Preparation method of self-repairing conductive hydrogel material

Abstract

The application discloses a preparation method of a self-repairing conductive hydrogel material, and comprises the following steps: S1: respectively preparing 20 mL of poly-2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL, and adjusting the pH of the two polymer aqueous solutions to 1-3 by using 1 mol / L hydrochloric acid; S2: adding 0.2 mL of a ferric chloride solution with a concentration of 1 mol / L into the PAMPS aqueous solution in step S1, and stirring for 10-30 minutes to obtain a PAMPS-Fe3+ composite solution; S3: uniformly mixing the PAMPS-Fe3+ composite solution in step S2 with the PAAm aqueous solution, continuously stirring for 20-30 minutes to obtain a precipitate, and collecting the precipitate by centrifugation and pressing into shape between glass plates; and S4: immersing the compound pressed into shape in step S3 in a NaCl solution with a concentration of 1.5 mol / L for 20-30 minutes to load NaCl. The application provides a method for preparing a self-repairing conductive hydrogel which is excellent in conductive performance and mechanical performance and environment-friendly, and adds non-toxic and harmless inorganic salt as a conductive filler in a polymer hydrogel matrix.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of conductive gel materials, and particularly to a preparation method of a self-repairing conductive hydrogel material. BACKGROUND

[0002] Conductive hydrogel is one of the key materials for manufacturing various wearable sensors, which needs to have excellent electrical conductivity, mechanical properties, biocompatibility, self-repairing and other properties, and is composed of conductive fillers and hydrogel matrix. The conductive fillers are usually inorganic substances or conductive polymers with good electrical conductivity, such as ionic liquid, carbon nanotube, graphene, metal nano-ion, Mexene, PEDOT:PSS, polyaniline, etc. The self-repairing performance is based on the dynamic reversible covalent bonds (including borate ester bond, disulfide bond, acylhydrazone bond, Schiff base bond) and non-covalent interactions (including hydrogen bond, electrostatic interaction, metal coordination, etc.) existing in the polymer system. It is of great significance to prepare self-repairing conductive hydrogel with excellent conductive performance and mechanical properties and environmental protection.

[0003] Patent document CN106866994A proposes a preparation method of a conductive hydrogel with polyaniline as a conductive polymer material and dopamine modified polymethylacrylamide as a self-repairing segment. The conductive hydrogel prepared by the method has good self-repairing and conductive properties, and its performance can be regulated by changing the content of methylacrylamide. However, the preparation steps of the conductive hydrogel are too complicated and time-consuming. Patent document CN112538176A proposes a conductive hydrogel with hydrophobically modified polyacrylamide as a hydrogel matrix, modified nanosilver wire as a conductive filler, and macromolecular dextran as a filler for improving the biocompatibility, mechanical strength and self-repairing performance of the hydrogel. The conductive hydrogel can be stretched to 1200%, and the tensile strength can reach 0.6MPa, and the elongation at break can reach 1631%. Patent document CN106632848A discloses a method for preparing a conductive hydrogel by photo-initiated polymerization of ionic liquid. The invention constructs an ionic liquid that can be polymerized by the electrostatic interaction between the zwitterionic liquid 3-(4-vinyl-1-pyridine) propanesulfonate and sodium p-styrenesulfonate, 2-acrylamide-2-methylpropanesulfonic acid or acrylic acid molecules. Then, by means of photo-initiated polymerization, high-strength and high-performance polyionic conductive hydrogel materials are formed by the strong electrostatic interaction between or within the polyionic liquid chains. However, the preparation method of the invention is complicated, the reaction conditions are harsh, and the time is too long. Patent document CN110240714A discloses a polyvinyl alcohol-based conductive hydrogel and a preparation method thereof. The invention is a self-repairing conductive hydrogel material with PEDOT:PSS as a conductive dopant, hydrochloric acid as a catalyst, and PVA as a gel matrix. Patent document CN108546334A provides a self-repairing graphene and polyamide acid composite conductive hydrogel. The invention uses graphene as a conductive filler and a crosslinking agent for polyamide acid, so that graphene and polyamide acid undergo crosslinking reaction to form a self-repairing conductive hydrogel material. SUMMARY

[0004] The purpose of the present application is to provide a preparation method of a self-repairing conductive hydrogel material to solve the problems in the background art.

