CN111848983A - Multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4Preparation method of composite hydrogel - Google Patents
Multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4Preparation method of composite hydrogel Download PDFInfo
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 118
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 76
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 76
- 239000000017 hydrogel Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 239000002071 nanotube Substances 0.000 claims abstract description 17
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 16
- 229940012189 methyl orange Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 2
- 239000006228 supernatant Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 abstract description 13
- 230000005389 magnetism Effects 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000003292 glue Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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Abstract
The invention provides multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4The preparation method of the composite hydrogel comprises the following steps: loading MnFe on polypyrrole nano-tube2SO4Nanoparticles to give polypyrrole/MnFe2SO4A nanocomposite; mixing polypyrrole/MnFe2SO4Adding the nano-composite into a polyvinyl alcohol aqueous solution to obtain polyvinyl alcohol/polypyrrole/MnFe2SO4Blending the liquid; to polyvinyl alcohol/polypyrrole/MnFe2SO4Adding borax as a cross-linking agent into the blending liquid to obtain multifunctional polyvinyl alcohol-polypyrrole/MnFe2SO4And (3) compounding the hydrogel. The multifunctional polyvinyl alcohol-polypyrrole/MnFe prepared by the invention2SO4The composite hydrogel has good conductivity and magnetism, self-healing property and adhesiveness, and excellent moldability, can be used for easily and quickly applying glue through an injector, randomly writing a conductive circuit and keeping the circuit smooth. Meanwhile, the hydrogel can also simulate human skin and be used as a touch screen pen. The preparation method is simple, does not need complex equipment, has short molding period and does not pollute the environment.
Description
Technical Field
The invention relates to the technical field of polymer functional materials, in particular to multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4A preparation method of composite hydrogel.
Background
Conductive hydrogels are considered ideal candidates for sensors for detecting human motion signals, medical diagnostics, human-machine connectivity, and artificial skin due to their high sensitivity, excellent flexibility, and good adhesion. However, many materials are limited by their single properties. Magnetic properties are considered another important property of hydrogels, but fewer hydrogels are available that are both magnetic and electrically conductive.
The main approach to introducing magnetism into hydrogels is to incorporate magnetic particles directly into the hydrogel. However, the magnetic particles are prone to agglomeration under electrostatic interaction and hydrogel hydrogen bonding. When magnetic particles are added to hydrogels alone, it is often difficult to disperse and even delaminate from the gel medium, and as such, most reports mainly investigate the conductivity of hydrogels, and despite the few reported materials that combine conductivity and magnetism, other important properties, such as moldability, self-healing, adhesion, and mechanical properties, are lacking, which limits their practical application in sensors. Therefore, the preparation of the multifunctional hydrogel with various excellent performances such as conductivity, magnetism and the like is still a challenge, and the preparation method is green, environment-friendly, simple and fast.
Disclosure of Invention
In view of the above, the present invention is to provide a multifunctional PVA/polypyrrole/MnFe2SO4The preparation method of the composite hydrogel aims to solve the problem of single function of the existing hydrogel.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4The preparation method of the composite hydrogel comprises the following steps:
1) adding polypyrrole nanotubes into deionized water, and performing ultrasonic dispersion to obtain a polypyrrole suspension with the mass fraction of 0.1% -10%;
2) adding iron salt and manganese salt into the polypyrrole suspension, stirring for 1-10h at 50-100 ℃, adjusting the pH to 7-13 by using sodium hydroxide, continuously stirring for 5-40min, then cooling to 0-25 ℃, washing, centrifuging, and freeze-drying to obtain polypyrrole/MnFe2SO4A nanocomposite;
3) adding polyvinyl alcohol into deionized water, stirring and dissolving to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 1-30%;
4) adding the polypyrrole/MnFe into the polyvinyl alcohol aqueous solution cooled to 20-50 DEG C2SO4The nano-composite is stirred to obtain polyvinyl alcohol/polypyrrole/MnFe2SO4Blending the liquid;
5) adding borax to the polyvinyl alcohol/polypyrrole/MnFe 2SO4Obtaining multifunctional polyvinyl alcohol/polypyrrole/MnFe in the blending liquid2SO4And (3) compounding the hydrogel.
