CN111333864A - Preparation method of environment-friendly self-healing conductive hydrogel - Google Patents

Preparation method of environment-friendly self-healing conductive hydrogel Download PDF

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CN111333864A
CN111333864A CN202010181928.XA CN202010181928A CN111333864A CN 111333864 A CN111333864 A CN 111333864A CN 202010181928 A CN202010181928 A CN 202010181928A CN 111333864 A CN111333864 A CN 111333864A
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conductive hydrogel
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friendly self
healing
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侯安然
王海旺
贾凯旗
李一凡
黄谦
傅渭杰
彭涛
袁毅
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Northeastern University Qinhuangdao Branch
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Abstract

The invention belongs to the field of conductive hydrogel, and particularly relates to a preparation method of environment-friendly self-healing conductive hydrogel. The method comprises the following steps: preparing sodium alginate aqueous solution as a solution A → adding pyrrole monomer to form a solution B → adding a mixed solution C of sodium dodecyl benzene sulfonate and multi-walled carbon nano tubes into the solution B to form a solution D → adding the mixed solution D into a glass conical tube with a round glass slide sheet fixed well → cleaning an ink-jet cartridge → injecting FeCl into the ink-jet cartridge3Solution → crosslinking printing to obtain the environmental-friendly self-healing conductive hydrogel three-dimensional structure sample. The invention takes sodium alginate as a matrix and takes carbon nano tubes and polypyrrole as conductive materials. The environment-friendly self-healing conductive hydrogel is prepared by adopting a 3D printing preparation process. The invention solves the problems of poor conductivity, complex preparation process and unsatisfactory self-healing effect of the traditional conductive hydrogel.

Description

Preparation method of environment-friendly self-healing conductive hydrogel
Technical Field
The invention belongs to the field of conductive hydrogel, and relates to a synthesis and 3D printing forming process of environment-friendly self-healing conductive hydrogel with sodium alginate as a matrix and carbon nanotubes and polypyrrole as conductive materials.
Background
Under the positive influence of the state on the new material support policy, the conductive hydrogel has many similarities with biological tissues in structure and property, and has the controllability of electricity, mechanics and biological functions, so the conductive hydrogel is unique in conductive high polymer materials. With the development of modern science and technology, conductive hydrogel has wide application space and development prospect in the emerging fields of flexible electronics, biomedicine, self-healing conductive coating, self-healing energy storage devices, adhesives for electronic assembly and the like.
Although the traditional single polyelectrolyte conductive hydrogel has certain practical value at the present stage, some short plates which are not promoted and optimized still exist: (1) the conductivity and the tensile stability are not ideal; (2) the preparation process is complex and easily causes the waste of raw materials; (3) in order to eliminate the hidden pollution danger, a large amount of economic cost is consumed, and the preparation concept of green environmental protection is violated.
The 3D printing and forming technology is a new trend of modern manufacturing development, and the future development prospect is good. The rapid forming technology has the advantages that the defects of the forming technology of the manufacturing industry at the current stage can be overcome, the process level and quality of the industrial manufacturing are improved, the process manufacturing efficiency is improved, the forming technology can meet the requirements of mass industrial production, and enterprises can be helped to reduce the production and manufacturing cost.