[0005] To achieve the purpose, the present application provides the following technical solution, a preparation method of a self-repairing conductive hydrogel material, which comprises the following steps:

[0006] S1: Prepare 20mL of poly-2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8mg / mL respectively, and use 1mol / L hydrochloric acid to adjust the pH of the two polymer aqueous solutions to 1-3;

[0007] S2: Add 0.2mL of 1mol / L ferric chloride solution to the PAMPS aqueous solution in step S1, and stir for 10-30 minutes to obtain a PAMPS-Fe3+ composite solution;

[0008] S3: The PAMPS-Fe 3+ composite solution was mixed with the above polyacrylamide aqueous solution uniformly, and the stirring was continued for 20-30 minutes to obtain a precipitate, which was collected by centrifugation and pressed into shape between glass plates;

[0009] S4: The pressed composite in step S3 was soaked in a NaCl solution with a concentration of 1.5 mol / L for 20-30 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel was obtained.

[0010] Preferably, the preparation method comprises the following steps:

[0011] S1: 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL were prepared respectively, and the pH of the two polymer aqueous solutions was adjusted to 1 using 1 mol / L hydrochloric acid;

[0012] S2: 0.2 mL of a ferric chloride solution with a concentration of 1 mol / L was added to the PAMPS aqueous solution in step S1, and stirring was continued for 10 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0013] S3: The PAMPS-Fe 3+ composite solution was mixed with the above polyacrylamide aqueous solution uniformly, and the stirring was continued for 20 minutes to obtain a precipitate, which was collected by centrifugation and pressed into shape between glass plates;

[0014] S4: The pressed composite in step S3 was soaked in a NaCl solution with a concentration of 1.5 mol / L for 20 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel was obtained.

[0015] Preferably, the preparation method comprises the following steps:

[0016] S1: 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL were prepared respectively, and the pH of the two polymer aqueous solutions was adjusted to 2 using 1 mol / L hydrochloric acid;

[0017] S2: 0.2 mL of a ferric chloride solution with a concentration of 1 mol / L was added to the PAMPS aqueous solution in step S1, and stirring was continued for 20 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0018] S3: The PAMPS-Fe 3+ The composite solution is mixed with the above-mentioned polyacrylamide aqueous solution uniformly, and the stirring is continued for 25 minutes to obtain a precipitate, which is collected by centrifugation and pressed into shape between glass plates;

[0019] S4: The pressed composite in step S3 is soaked in a NaCl solution with a concentration of 1.5 mol / L for 25 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-repairing hydrogel is obtained.

[0020] Preferably, the preparation method comprises the following steps:

[0021] S1: 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL are prepared respectively, and the pH of the two polymer aqueous solutions is adjusted to 3 by using 1 mol / L hydrochloric acid;

[0022] S2: 0.2 mL of a ferric chloride solution with a concentration of 1 mol / L is added to the PAMPS aqueous solution in step S1, and stirring is continued for 30 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0023] S3: The PAMPS-Fe 3+ composite solution in step S2 is mixed with the above-mentioned polyacrylamide aqueous solution uniformly, and the stirring is continued for 30 minutes to obtain a precipitate, which is collected by centrifugation and pressed into shape between glass plates;

[0024] S4: The pressed composite in step S3 is soaked in a NaCl solution with a concentration of 1.5 mol / L for 30 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-repairing hydrogel is obtained.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] The present application provides a method for preparing a self-repairing conductive hydrogel which is excellent in conductive performance and mechanical performance and environmentally friendly, wherein a non-toxic and harmless inorganic salt is added to a polymer hydrogel matrix as a conductive filler, so as to simultaneously control the mechanical properties and antifreezing properties of the hydrogel matrix material.

