CN114656655B - Oil-water gel for storing circulation information under visible light and preparation method and application thereof - Google Patents

Oil-water gel for storing circulation information under visible light and preparation method and application thereof Download PDF

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CN114656655B
CN114656655B CN202210322579.8A CN202210322579A CN114656655B CN 114656655 B CN114656655 B CN 114656655B CN 202210322579 A CN202210322579 A CN 202210322579A CN 114656655 B CN114656655 B CN 114656655B
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information
oil
water gel
hydrogel
solvent
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CN114656655A (en
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陈涛
单福庆
乐晓霞
谷金翠
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Ningbo Institute of Material Technology and Engineering of CAS
Ningbo University
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Ningbo University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F2/00—Processes of polymerisation
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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F21/00—Security arrangements for protecting computers, components thereof, programs or data against unauthorised activity
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    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

The invention discloses an oil-water gel for storing circulation information under visible light and a preparation method and application thereof. The preparation method comprises the following steps: polymerizing a first mixed reaction system comprising a first monomer, a first initiator, a first crosslinking agent and a first solvent to obtain hydrogel, and then soaking and drying the hydrogel in acetone to obtain dehydrated hydrogel; and carrying out photopolymerization on a second mixed reaction system containing a second monomer, a second initiator, a second crosslinking agent, a second solvent and the dehydrated hydrogel to prepare the oil-water gel for storing circulation information under visible light. The hydrogel prepared by the invention can realize at least 50 times of cyclic information loading, encryption, decryption and erasure under visible light, solves the problems that specific equipment is needed for reading hydrogel information and the repeated editability is poor at present, and has wide application prospects in the fields of information encryption, anti-counterfeiting, imaging and the like.

Description

Oil-water gel for storing circulation information under visible light and preparation method and application thereof
Technical Field
The invention belongs to the field of intelligent high polymer materials and information storage materials, and particularly relates to an oil-water gel for circulating information storage under visible light, a preparation method and application thereof.
Background
People have entered the information age, and people have to face the threat and challenge of information security while enjoying the convenience of life brought by informatization.
The intelligent hydrogel can show shape deformation or color conversion under external stimulus (such as temperature, pH, light, special chemical substances, magnetic field, electric field and the like), and has great application potential in the fields of soft robots, flexible sensors, camouflage, information storage and the like. The intelligent hydrogel has unique response capability to specific stimulus, so that hidden information can be decrypted under certain conditions, and the intelligent hydrogel is a promising information storage candidate material. In recent years, researchers have focused on applying hydrogels to explore modern information storage strategies, such as Zhang Lidong, etc., to propose a light-operated coordination switching mechanism that achieves reversible color changes by altering localized surface plasmon resonance of silver nanoparticles (AgNPs) in the hydrogel network. Through a high precision mask, it can write, store and erase complex information on the hydrogel surface (Advanced Optical Materials, 2021:2101505). Wu Ziliang et al propose a tough hydrogel with good shape memory and tunable fluorescence, and the fluorescence information encrypted in the built hydrogel must be sequentially recovered in shape and irradiated with ultraviolet light to be readable, providing programmable shape design and information encoding for double encryption (Advanced Materials, 2021:2102023). These attempts provide new ideas for developing hydrogel-based information storage materials. However, these strategies also suffer from drawbacks such as the need for specific equipment for information reading, poor repeatability, etc. Therefore, development of a programmable security platform with easy information reading is urgent but quite challenging.
Disclosure of Invention
The invention mainly aims to provide an oil-water gel for storing circulation information under visible light and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an oil-water gel for circulating information storage under visible light, which comprises the following steps:
polymerizing a first mixed reaction system comprising a first monomer, a first initiator, a first crosslinking agent and a first solvent to obtain hydrogel, and then soaking and drying the hydrogel in acetone to obtain dehydrated hydrogel;
and carrying out photopolymerization on a second mixed reaction system containing a second monomer, a second initiator, a second crosslinking agent, a second solvent and the dehydrated hydrogel to prepare the oil-water gel for storing circulation information under visible light. The embodiment of the invention also provides the oil-water gel for storing the circulation information under the visible light prepared by the method.
The embodiment of the invention also provides application of the oil-water gel for circulating information storage under the visible light in the fields of soft robots, flexible sensors, camouflage or information storage.
The embodiment of the invention also provides an information writing and erasing method, which comprises the following steps:
providing the oil-water gel for storing the circulating information under the visible light;
loading information into the oil-water gel in a printing and dyeing mode;
and erasing the information loaded in the oil-water gel by adopting a solvent replacement mode.