In recent years, along with the rapid development of social economy and scientific and technical strength, the problems of large energy consumption demand, resource shortage and the like are gradually revealed, and the problem of energy storage is highly emphasized by the nation, so that the selection of materials of the energy storage device is particularly important. Meanwhile, the flexible electronic products and other emerging fields are vigorously developed under the positive influence of national policies, and the service life of the products also becomes one of the most important development factors. The conductive hydrogel is unique in conductive polymer materials due to the controllability of electricity, mechanics and biological functions, and is favored in the fields of flexible electronics, biomedicine, self-healing conductive coatings, self-healing energy storage devices, adhesives for electronic assembly and the like. However, the traditional conductive hydrogel at the present stage has the problems of poor conductivity, complex preparation process, non-ideal self-healing effect and the like, so that the application prospect of the conductive hydrogel has certain limitations.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly self-healing conductive hydrogel, aiming at solving the problems of poor conductivity, complex preparation process and unsatisfactory self-healing effect of the traditional conductive hydrogel at the present stage.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of environment-friendly self-healing conductive hydrogel comprises the following steps:
(1) dissolving 0.020-0.030 mass part of sodium alginate in deionized water at room temperature, stirring at constant temperature until the sodium alginate and the deionized water are uniformly mixed, and marking the obtained solution as solution A;
(2) adding 0.3-0.5 part by mass of pyrrole monomer into the solution A, and ultrasonically dispersing the obtained mixture uniformly to obtain a solution B;
(3) dissolving 2-3 parts by mass of sodium dodecyl benzene sulfonate in deionized water at room temperature, adding 0.6-1.0 part by mass of multi-walled carbon nanotubes into the deionized water, and uniformly dispersing the mixture by ultrasonic waves to obtain a solution C;
(4) adding the prepared solution C into the solution B, and uniformly dispersing by ultrasonic to form a mixed solution D;
(5) taking a glass conical tube with a rubber plug base at the bottom, and enabling a metal rod connected with a stepping motor to penetrate through the rubber plug base and enter the glass conical tube;
(6) fixing a circular glass slide sheet with the diameter of 2-3 cm at the top end of a metal rod in a glass conical tube, and then adding a mixed solution D into the glass conical tube; the glass tapered tube is used as a three-dimensional sample 3D forming place, and the circular glass slide sheet is used as an elevator lifting platform;
(7) emptying the ink-jet cartridge of the 3D printer, and repeatedly and thoroughly flushing the ink-jet cartridge by using double distilled water and 100% ethanol by mass until no ink exists;
(8) taking FeCl with the molar concentration of 0.2-0.25 mol/L3Injecting 1-2 parts by volume of the aqueous solution into an ink-jet cartridge;
(9) the three-dimensional sample 3D printing process is as follows: FeCl is ejected out by moving a 3D printer ink box nozzle above a circular glass slide sheet3The sprayed solution is crosslinked with the mixed solution in the glass tapered tube to form polymer gel on the circular glass slide plate; then, controlling the electronic equipment of the stepping motor to enable the circular glass slide sheet to move downwards, and continuously printing a next layer of structure on the polymer gel formed before by the solution sprayed by the ink box spray head; repeating the process to realize cross-linked printing layer by layer to obtain a 3D printing and forming three-dimensional sample structure;
(10) placing the three-dimensional sample structure obtained in the step (10) onFeCl with molar concentration of 0.2-0.25 mol/L3Soaking in the aqueous solution for a period of time to obtain an environment-friendly self-healing conductive hydrogel sample;
in the above step, parts by volume are in ml, and parts by mass are in g.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (1) of stirring at a constant temperature in a water bath kettle at the temperature of 60-70 ℃.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (1) of stirring at a constant temperature for 1.5-2 hours.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (2) of performing ultrasonic dispersion for 10-20 min.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (3) of performing ultrasonic dispersion for 45-60 min.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (4) of carrying out ultrasonic dispersion for 10-15 min.
According to the preparation method of the environment-friendly self-healing conductive hydrogel, the mass ratio of the sodium dodecyl benzene sulfonate to the multi-walled carbon nano tubes is 2-3: 1.
The preparation method of the environment-friendly self-healing conductive hydrogel comprises the step (10) of soaking for 5-10 min.
In the preparation method of the environment-friendly self-healing conductive hydrogel, in the step (6), the structure of a three-dimensional sample 3D forming place is as follows: the vertical metal rod in the glass conical tube penetrates through the bottom of the glass conical tube with the rubber plug base and is connected with the stepping motor, and the lifting of the circular glass slide sheet connected with the top end of the metal rod is controlled by electronic equipment for controlling the stepping motor.
The design idea of the invention is as follows:
the invention uses nontoxic and harmless natural seaweed extracted sodium alginate as a raw material, fills a carbon nano tube and pyrrole monomer conductive composite material, and adopts a 3D printing and forming preparation technology to obtain the environment-friendly self-healing conductive hydrogel. The conductive high molecular material polypyrrole becomes a conductive hot door material with stable electrical properties, stimulation responsiveness and good biocompatibility, but the structure of the polypyrrole is a rigid hydrophobic polymer chain, so that the polypyrrole is not easy to dissolve, and further development of the conductive performance is limited. The invention adopts ferric ion oxidation to induce pyrrole monomer to polymerize, thereby solving the problem that polypyrrole is not easy to dissolve, and in addition, the invention introduces a novel carbon nano tube material with high tensile strength, Young modulus, breaking strain and excellent conductivity as a filling composite material.