Optionally, the polypyrrole nanotubes in the step 1) are prepared by the following method:
and mixing the methyl orange aqueous solution and pyrrole, stirring, adding ferric salt, uniformly mixing, washing, filtering, and drying to obtain the polypyrrole nanotube.
Optionally, the mass fraction of the methyl orange aqueous solution is 0.1% -0.5%; the ferric salt is one of ferric nitrate, ferric sulfate and ferric chloride.
Optionally, the ratio of the methyl orange aqueous solution, the pyrrole and the iron salt is 500-800 mL: 1-3 mL: 20-40 g.
Optionally, the dispersing temperature of the ultrasonic dispersion in the step 1) is 0-35 ℃, and the dispersing time is 5-40 min.
Optionally, the mass ratio of the iron salt to the manganese salt in the step 2) is (0.5-20): (0.2-10).
Optionally, in the step 2), the iron salt is one of ferric chloride, ferric sulfate and ferric nitrate, and the manganese salt is one of manganese sulfate, manganese carbonate and manganese chloride.
Optionally, the dissolving temperature of the stirring dissolution in the step 3) is 90-105 ℃.
Optionally, the polyvinyl alcohol in the step 3) and the polypyrrole/MnFe in the step 4) are mixed 2SO4The mass ratio of the nano-composite is (0.2-5) to (0.05-0.5).
Optionally, the mass ratio of the polyvinyl alcohol in the step 3) to the borax in the step 5) is (2-20) to 1.
Compared with the prior art, the multifunctional polyvinyl alcohol/polypyrrole/MnFe material provided by the invention2SO4The preparation method of the composite hydrogel has the following advantages:
1. polypyrrole/MnFe in the invention2SO4The addition of the nano-composite enables the composite hydrogel to have good conductivity and magnetism, and the interaction of the components in the composite hydrogel enables the composite hydrogel to have self-repairing capability, and the composite hydrogel is cut off and then contacted again, so that the composite hydrogel still has good conductivity.
2. Polyvinyl alcohol, polypyrrole/MnFe in the invention2SO4The hydrogen bond interaction between the nano-composite and the borax ensures that the polyvinyl alcohol/the polypyrrole/the MnFe2SO4The conductive magnetic hydrogel has good tensile property, and compared with the polyvinyl alcohol-polypyrrole hydrogel polymerized in situ, the tensile rate is improved by about 10-20 times.
3. In the hydrogel obtained by the invention, under the condition that water exists, the surface hydroxyl of the polyvinyl alcohol can form hydrogen bonds between the surfaces of various materials, so that the polyvinyl alcohol/polypyrrole/MnFe2SO4The conductive magnetic hydrogel has good adhesion performance and can be adhered to the surfaces of different substrates.
4. The invention passes through the controlAdding polypyrrole/MnFe2SO4The multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel with different tensile properties can be prepared by the content of the nano composite.
5. The preparation method is simple, does not need complex equipment, has short molding period and does not pollute the environment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a multi-functional PVA/polypyrrole/MnFe prepared according to example 1 of the present invention2SO4A graph of tensile properties of the composite hydrogel;
FIG. 2 shows a multi-functional PVA/polypyrrole/MnFe film prepared according to example 1 of the present invention2SO4Adhesion experiment pictures of the composite hydrogel;
FIG. 3 shows a multi-functional PVA/polypyrrole/MnFe film prepared according to example 1 of the present invention2SO4Magnetic attraction experimental pictures of the composite hydrogel;
FIG. 4 shows a multi-functional PVA/polypyrrole/MnFe film prepared according to example 1 of the present invention2SO4And (3) a self-repairing conductive performance experiment photo of the composite hydrogel.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A preparation method of multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel comprises the following specific steps:
1) preparing a certain amount of methyl orange into an aqueous solution with the mass fraction of 0.2%, stirring 640mL of the aqueous solution of methyl orange and 1mL of pyrrole for one day, adding about 29g of ferric nitrate, uniformly mixing, washing, filtering, and drying to obtain a polypyrrole nanotube;
2) adding 0.05g of the polypyrrole nanotube obtained in the step 1) into 10mL of water, and performing ultrasonic dispersion at 25 ℃ for 20min to obtain a polypyrrole suspension with the mass fraction of 0.5%; adding 15.5g of ferric chloride and 4.8g of manganese sulfate into the polypyrrole suspension, controlling the temperature to be 50 ℃, stirring for 3h, adjusting the pH to be 11 by using 8mol/L sodium hydroxide, continuously stirring for 10min, naturally cooling to 25 ℃, washing, centrifuging for 3 times, and freeze-drying to obtain polypyrrole/MnFe2SO4A nanocomposite;
3) adding 1g of polyvinyl alcohol into 30mL of water, stirring and dissolving at 90 ℃ to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 3%, naturally cooling to 40 ℃, and adding 0.5g of polypyrrole/MnFe obtained in the step 2)2SO4Stirring the nano-composite for 20min to obtain polyvinyl alcohol-polypyrrole/MnFe 2SO4Blending the liquid;
4) adding 0.2g of borax into the step 3) to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4In the mixed solution, multifunctional polyvinyl alcohol/polypyrrole/MnFe with the functions of moldability, stretchability, self-healing, adhesion, conductivity and magnetism is obtained2SO4And (3) compounding the hydrogel.