Compared with the prior art, the invention has the beneficial effects that:
(1) The oil-water gel for storing the circulation information under the visible light can generate phase change under the stimulation of temperature and solvent, so that the polymer chains are contracted and gathered, the light transmission is reduced, the transparency of the material surface is changed, and the local optical characteristic difference of the gel surface is cooperatively regulated and controlled through external stimulation, so that the information is stored; the reading of the decryption information can realize visual observation without the help of specific equipment, and has wide application prospect in the fields of information encryption, anti-counterfeiting, imaging and the like;
(2) The oil-water gel for storing the circulating information under the visible light prepared by the invention realizes the loading of the information and the encryption-decryption process thereof by introducing external stimulus, and the stored information can be erased simply by replacing the solvent by the erasing agent, thus the repeated editing of the encrypted information can be realized;
(3) The preparation method of the oil-water gel provided by the invention is simple, is convenient to operate, and does not need expensive preparation instruments, high-temperature actions and catalysts.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic diagram of an oil-water gel for circulating information storage for information storage and decryption under visible light according to an exemplary embodiment of the present invention;
FIGS. 2 a-2 b are graphs showing response mechanisms of an oil-water gel for storing circulation information under different stimuli in a visible light according to an exemplary embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of an oil-water gel for circulation information storage under visible light prepared in example 4 of the present invention;
FIG. 4 is a schematic diagram showing the process of erasing information and recycling materials in embodiment 4 of the present invention;
FIG. 5 is a schematic diagram showing the loading process of the pure oleogel information of comparative example 2 of the present invention;
fig. 6 is a schematic diagram showing the loading and hiding encryption process of information of the non-responsive oil hydrogel of comparative example 3 of the present invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the oil-water gel for storing the circulation information under the visible light comprises the following steps:
polymerizing a first mixed reaction system comprising a first monomer, a first initiator, a first crosslinking agent and a first solvent to obtain hydrogel, and then soaking and drying the hydrogel in acetone to obtain dehydrated hydrogel;
and carrying out photopolymerization on a second mixed reaction system containing a second monomer, a second initiator, a second crosslinking agent, a second solvent and the dehydrated hydrogel to prepare the oil-water gel for storing circulation information under visible light.
In some preferred embodiments, the preparation method specifically comprises:
mixing a first monomer, a first initiator, a first cross-linking agent and a first solvent to form hydrogel prepolymer liquid, and then carrying out polymerization reaction for 2-48 h at 4-80 ℃ to prepare hydrogel;
and placing the hydrogel in acetone for soaking for 3-8 hours, and then drying for 3-5 hours at 20-40 ℃ to obtain the dehydrated hydrogel.
Further, the first monomer includes any one or a combination of two or more of N, N' -dimethylacrylamide, acrylamide, and acrylic acid, and is not limited thereto.
Still further, the first monomer is N, N' -dimethylacrylamide.
Further, the first initiator includes potassium persulfate and/or ammonium persulfate, and is not limited thereto.
Further, the first crosslinking agent includes N, N' -methylenebisacrylamide, and is not limited thereto.
Further, the first solvent includes water, and is not limited thereto.
Further, the mass ratio of the first monomer to the first solvent is 1-3:5.
Further, the mass ratio of the first initiator to the first solvent is 10-50 mg/5 g.
Further, the mass ratio of the first cross-linking agent to the first solvent is 1-5 mg/5 g.
In some preferred embodiments, the preparation method specifically comprises: and mixing a second monomer, a second initiator, a second cross-linking agent and a second solvent to form an oil gel pre-polymerization solution, swelling the dehydrated hydrogel in the oil gel pre-polymerization solution, and carrying out photopolymerization at 20-60 ℃ for 2-60 min to obtain the oil-water gel for circulating information storage under the visible light.
Further, the second monomer comprises stearyl methacrylate and/or lauryl methacrylate, wherein the second monomer is a long-chain acrylic ester crystalline monomer.
Further, the second initiator comprises 2, 2-diethoxyacetophenone, wherein the second initiator is an ultraviolet-initiated oil-soluble initiator.
Further, the second crosslinking agent includes ethylene glycol dimethacrylate, and is not limited thereto.
Further, the second solvent includes ethanol, and is not limited thereto.
Further, the mass ratio of the second monomer to the second solvent is 1-3:5.
Further, the mass ratio of the second initiator to the second solvent is 10-50 mg/5 g.
Further, the mass ratio of the second crosslinking agent to the second solvent is 1-5 mg/5 g.
Further, the mass ratio of the dehydrated hydrogel to the oil gel prepolymer is 1:2-7.
Further, the photopolymerization reaction employs a light wavelength of 365nm.