[0027] The polymer hydrogel of the present application can realize self-repairing due to the dynamic covalent bond force, the tensile rate is 0.1 to 1000%, and the compression sensing range is 0.1 to 20 kPa.

[0028] The preparation steps of the conductive hydrogel are simple and no toxic chemicals are used. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0030] The present application provides a technical solution: the technical solution of the present patent is further described in detail below in combination with the specific embodiments.

[0031] A preparation method of a self-repairing conductive hydrogel material, the preparation method comprising the following steps:

[0032] S1: 20 mL of poly-2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL are respectively prepared, and the pH of the two polymer aqueous solutions is adjusted to 1-3 by using 1 mol / L hydrochloric acid;

[0033] S2: 0.2 mL of a ferric chloride solution with a concentration of 1 mol / L is added to the PAMPS aqueous solution in step S1, and stirred for 10-30 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0034] S3: the PAMPS-Fe 3+ composite solution in step S2 is mixed with the above-mentioned polyacrylamide aqueous solution, and stirred for 20-30 minutes to obtain a precipitate, which is then collected by centrifugation and pressed into shape between glass plates;

[0035] S4: the composite pressed into shape in step S3 is soaked in a NaCl solution with a concentration of 1.5 mol / L for 20-30 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-repairing hydrogel is obtained. EMBODIMENT

[0036] A preparation method of a self-repairing conductive hydrogel material, the preparation method comprising the following steps:

[0037] S1: 20 mL of poly-2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL are respectively prepared, and the pH of the two polymer aqueous solutions is adjusted to 1 by using 1 mol / L hydrochloric acid;

[0038] S2: 0.2 mL of 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 10 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0039] S3: The PAMPS-Fe 3+ composite solution in step S2 was mixed with the above-mentioned polyacrylamide aqueous solution, and stirred for 20 minutes to obtain a precipitate, which was then collected by centrifugation and pressed between glass plates to form a composite;

[0040] S4: The pressed composite in step S3 was soaked in a 1.5 mol / L NaCl solution for 20 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel was obtained. Embodiment

[0041] A preparation method of a self-repairing conductive hydrogel material, comprising the following steps:

[0042] S1: 20 mL of 8 mg / mL poly-2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions were prepared respectively, and the pH of the two polymer aqueous solutions was adjusted to 2 using 1 mol / L hydrochloric acid;

[0043] S2: 0.2 mL of 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 20 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0044] S3: The PAMPS-Fe 3+ composite solution in step S2 was mixed with the above-mentioned polyacrylamide aqueous solution, and stirred for 25 minutes to obtain a precipitate, which was then collected by centrifugation and pressed between glass plates to form a composite;

[0045] S4: The pressed composite in step S3 was soaked in a 1.5 mol / L NaCl solution for 25 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel was obtained. Embodiment

[0046] A preparation method of a self-repairing conductive hydrogel material, comprising the following steps:

[0047] S1: 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL were prepared respectively, and the pH of the two polymer aqueous solutions was adjusted to 3 using 1 mol / L hydrochloric acid;

[0048] S2: 0.2 mL of a 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 30 minutes to obtain a PAMPS-Fe 3+ composite solution;

[0049] S3: The PAMPS-Fe 3+ composite solution in step S2 was mixed with the above polyacrylamide aqueous solution and stirred for 30 minutes to obtain a precipitate, which was then collected by centrifugation and pressed between glass plates to form a composite;

[0050] S4: The pressed composite in step S3 was immersed in a 1.5 mol / L NaCl solution for 30 minutes to load NaCl, and finally a NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel was obtained.