The multifunctional PVA/polypyrrole/MnFe prepared in this example was taken2SO4The hydrogel was compounded, and a sample of 1 cm. times.0.25 cm was prepared, and a tensile test was conducted at a tensile speed of about 0.5cm/s, the test results being shown in FIG. 1.
As can be seen from FIG. 1, the multifunctional PVA/polypyrrole/MnFe prepared in this example2SO4The elongation of the composite hydrogel was 1159%.
The multifunctional PVA/polypyrrole/MnFe prepared in this example2SO4The adhesion test results of the composite hydrogel are shown in fig. 2.
As can be seen from FIG. 2, the multifunctional PVA/polypyrrole/MnFe prepared in this example2SO4The composite hydrogel has remarkable self-adhesive capacity to various base materials, and can adhere to an object which is about 10000 times heavier than the self weight to the maximum.
The multifunctional PVA/polypyrrole/MnFe prepared in this example2SO4The composite hydrogel magnetic experiment shows that the test result is shown in figure 3.
As can be seen from FIG. 3, the multifunctional PVA/polypyrrole/MnFe prepared in this example 2SO4The composite hydrogel may be attracted to a magnet at an angle off the vertical.
The test result of the self-repairing conductive performance test of the multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel prepared in this embodiment is shown in FIG. 4.
As can be seen from fig. 4, when the external power source is turned on, the small bulb is lighted; after cutting the composite hydrogel of this example, the small bulb was extinguished; after the composite hydrogel of this example re-contacts the self-repair, the small bulb is lit up again.
Example 2
A preparation method of multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel comprises the following specific steps:
1) preparing a certain amount of methyl orange into an aqueous solution with the mass fraction of 0.3%, stirring 500mL of the aqueous solution of methyl orange and 1.5mL of pyrrole for one day, adding about 35g of ferric sulfate, mixing uniformly, washing, filtering, and drying to obtain a polypyrrole nanotube;
2) adding 0.8g of polypyrrole nanotubes obtained in the step 1) into 8mL of water, and performing ultrasonic dispersion at 5 ℃ for 40min to obtain a polypyrrole suspension with the mass fraction of 10%; adding 10g of ferric chloride and 2g of manganese sulfate into the polypyrrole suspension, controlling the temperature to be 50 ℃, stirring for 5h, adjusting the pH to be 13 by using 1mol/L of sodium hydroxide, continuously stirring for 40min, naturally cooling to 20 ℃, washing, centrifuging for 1 time, and freeze-drying to obtain polypyrrole/MnFe 2SO4A nanocomposite;
3) adding 2g of polyvinyl alcohol into 20mL of water, stirring and dissolving at 100 ℃ to obtain a 10% polyvinyl alcohol aqueous solution, naturally cooling to 20 ℃, and adding 1.5g of polypyrrole/MnFe obtained in the step 2)2SO4Stirring the nano composite for 30min to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4Blending the liquid;
4) adding 0.3g of borax into the step 3) to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4In the mixed solution, multifunctional polyvinyl alcohol/polypyrrole/MnFe with the functions of moldability, stretchability, self-healing, adhesion, conductivity and magnetism is obtained2SO4And (3) compounding the hydrogel.
The multifunctional PVA/polypyrrole/MnFe obtained in the example is tested2SO4The elongation of the composite hydrogel was 800%.