In some more specific embodiments, the method for preparing the oil-water gel for circulating information storage under visible light comprises the following steps:
(1) Preparation of dehydrated hydrogels: mixing and dissolving a first monomer, a first initiator, a first cross-linking agent and water to form hydrogel prepolymer, carrying out polymerization reaction on the prepolymer to obtain hydrogel, then soaking the hydrogel in acetone, and then drying to obtain dehydrated hydrogel; ( Wherein acetone is used for swelling the hydrogel and removing unreacted monomers; the water solvent is replaced, so that the water in the system is prevented from affecting the swelling of the oleogel prepolymer in the next step; acetone and water are mutually soluble and volatile, which is favorable for later removal )
(2) Preparing an oil-water gel: and mixing and dissolving a second monomer, a second initiator and a second crosslinking agent with ethanol to form an oil gel prepolymer, swelling the dehydrated hydrogel in the oil gel prepolymer to reach equilibrium, and carrying out photopolymerization on the prepolymer to obtain the oil-water gel.
Further, in the step (1), the first monomer is N, N '-dimethylacrylamide, the first initiator comprises one of potassium persulfate and ammonium persulfate, the first crosslinking agent is N, N' -methylenebisacrylamide, wherein the content of the first monomer is 1-3 g/5g of water, the content of the first initiator is 10-50 mg/5g of water, and the content of the first crosslinking agent is 1-5 mg/5g of water.
Further, in the step (1), the temperature of the polymerization reaction is 4-80 ℃ and the time is 2-48 h, and in the step (1), the reaction is carried out in acetone for 3-8 h, the drying temperature is 20-40 ℃ and the drying time is 3-5 h.
Further, in the step (2), the second monomer is stearyl methacrylate, the second initiator is 2, 2-diethoxyacetophenone, the second crosslinking agent is ethylene glycol dimethacrylate, wherein the content of the second monomer is 1-3 g/5g ethanol, the content of the second initiator is 10-50 mg/5g ethanol, and the content of the second crosslinking agent is 1-5 mg/5g ethanol.
Further, in the step (2), the temperature of the photopolymerization reaction is 20-60 ℃ and the time is 2-60 min.
In another aspect, the embodiment of the invention also provides the oil-water gel for storing the circulation information under the visible light prepared by the method.
Another aspect of the embodiments of the present invention further provides an application of the aforementioned hydrogel for circulating information storage under visible light in the field of soft robots, flexible sensors, camouflage, or information storage.
Another aspect of the embodiment of the present invention further provides an information writing and erasing method, including:
providing the oil-water gel for storing the circulation information under the visible light;
loading information into the oil-water gel in a printing and dyeing mode;
and erasing the information loaded in the oil-water gel by adopting a solvent replacement mode.
In some preferred embodiments, the method of making further comprises: and carrying out low-temperature treatment on the oil-water gel loaded with the information so as to realize information encryption, and then carrying out high-temperature treatment so as to realize information decryption.
In some preferred embodiments, the preparation method specifically comprises:
applying a printing and dyeing agent on the surface of the oil-water gel so as to perform solvent replacement, thereby realizing information loading;
carrying out low-temperature treatment on the oil-water gel loaded with information at 0-20 ℃ for 1-10 min, so as to realize information encryption;
the oil-water gel with the encrypted information is subjected to high-temperature treatment for 2 to 20 minutes at the temperature of between 30 and 40 ℃ so as to realize information decryption;
and applying an erasing agent to the surface of the oil-water gel for decrypting the information so as to replace the solvent, thereby realizing information erasing.
Further, the printing and dyeing agent comprises any one or more than two of water, ethanol and methanol, wherein the printing and dyeing agent is a polar solvent.
Further, the erasing agent comprises dimethyl sulfoxide and/or N, N-dimethylformamide, wherein the erasing agent is an amphiphilic solvent.
In some preferred embodiments, the schematic diagram of the process of the oil-water gel for storing and decrypting information under the visible light in the invention is shown in fig. 1.
In some preferred embodiments, the response mechanism diagrams of the oil-water gel for circulation information storage under the visible light in the invention under different stimuli are shown in fig. 2 a-2 b.
In some more specific embodiments, the information writing and erasing method includes: and (3) placing the patterning mould on the surface of the oil-water gel, dropwise adding a printing and dyeing agent onto the mould, wherein the printing and dyeing agent can permeate into the oil-water gel to replace a solvent, so as to realize information loading, then placing the oil-water gel in a low-temperature environment of 0-20 ℃ to realize information encryption, and raising the environment temperature to 30-40 ℃ to realize information decryption. And finally, performing solvent replacement by dimethyl sulfoxide to realize information erasure.