The network structure of the novel material of the filled carbon nano tube provides a rigid bracket for the composite hydrogel, keeps the shape of the gel and has stronger mechanical property. And a conductive path is formed among the carbon nano tubes, and carriers are transferred and conducted. Fe3+The polypyrrole is induced to polymerize to form polypyrrole, and the polypyrrole coats the carbon nanotube network structure, so that the conductive path of the carbon nanotube is widened, more conductive paths are formed in the hydrogel matrix, and the conductive performance of the composite hydrogel is further improved. On the other hand, Fe3+A large number of hydrogen bonds exist in a polymer chain formed by crosslinking with a sodium alginate matrix, and after the polymer chain is damaged by external force, the composite hydrogel is restored to the original shape under the strong mutual attraction of the hydrogen bonds. Therefore, the composite hydrogel prepared by the invention has stronger mechanical property, excellent conductivity and ideal self-healing effect.
The invention has the following advantages and beneficial effects:
1. the carbon nano tube has a unique one-dimensional nano structure and excellent mechanical, electrical, thermal stability and magnetic properties, and has excellent conductivity while the mechanical property of the matrix hydrogel is enhanced by taking the carbon nano tube as a conductive material.
2. The invention introduces Fe3+As a cross-linking agent, a large number of hydrogen bonds exist in a polymer chain formed by cross-linking with a sodium alginate matrix, and after the polymer chain is damaged by external force, the composite hydrogel is restored under the strong mutual attraction of the hydrogen bonds, so that the self-healing hydrogel has an ideal self-healing effect.
3. The product of the invention adopts a 3D printing and forming preparation process, makes up the defects of the forming technology of the manufacturing industry at the present stage, improves the process level and quality of the industrial manufacturing, improves the process manufacturing efficiency, and thus effectively reduces the production cost.
Drawings
FIG. 1 is a flow chart of a preparation method of the environment-friendly self-healing conductive hydrogel.
Fig. 2(a) is a schematic diagram of the 3D printing according to the present invention. In the figure, 1 stepper motor, 2 metal rod, 3 glass taper tube, 4 round glass slide sheet, 5 ink-jet cartridge, 6 cartridge nozzle, 7 polymer gel, 8 stepper motor control switch, 9 power.
Fig. 2(b) is a layer-by-layer cross-linked printing process diagram.
Detailed Description
As shown in fig. 1, the process of the preparation method of the environment-friendly self-healing conductive hydrogel of the invention is as follows: sodium alginate aqueous solution (solution A) → adding pyrrole monomer to form solution B → mixing Sodium Dodecyl Benzene Sulfonate (SDBS) and multi-walled carbon nano-tubes uniformly to form mixed solution C → mixing and dispersing solution C and solution B uniformly to form solution D, adding multi-walled carbon nano-tubes (MWCNTs) to form mixed solution D → adding mixed solution D into a glass conical tube with a round glass slide sheet fixed well → cleaning an ink-jet cartridge → injecting FeCl into the ink-jet cartridge3And (3) solution.
