CN114316145A - Preparation method of tough type double-network photochromic hydrogel - Google Patents
Preparation method of tough type double-network photochromic hydrogel Download PDFInfo
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- CN114316145A CN114316145A CN202210097902.6A CN202210097902A CN114316145A CN 114316145 A CN114316145 A CN 114316145A CN 202210097902 A CN202210097902 A CN 202210097902A CN 114316145 A CN114316145 A CN 114316145A
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract 1
- 229920000083 poly(allylamine) Polymers 0.000 description 23
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a tough type double-network photochromic hydrogel, belonging to the technical field of photochromism. Sequentially adding a polymer monomer and polyoxometallate powder into deionized water at room temperature, and stirring for dissolving; adding a cross-linking agent, an initiator and a catalyst; when the solution is completely changed into a clear state, pouring the solution into a fixed forming die, and crosslinking for 18-40 h at the temperature of 20-40 ℃ to obtain the toughness double-network photochromic hydrogel. The preparation method is simple in preparation process and low in preparation cost, and the prepared hydrogel has excellent mechanical properties and good optical properties.
Description
Technical Field
The invention belongs to the technical field of photochromism, and particularly relates to a preparation method of a tough type hydrogel photochromism material.
Background art:
the photochromic material is a material capable of undergoing a reversible color change upon irradiation with light. The light source capable of initiating the discoloration of the material is mostly ultraviolet light. The materials can change the structure of the materials or undergo chemical reaction after obtaining the energy of ultraviolet light, so that the absorbance of the materials is changed, and the materials show the change of color. The characteristic makes the display device have larger application in the fields of display, information prompt and the like.
The storage medium is an indispensable recording tool in human productive life. Optical storage media, such as optical disks, are most commonly used in our daily life as materials based on rigid disk structures. However, such rigid materials are fragile and brittle under external forces, resulting in loss of information. Therefore, a stretchable flexible optical storage material with a certain resistance to external force is produced. However, most of the optical storage materials based on hydrogel reported at present have poor mechanical properties, which seriously affect the application of the optical storage materials in real life. Therefore, the hydrogel is subjected to toughening treatment, and the mechanical property of the hydrogel is improved, so that the hydrogel can be better applied to actual life.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible, transparent and tough type double-network photochromic hydrogel, which is simple and can obtain the tough type photochromic hydrogel.
The technical scheme of the invention is as follows:
a preparation method of a tough type double-network photochromic hydrogel comprises the following steps:
1) sequentially adding a polymer monomer and polyoxometallate powder into deionized water at room temperature, and completely dissolving the medicines by adopting a magnetic stirring mode; the polymer monomer is acrylamide and sodium alginate, and the polyoxometallate is isopoly acid; the mass fraction of acrylamide in the system after dissolution is 1-20%, the mass fraction of sodium alginate is 1-5%, and the mass fraction of isopolyacid is 1.5-5%;
2) adding a cross-linking agent, an initiator and a catalyst into the solution obtained in the step 1) in sequence;
3) when the solution is completely changed into a clear state, pouring the solution into a fixed forming die, and crosslinking for 18-40 h at the temperature of 20-40 ℃ to obtain the toughness double-network photochromic hydrogel.
The isopolyacid described in step 1) is preferably ammonium molybdate.
The cross-linking agent in the step 2) is preferably N, N-methylene bisacrylamide, and the mass fraction of the cross-linking agent relative to the acrylamide monomer is preferably 0.001-0.1%.
The initiator in the step 2) is preferably potassium persulfate (KPS) or Ammonium Persulfate (AP), and the mass fraction of the initiator relative to the acrylamide monomer is preferably 0.001-1%.
The catalyst in the step 2) is preferably N, N, N ', N' -tetramethyldiethylamine, and the mass fraction of the N, N, N ', N' -tetramethyldiethylamine relative to the acrylamide monomer is preferably 0.001-1%.
Has the advantages that:
the double-network hydrogel is the same as other hydrogels, has good flexibility, and is simple in preparation process and low in manufacturing cost. Compared with PAAm hydrogel, the rupture stress of the PAAm/SA-Mo7 hydrogel prepared by the invention is increased by nearly 7 times, and the rupture stress reaches the following values: 170 KPa; the elongation at break is increased by nearly 30 times, reaching 3300%. The mechanical property is considered, the hydrogel also has good optical property, and the initial transmittance of PAAm/SA-Mo7 hydrogel reaches more than 90%. Due to the excellent mechanical property, the hydrogel can not generate permanent deformation after being stretched properly, which brings strong mechanical stability to the application of the hydrogel in various environments. In addition, PAAm/SA-Mo7 hydrogel can rapidly respond to ultraviolet light, and can be converted into a colored state from a transparent state within 15s under the irradiation of the ultraviolet light; meanwhile, the hydrogel has high stability under daily illumination, and cannot be re-colored or aged due to ultraviolet light contained in solar illumination. Which can utilize in air as well as some previously reported hydrogelsO2The discoloration is carried out, thereby realizing the photochromic-discoloration cycle process.