Example 3
A preparation method of multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel comprises the following specific steps:
1) preparing a certain amount of methyl orange into an aqueous solution with the mass fraction of 0.4%, stirring 600mL of the aqueous solution of methyl orange and 2mL of pyrrole for one day, adding about 40g of ferric chloride, uniformly mixing, washing, filtering, and drying to obtain a polypyrrole nanotube;
2) adding 1g of the polypyrrole nanotube obtained in the step 1) into 20mL of water, and performing ultrasonic dispersion at 10 ℃ for 20min to obtain a polypyrrole suspension with the mass fraction of 5%; adding 20g of ferric chloride and 7g of manganese sulfate into the polypyrrole suspension, controlling the temperature to be 65 ℃, stirring for 8h, adjusting the pH to be 12 by using 3mol/L sodium hydroxide, continuously stirring for 20min, naturally cooling to 15 ℃, washing, centrifuging for 2 times, and freeze-drying to obtain polypyrrole/MnFe 2SO4A nanocomposite;
3) adding 1.5g of polyvinyl alcohol into 30mL of water, stirring and dissolving at 100 ℃ to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 5%, naturally cooling to 15 ℃, and adding 1.5g of polypyrrole/MnFe obtained in the step 2)2SO4Stirring the nano-composite for 25min to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4Blending the liquid;
4) adding 0.5g of borax into the step 3) to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4In the mixed solution, multifunctional polyvinyl alcohol/polypyrrole/MnFe with the functions of moldability, stretchability, self-healing, adhesion, conductivity and magnetism is obtained2SO4And (3) compounding the hydrogel.
The multifunctional PVA/polypyrrole/MnFe obtained in the example is tested2SO4The elongation of the composite hydrogel was 700%.
Example 4
A preparation method of multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel comprises the following specific steps:
1) preparing a certain amount of methyl orange into an aqueous solution with the mass fraction of 0.5%, stirring 700mL of the aqueous solution of methyl orange and 2.5mL of pyrrole for 24h, adding about 40g of ferric sulfate, uniformly mixing, washing, filtering, and drying to obtain a polypyrrole nanotube;
2) adding 0.5g of polypyrrole nanotubes obtained in the step 1) into 50mL of water, and performing ultrasonic dispersion at 10 ℃ for 20min to obtain a polypyrrole suspension with the mass fraction of 1%; adding 15g of ferric chloride and 5g of manganese sulfate into the polypyrrole suspension, controlling the temperature to be 70 ℃, stirring for 5h, adjusting the pH to be 11 by using 5mol/L sodium hydroxide, continuously stirring for 15min, naturally cooling to 15 ℃, washing, centrifuging for 3 times, and freeze-drying to obtain polypyrrole/MnFe 2SO4A nanocomposite;
3) adding 0.1g of polyvinyl alcohol into 5mL of water, stirring and dissolving at 100 ℃ to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 2%, naturally cooling to 12 ℃, and adding 0.12g of polypyrrole/MnFe obtained in the step 2)2SO4Stirring the nano-composite for 35min to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4Blending the liquid;
4) adding 0.03g of borax into the step 3) to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4In the mixed solution, multifunctional polyvinyl alcohol/polypyrrole/MnFe with the functions of moldability, stretchability, self-healing, adhesion, conductivity and magnetism is obtained2SO4And (3) compounding the hydrogel.
The multifunctional PVA/polypyrrole/MnFe obtained in the example is tested2SO4The elongation of the composite hydrogel is 600%.