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
In this embodiment, the preparation method of the environment-friendly self-healing conductive hydrogel includes the following steps:
(1) taking 1 beaker with the volume of 100ml, weighing 0.025g of sodium alginate at room temperature, adding 20ml of deionized water into the beaker, stirring for 2 hours at the constant temperature of a 65 ℃ water bath kettle, and marking as solution A;
(2) adding 0.4g of pyrrole monomer into the beaker of the solution A in the step (1), and ultrasonically dispersing the obtained mixed solution in an ultrasonic instrument for 15min to obtain a solution B;
(3) taking 3g of Sodium Dodecyl Benzene Sulfonate (SDBS) (the mass ratio of SDBS: MWCNTs is 3:1) into deionized water, adding 1g of multi-walled carbon nanotubes (MWCNTs) into the deionized water, and ultrasonically dispersing the obtained mixed solution in an ultrasonic instrument for 50min to form a solution C;
(4) mixing the solution B in the step (2) with the solution C in the step (3), and ultrasonically dispersing the obtained solution in an ultrasonic instrument for 10min to obtain a mixed solution D;
(5) as shown in fig. 2(a), a glass conical tube 3 with a plug base at the bottom and a specification of 50ml is taken, and a metal rod 2 connected with a stepping motor 1 penetrates through the plug base and enters the glass conical tube 3;
(6) as shown in fig. 2(a), a circular glass slide 4 with a diameter of 2.5cm is fixed at the top end of the metal rod 2 in the glass tapered tube 3, and then the mixed solution D is added into the glass tapered tube 3 (wherein the glass tapered tube 3 is used as a three-dimensional sample 3D forming place, and the circular glass slide 4 is used as an elevator lifting platform instead of a 3D printing lifting platform);
(7) as shown in fig. 2(a), the ink-jet cartridge 5 of the 3D printer was emptied, and repeatedly and thoroughly rinsed with double distilled water and 100% by mass ethanol until there was no ink at all;
(8) as shown in FIG. 2(a), FeCl was taken at a molar concentration of 0.25mol/L31.5ml of water solution is injected into an ink-jet ink box 5, an ink box spray head 6 is arranged at the bottom of the ink-jet ink box 5, and the lower part of the ink box spray head 6 corresponds to the glass conical tube 3;
(9) three-dimensional sample 3D modeling site architecture description: as shown in fig. 2(a) -2 (b), the vertical metal rod 2 passes through the bottom of the glass conical tube 3 with the rubber plug base and is connected with the stepping motor 1, and the circular glass slide 4(3D printing lifting platform) connected with the top end of the metal rod 2 is controlled to lift by controlling the electronic equipment of the stepping motor 1 (the power supply 9 is connected with the stepping motor 1 through the stepping motor control switch 8).
3D printing process of the three-dimensional sample: as shown in FIGS. 2(a) -2 (b), the 3D printer cartridge head 6 moves above the circular glass slide 4 to eject FeCl3Aqueous solution, ejected FeCl3The aqueous solution and the mixed solution in the glass tapered tube 3 are crosslinked, and a polymer gel 7 with a specific shape is formed on the circular glass slide 4. And then the electronic equipment for controlling the stepping motor 1 (a power supply 9 is connected with the stepping motor 1 through a stepping motor control switch 8) enables the circular glass slide 4 to move downwards. The ink box nozzle 6 sprays out the solutionThe liquid continues to print the next layer of structure on the previously formed polymer gel 7. And repeating the process to realize the cross-linking printing layer by layer to obtain the 3D printing forming three-dimensional sample structure.
According to the invention, a glass tapered tube is used as a three-dimensional sample 3D forming place, a circular glass slide sheet is used as a 3D printing lifting platform, and the environment-friendly self-healing conductive hydrogel is prepared in a 3D printer local assembly through 3D printing forming, which is specifically shown in the following steps: thomas Bolanda, Xu Tao, Brook J.Damon, Brian Manleya, Priya Kesaria, Sahil Jalotac, Sarit Bhadric. drop-on-demand printing of cells and Materials for designer tissue constraints, Materials Science & Engineering C-biological and statistical applies systems 27(2007)372-376.
(10) Placing the three-dimensional structure sample obtained in the step (10) in FeCl with the molar concentration of 0.25mol/L3Soaking in the aqueous solution for 10min to obtain the environment-friendly self-healing conductive hydrogel sample.
Example 2
The difference from example 1 is that: in the step (3), Sodium Dodecyl Benzene Sulfonate (SDBS) is prepared by mixing a multi-wall carbon nano tube (MWCNTs) 2: 1, the rest is the same as example 1.
Example 3
The difference from example 1 is that: in the step (9), FeCl with the molar concentration of 0.2mol/L is taken31.5ml of aqueous solution, the same as in example 1.
Example 4
The difference from example 1 is that: in step (4), 0.8g of multi-walled carbon nanotubes (MWCNTs) were added, and the rest was the same as in example 1.
For the invention, on one hand, the carbon nano tube has a unique one-dimensional nano structure and excellent mechanical, electrical, thermal stability and magnetic properties, and meanwhile, the polypyrrole covers the network structure of the carbon nano tube, so that the conductive path of the carbon nano tube is widened, and the mechanical property and the electrical property of the filled conductive composite material are greatly improved compared with those of the traditional conductive hydrogel. On the other hand, Fe3+A large number of hydrogen bonds exist in a polymer chain formed by crosslinking the sodium alginate matrix serving as a crosslinking agent, and after the polymer chain is damaged by external force, the hydrogen bondsThe composite hydrogel is restored to the original shape under the strong mutual attraction of the bonds, the self-healing capacity of the traditional conductive hydrogel is remarkably improved, and the application prospect is very ideal.