Drawings
FIG. 1 is a graph comparing the mechanical properties of the photochromic hydrogels of the present invention.
FIG. 2 is a graph showing photochromic properties of the photochromic hydrogel according to the present invention.
FIG. 3 shows the UV-visible spectra of the photochromic hydrogels of the present invention under different illumination times
Detailed Description
The technical solution of the present invention is further explained and illustrated below by way of specific examples.
Example 1: preparation of PAAm/SA double-network hydrogel
At room temperature, 20mL of deionized water was placed in a beaker, 0.50162g of sodium alginate and 4.51462g of acrylamide were added to the beaker in sequence, and the drug was completely dissolved by magnetic stirring.
0.00181g N, N-methylenebisacrylamide, 0.02708g ammonium persulfate and 46.86. mu. L N, N, N ', N' -tetramethyldiethylamine were then added to the above solution in the stated amounts.
And when the solution is completely clarified, pouring the solution into a fixed forming die, and crosslinking the solution at 30 ℃ for 24 hours to obtain the PAAm/SA double-network hydrogel.
Example 2: preparation of PAAm/SA-Mo7 tough type double-network photochromic hydrogel
At room temperature, 20mL of deionized water was placed in a beaker, and 0.50162g of sodium alginate, 4.51462g of acrylamide and 0.90g of ammonium molybdate powder were sequentially added to the beaker, and the above drug was completely dissolved by magnetic stirring.
0.00181g N, N-methylenebisacrylamide, 0.02708g ammonium persulfate and 46.86. mu. L N, N, N ', N' -tetramethyldiethylamine were then added to the above solution in the stated amounts.
And pouring the solution into a fixed forming die when the solution is completely clarified, and crosslinking the solution at 30 ℃ for 24 hours to obtain the PAAm/SA-Mo7 double-network photochromic hydrogel.
Example 3: mechanical Property test
The instrument model is as follows: universal testing machine SHIMADZU, model AGS-X. And (3) testing conditions are as follows: the drawing rate was 80 mm/min. Sample preparation: and cutting the hydrogel sample to be detected into a dumbbell shape, wherein the size of the dumbbell sample is 30mm in length, 4mm in width, 3mm in thickness and 12mm in gauge length. The test results are shown in fig. 1.
The stress strain of the different hydrogels can be seen in fig. 1 (a). Comparing the stress-strain curves of PAAm and PAAm/SA prepared by the traditional method, it can be seen that the stress at break and the elongation at break of the hydrogel are both increased greatly with the addition of SA. The original PAAm hydrogel has a breaking stress of less than 25KPa, and the breaking stress reaches 230KPa after SA is added. The maximum breaking elongation is improved to be close to 1900% from the original 120%. The chemical crosslinking PAAm network penetrates through a plurality of macromolecular SA chains, the linear macromolecular SA and the chemical crosslinking PAAm macromolecular chains are intertwined, and the linear macromolecular SA fills gaps among the PAAm polymer networks, so that the compactness of the whole hydrogel network system is greatly increased. When an external force acts on the hydrogel, stress can be well dispersed, so that tensile strength and elongation at break are increased. Comparing PAAm with PAAm/SA-Mo7 prepared by the invention, it can be found that after Mo7 is added, the breaking stress of the hydrogel is reduced to about 170KPa, and the maximum breaking elongation is increased to about 3300%, because the original tightly wound structure of the hydrogel is loosened due to the addition of Mo7, the mobility of the molecular chain is increased, when an external force acts on the hydrogel, the free moving space of the molecular chain is enlarged, the flexibility of the hydrogel is increased, and therefore the breaking elongation is increased. At the same time, the tightly wound structure becomes loose, which means that the whole network structure of the hydrogel is looser, so the breaking strength is reduced.
The toughness of the different hydrogels can be seen in FIG. 1 (b). The toughness of PAAm hydrogel is 36.89KJ/m3After macromolecular SA is added, the toughness of PAAm/SA is greatly increased to reach 2094.52KJ/m3The improvement of toughness is benefited by a double-network structure formed by PAAm and SA, and the double networks act synergistically in the stretching process to cause the fracture of the PAAm and SA to be more costlyMuch energy. The toughness of PAAm/SA-Mo7 hydrogel reaches 3177.03KJ/m3This is because Mo7 loosens the chain structure of the entire hydrogel, increasing the toughness, and thus further dissipating energy during stretching, and ultimately making it more tough.
