1~0.5 atm。6. a kind of preparation method based on one-dimensional nano polypyrrole conductive hydrogel according to claim 1, is characterized in that, described decompression and vacuuming condition is 0.1～0.5 atm.7.根据权利要求1所述的一种基于一维纳米聚吡咯导电水凝胶的制备方法，其特征在于，所述能形成物理交联的高分子溶液为分子量为6万~20万、浓度为5~20wt%的聚乙烯醇溶液或分子量为100万~200万、浓度为3~8%的聚丙烯酰胺溶液；所述能形成化学交联的高分子溶液为聚丙烯酸水溶液，其相应的交联剂为0.02 mol/L~0.05 mol/L的Fe³⁺、Zn²⁺或Al³⁺离子溶液中的一种，相应于1份浓度为10~40%的聚丙烯酸水溶液，采用0.5份的交联剂进行交联。7. a kind of preparation method based on one-dimensional nano-polypyrrole conductive hydrogel according to claim 1, is characterized in that, described polymer solution that can form physical crosslinking is that molecular weight is 60,000～200,000, concentration It is a polyvinyl alcohol solution with a molecular weight of 5 to 20 wt% or a polyacrylamide solution with a molecular weight of 1 million to 2 million and a concentration of 3 to 8%; the polymer solution that can form chemical crosslinking is an aqueous polyacrylic acid solution, and its corresponding The cross-linking agent is one of Fe³⁺ , Zn²⁺ or Al³⁺ ion solutions of 0.02 mol/L~0.05 mol/L, corresponding to 1 part of polyacrylic acid aqueous solution with a concentration of 10 to 40%, using 0.5 part of cross-linking agent for cross-linking.

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