Therefore, the environment-friendly self-healing conductive hydrogel prepared by the 3D printing and forming process has a very positive influence on the development of the emerging fields of the manufacturing industry at the present stage, flexible electronics and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, which is defined by the appended claims.

Claims (9)

1. The preparation method of the environment-friendly self-healing conductive hydrogel is characterized by comprising the following steps of:
(1) dissolving 0.020-0.030 mass part of sodium alginate in deionized water at room temperature, stirring at constant temperature until the sodium alginate and the deionized water are uniformly mixed, and marking the obtained solution as solution A;
(2) adding 0.3-0.5 part by mass of pyrrole monomer into the solution A, and ultrasonically dispersing the obtained mixture uniformly to obtain a solution B;
(3) dissolving 2-3 parts by mass of sodium dodecyl benzene sulfonate in deionized water at room temperature, adding 0.6-1.0 part by mass of multi-walled carbon nanotubes into the deionized water, and uniformly dispersing the mixture by ultrasonic waves to obtain a solution C;
(4) adding the prepared solution C into the solution B, and uniformly dispersing by ultrasonic to form a mixed solution D;
(5) taking a glass conical tube with a rubber plug base at the bottom, and enabling a metal rod connected with a stepping motor to penetrate through the rubber plug base and enter the glass conical tube;
(6) fixing a circular glass slide sheet with the diameter of 2-3 cm at the top end of a metal rod in a glass conical tube, and then adding a mixed solution D into the glass conical tube; the glass tapered tube is used as a three-dimensional sample 3D forming place, and the circular glass slide sheet is used as an elevator lifting platform;
(7) emptying the ink-jet cartridge of the 3D printer, and repeatedly and thoroughly flushing the ink-jet cartridge by using double distilled water and 100% ethanol by mass until no ink exists;
(8) taking FeCl with the molar concentration of 0.2-0.25 mol/L3Injecting 1-2 parts by volume of the aqueous solution into an ink-jet cartridge;
(9) the three-dimensional sample 3D printing process is as follows: FeCl is ejected out by moving a 3D printer ink box nozzle above a circular glass slide sheet3The sprayed solution is crosslinked with the mixed solution in the glass tapered tube to form polymer gel on the circular glass slide plate; then, controlling the electronic equipment of the stepping motor to enable the circular glass slide sheet to move downwards, and continuously printing a next layer of structure on the polymer gel formed before by the solution sprayed by the ink box spray head; repeating the process to realize cross-linked printing layer by layer to obtain a 3D printing and forming three-dimensional sample structure;
(10) placing the three-dimensional sample structure obtained in the step (10) in FeCl with the molar concentration of 0.2-0.25 mol/L3Soaking in the aqueous solution for a period of time to obtain an environment-friendly self-healing conductive hydrogel sample;
in the above step, parts by volume are in ml, and parts by mass are in g.
2. The method for preparing the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (1), the stirring at a constant temperature is performed in a water bath at a temperature of 60-70 ℃.
3. The preparation method of the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (1), the stirring is carried out at a constant temperature for 1.5 to 2 hours.
4. The preparation method of the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (2), the ultrasonic dispersion time is 10-20 min.
5. The preparation method of the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (3), the ultrasonic dispersion time is 45-60 min.
6. The preparation method of the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (4), the ultrasonic dispersion time is 10-15 min.
7. The preparation method of the environment-friendly self-healing conductive hydrogel according to claim 1, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the multi-walled carbon nanotubes is 2-3: 1.
8. The method for preparing the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (10), the soaking time is 5-10 min.
9. The method for preparing the environment-friendly self-healing conductive hydrogel according to claim 1, wherein in the step (6), the structure of the three-dimensional sample 3D forming site is as follows: the vertical metal rod in the glass conical tube penetrates through the bottom of the glass conical tube with the rubber plug base and is connected with the stepping motor, and the lifting of the circular glass slide sheet connected with the top end of the metal rod is controlled by electronic equipment for controlling the stepping motor.
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Application publication date: 20200626