Example 4: optical Performance testing
The instrument model is as follows: an ultraviolet-visible spectrophotometer UV755 b. And (3) testing conditions are as follows: the scanning range is 400-800 nm. The scanning speed was 60 nm/min. Sample preparation: the thickness of the hydrogel was 2 mm. When in testing, the sample is fixed on the sample holder to start the test. The test results are shown in fig. 2 and 3.
The color change of the photochromic hydrogel at different illumination times can be seen in fig. 2. The photochromic hydrogel changes very rapidly, exhibiting a color change at 15 seconds, and gradually darkens with time. The photochromic principle of PAAm/SA-Mo7 hydrogel is: mo in ammonium molybdate molecules is Mo (VI) under the conventional condition, and can be reduced into Mo (V) under the action of ultraviolet light. Whether Mo shows color or not is that whether electrons exist on a d orbital or not, and after Mo (VI) is reduced into Mo (V), electrons are arranged on the d orbital, so that the color is displayed macroscopically. Mo (VI) has no electrons in the d-orbital and thus exhibits a colorless state. On the UV-visible spectrum, two absorption peaks at 620nm and 740nm are assigned to the d-d transition of Mo (V), and the valence charge transfer (IVCT) of Mo (V) -Mo (VI), respectively.
As can be seen from FIG. 3, after the PAAm/SA-Mo7 hydrogel is irradiated by ultraviolet light for 30s, the absorbance is obviously increased, and two obvious absorption peaks are respectively shown at 620nm and 740nm on the spectrum. The absorbance of the hydrogel increased with the increase of the light irradiation time within 180s, and at 180s, the absorbance of the hydrogel reached a maximum, at which time the absorbance at 740nm reached 1.4 units.
Claims (3)
1. A preparation method of a tough type double-network photochromic hydrogel comprises the following steps:
1) sequentially adding a polymer monomer and polyoxometallate powder into deionized water at room temperature, and completely dissolving the medicines by adopting a magnetic stirring mode; the polymer monomer is acrylamide and sodium alginate, and the polyoxometallate is isopoly acid; the mass fraction of acrylamide in the system after dissolution is 1-20%, the mass fraction of sodium alginate is 1-5%, and the mass fraction of isopolyacid is 1.5-5%;
2) adding a cross-linking agent, an initiator and a catalyst into the solution obtained in the step 1) in sequence;
3) when the solution is completely changed into a clear state, pouring the solution into a fixed forming die, and crosslinking for 18-40 h at the temperature of 20-40 ℃ to obtain the toughness double-network photochromic hydrogel.
2. The method for preparing the tough type double-network photochromic hydrogel according to claim 1, wherein the isopolyacid in the step 1) is ammonium molybdate.
3. The preparation method of the tough double-network photochromic hydrogel according to claim 1, wherein the crosslinking agent in the step 2) is N, N-methylene bisacrylamide, and the mass fraction of the crosslinking agent relative to the acrylamide monomer is 0.001-0.1%; the initiator is potassium persulfate or ammonium persulfate, and the mass fraction of the initiator relative to the acrylamide monomer is 0.001-1%; the catalyst is N, N, N ', N' -tetramethyl diethylamine, and the mass fraction of the catalyst relative to the acrylamide monomer is 0.001-1%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115716939A (en) * | 2022-06-29 | 2023-02-28 | 湖南师范大学 | Sodium alginate-based ink-free photoetching printing paper capable of being repeatedly erased, dissolved and regenerated |
| CN116253820A (en) * | 2023-05-09 | 2023-06-13 | 北京石油化工学院 | Photochromic gel, multi-response color-changing xerogel prepared from same and color-changing method |
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Patent Citations (2)
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| CN103396562A (en) * | 2013-07-09 | 2013-11-20 | 西安交通大学 | Preparation method for sodium alginate-acrylamide-based hydrogel |
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Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115716939A (en) * | 2022-06-29 | 2023-02-28 | 湖南师范大学 | Sodium alginate-based ink-free photoetching printing paper capable of being repeatedly erased, dissolved and regenerated |
| CN115716939B (en) * | 2022-06-29 | 2024-01-26 | 湖南师范大学 | Sodium alginate-based ink-free photoetching printing paper capable of repeatedly erasing, writing, dissolving and regenerating |
| CN116253820A (en) * | 2023-05-09 | 2023-06-13 | 北京石油化工学院 | Photochromic gel, multi-response color-changing xerogel prepared from same and color-changing method |
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