Example 5
A preparation method of multifunctional polyvinyl alcohol/polypyrrole/MnFe 2SO4 composite hydrogel comprises the following specific steps:
1) preparing a certain amount of methyl orange into an aqueous solution with the mass fraction of 0.1%, stirring 500mL of the aqueous solution of methyl orange and 3mL of pyrrole for one day, adding about 20g of ferric chloride, uniformly mixing, washing, filtering, and drying to obtain a polypyrrole nanotube;
2) adding 0.1g of polypyrrole nanotubes obtained in the step 1) into 20mL of water, and performing ultrasonic dispersion at 10 ℃ for 20min to obtain a polypyrrole suspension with the mass fraction of 0.5%; adding 3.5g of ferric chloride and 0.9g of manganese sulfate into the polypyrrole suspension, controlling the temperature to be 80 ℃, stirring for 3h, adjusting the pH to 10 by using 8mol/L sodium hydroxide, continuously stirring for 10min, naturally cooling to 15 ℃, washing, centrifuging for 3 times, and freeze-drying to obtain polypyrrole/MnFe 2SO4A nanocomposite;
3) adding 0.2g of polyvinyl alcohol into 10mL of water, stirring and dissolving at 100 ℃ to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 2%, naturally cooling to 40 ℃, and adding 0.3g of polypyrrole/MnFe obtained in the step 2)2SO4Stirring the nano composite for 40min to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4Blending the liquid;
4) adding 0.04g of borax into the step 3) to obtain polyvinyl alcohol-polypyrrole/MnFe2SO4In the mixed solution, multifunctional polyvinyl alcohol/polypyrrole/MnFe with the functions of moldability, stretchability, self-healing, adhesion, conductivity and magnetism is obtained2SO4And (3) compounding the hydrogel.
The multifunctional PVA/polypyrrole/MnFe obtained in the example is tested2SO4The elongation of the composite hydrogel was 900%.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Multifunctional polyvinyl alcohol/polypyrrole/MnFe2SO4The preparation method of the composite hydrogel is characterized by comprising the following steps:
1) adding polypyrrole nanotubes into deionized water, and performing ultrasonic dispersion to obtain a polypyrrole suspension with the mass fraction of 0.1% -10%;
2) To the polypyrrole suspensionAdding ferric salt and manganese salt into the supernatant, stirring at 50-100 deg.C for 1-10h, adjusting pH to 7-13 with sodium hydroxide, stirring for 5-40min, cooling to 0-25 deg.C, washing, centrifuging, and lyophilizing to obtain polypyrrole/MnFe2SO4A nanocomposite;
3) adding polyvinyl alcohol into deionized water, stirring and dissolving to obtain a polyvinyl alcohol aqueous solution with the mass fraction of 1-30%;
4) adding the polypyrrole/MnFe into the polyvinyl alcohol aqueous solution cooled to 20-50 DEG C2SO4The nano-composite is stirred to obtain polyvinyl alcohol/polypyrrole/MnFe2SO4Blending the liquid;
5) adding borax to the polyvinyl alcohol/polypyrrole/MnFe2SO4Obtaining multifunctional polyvinyl alcohol/polypyrrole/MnFe in the blending liquid2SO4And (3) compounding the hydrogel.
2. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that the polypyrrole nanotubes in the step 1) are prepared by the following method:
and mixing the methyl orange aqueous solution and pyrrole, stirring, adding ferric salt, uniformly mixing, washing, filtering, and drying to obtain the polypyrrole nanotube.
3. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 2 2SO4The preparation method of the composite hydrogel is characterized in that the mass fraction of the methyl orange aqueous solution is 0.1-0.5%; the ferric salt is one of ferric nitrate, ferric sulfate and ferric chloride.
4. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 22SO4The preparation method of the composite hydrogel is characterized in that the dosage ratio of the methyl orange aqueous solution, the pyrrole and the ferric salt is 500-800 mL: 1-3 mL: 20-40 g.
5. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 22SO4The preparation method of the composite hydrogel is characterized in that the dispersion temperature of the ultrasonic dispersion in the step 1) is 0-35 ℃, and the dispersion time is 5-40 min.
6. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that the mass ratio of the ferric salt to the manganese salt in the step 2) is (0.5-20) to (0.2-10).
7. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that in the step 2), the ferric salt is one of ferric chloride, ferric sulfate and ferric nitrate, and the manganese salt is one of manganese sulfate, manganese carbonate and manganese chloride.
8. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that the dissolving temperature of the stirring dissolution in the step 3) is 90-105 ℃.
9. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that the polyvinyl alcohol in the step 3) and the polypyrrole/MnFe in the step 4) are mixed2SO4The mass ratio of the nano-composite is (0.2-5) to (0.05-0.5).
10. The multifunctional polyvinyl alcohol/polypyrrole/MnFe of claim 12SO4The preparation method of the composite hydrogel is characterized in that the mass ratio of the polyvinyl alcohol in the step 3) to the borax in the step 5) is (2-20) to 1.
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