[0051] The properties of the self-repairing conductive hydrogel materials prepared in the above three examples are shown in Table 1:

[0052] Mechanical properties Freeze resistance Conductive properties Self-repairing Tensile rate Compression sensing range Example 1 Excellent Excellent Excellent Yes 0.1 to 1000% 0.1 to 20 kPa Example 2 Excellent Excellent Excellent Yes 0.1 to 1000% 0.1 to 20 kPa Example 3 Excellent Excellent Excellent Yes 0.1 to 1000% 0.1 to 20 kPa

[0053] Table 1

[0054] Although embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a self-healing conductive hydrogel material, characterized by: The preparation method comprises the following steps: S1: respectively prepare 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL, and use 1 mol / L hydrochloric acid to adjust the pH of the two polymer aqueous solutions to 1-3; S2: 0.2 mL of a 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 10-30 minutes to obtain a PAMPS-Fe mixture 3+ composite solution; S3: The PAMPS-Fe prepared in step S2 is mixed with the above polyacrylamide aqueous solution and stirred for 20-30 minutes to obtain a precipitate, which is collected by centrifugation and pressed into a glass plate. 3+ The composite solution is mixed with the above polyacrylamide aqueous solution and stirred for 20-30 minutes to obtain a precipitate, which is collected by centrifugation and pressed into a glass plate. S4: The compound pressed in step S3 is soaked in a NaCl solution with a concentration of 1.5 mol / L for 20-30 minutes to load NaCl, and finally NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel.

2. The method for preparing a self-healing conductive hydrogel material according to claim 1, characterized in that: The preparation method comprises the following steps: S1: respectively prepare 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL, and use 1 mol / L hydrochloric acid to adjust the pH of the two polymer aqueous solutions to 1; S2: 0.2 mL of a 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 10 minutes to obtain a PAMPS-Fe mixture 3+ composite solution; S3: The PAMPS-Fe prepared in step S2 was mixed with the above polyacrylamide aqueous solution and stirred for 20 minutes to obtain a precipitate, which was collected by centrifugation and pressed between glass plates to form a film. 3+ The composite solution was mixed with the above polyacrylamide aqueous solution and stirred for 20 minutes to obtain a precipitate, which was collected by centrifugation and pressed between glass plates to form a film. S4: The compound pressed in step S3 was soaked in a NaCl solution with a concentration of 1.5 mol / L for 20 minutes to load NaCl, and finally NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel.

3. The method for preparing a self-healing conductive hydrogel material according to claim 1, characterized in that: The preparation method comprises the following steps: S1: respectively prepare 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL, and use 1 mol / L hydrochloric acid to adjust the pH of the two polymer aqueous solutions to 2; S2: 0.2 mL of a 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 20 minutes to obtain a PAMPS-Fe mixture 3+ composite solution; S3: The PAMPS-Fe prepared in step S2 was mixed with the above polyacrylamide aqueous solution and stirred for 25 minutes to obtain a precipitate, which was collected by centrifugation and pressed into a glass plate. 3+ The composite solution was mixed with the above polyacrylamide aqueous solution and stirred for 25 minutes to obtain a precipitate, which was collected by centrifugation and pressed into a glass plate. S4: The compound pressed in step S3 was soaked in a NaCl solution with a concentration of 1.5 mol / L for 25 minutes to load NaCl, and finally NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel.

4. The method for preparing a self-healing conductive hydrogel material according to claim 1, characterized in that: The preparation method comprises the following steps: S1: respectively prepare 20 mL of poly 2-acrylamide-2-methyl-1-propanesulfonic acid and polyacrylamide aqueous solutions with a concentration of 8 mg / mL, and use 1 mol / L hydrochloric acid to adjust the pH of the two polymer aqueous solutions to 3; S2: 0.2 mL of a 1 mol / L ferric chloride solution was added to the PAMPS aqueous solution in step S1, and stirred for 30 minutes to obtain a PAMPS-Fe mixture 3+ composite solution; S3: The PAMPS-Fe prepared in step S2 was mixed with the above polyacrylamide aqueous solution and stirred for 30 minutes to obtain a precipitate, which was collected by centrifugation and pressed between glass plates to form a film. 3+ The composite solution was mixed with the above polyacrylamide aqueous solution and stirred for 30 minutes to obtain a precipitate, which was collected by centrifugation and pressed between glass plates to form a film. S4: The compound pressed in step S3 was soaked in a NaCl solution with a concentration of 1.5 mol / L for 30 minutes to load NaCl, and finally NaCl / Fe 3+ / PAMPS-PAAm polymer conductive self-healing hydrogel.