Compared with the traditional hydrogel, the hydrogel for storing the circulation information under the visible light can realize at least 50 times of circulation information loading, encryption, decryption and erasure under the visible light, and solves the problems that the conventional hydrogel information reading requires specific equipment and has poor repeated editing property.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
(1) Preparation of hydrogels: 1g of N, N '-dimethylacrylamide, 10mg of ammonium persulfate and 1g of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 4 ℃ and the reaction time is 48 hours, so as to obtain hydrogel; soaking the hydrogel in acetone for 3 hours, taking out, and drying in a ventilation place for 3 hours at 20 ℃;
(2) Preparation of the oil-water gel: adding the dehydrated hydrogel into a mixed solution of 1g of stearyl methacrylate, 5g of absolute ethyl alcohol, 10mg of 2, 2-diethoxyacetophenone and 1mg of ethylene glycol dimethacrylate, soaking for 6 hours, taking out the dehydrated hydrogel, irradiating the dehydrated hydrogel for 60 minutes in a 20 ℃ environment by using a 365nm ultraviolet lamp, and then putting the dehydrated hydrogel into dimethyl sulfoxide to obtain oil-water gel;
(3) And (3) loading information: placing a "sakura" pattern mold on the surface of the oil-water gel in the step (2), adding water drops on the mold, and allowing water molecules to permeate into the oil-water gel to replace solvents, so as to realize information loading under visible light;
(4) Information encryption: cooling the oil-water gel carrying information prepared in the step (3) at 0 ℃ for 10min to hide patterns on the oil-water gel, so as to encrypt the information under visible light;
(5) Decrypting information: heating the oil-water gel encrypted in the step (4) at 40 ℃ for 4min to make the hidden pattern information show again, so as to realize information decryption under visible light;
(6) And (3) information erasure: soaking the oil-water gel loaded with information in dimethyl sulfoxide at 25 ℃ for 20min, and eliminating pattern information on the oil-water gel to realize information erasure under visible light;
(7) And (3) circularly storing information: the oil-water gel with the information erased in the step (6) is subjected to the cyclic operation from the step (3) to the step (6), and experiments show that the oil-water gel can realize 60-time cyclic information storage.
Example 2
(1) Preparation of hydrogels: 1.5g of N, N '-dimethylacrylamide, 30mg of ammonium persulfate and 3mg of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 42 ℃ and the reaction time is 25 hours, so that hydrogel is obtained; soaking the hydrogel in acetone for 6 hours, taking out, and drying in a ventilation place for 4 hours at a drying temperature of 30 ℃;
(2) Preparation of the oil-water gel: adding the dehydrated hydrogel into a mixed solution of 2g of stearyl methacrylate, 5g of absolute ethyl alcohol, 30mg of 2, 2-diethoxyacetophenone and 3mg of ethylene glycol dimethacrylate, soaking for 6 hours, taking out the dehydrated hydrogel, irradiating for 30 minutes in a 40 ℃ environment by using a 365nm ultraviolet lamp, and then putting the dehydrated hydrogel into dimethyl sulfoxide to obtain oil-water gel;
(3) And (3) loading information: placing a "sakura" pattern mold on the surface of the oil-water gel in the step (2), adding water drops on the mold, and allowing water molecules to permeate into the oil-water gel to replace solvents, so as to realize information loading under visible light;
(4) Information encryption: cooling the oil-water gel carrying information prepared in the step (3) at 0 ℃ for 10min to hide patterns on the oil-water gel, so as to encrypt the information under visible light;
(5) Decrypting information: heating the oil-water gel encrypted in the step (4) at 40 ℃ for 3min to make the hidden pattern information show again, so as to realize information decryption under visible light;
(6) And (3) information erasure: soaking the oil-water gel loaded with information in dimethyl sulfoxide at 25 ℃ for 20min, and eliminating pattern information on the oil-water gel to realize information erasure under visible light;
(7) And (3) circularly storing information: the oil-water gel with the information erased in the step (6) is subjected to the cyclic operation from the step (3) to the step (6), and experiments show that the oil-water gel can realize 65-time cyclic information storage.
Example 3
(1) Preparation of hydrogels: 3g of N, N '-dimethylacrylamide, 50mg of ammonium persulfate and 5mg of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 80 ℃ and the reaction time is 2 hours, so that hydrogel is obtained; soaking the hydrogel in acetone for 8 hours, taking out, and drying in a ventilation place for 5 hours at a drying temperature of 40 ℃;
(2) Preparation of the oil-water gel: adding the dehydrated hydrogel into a mixed solution of 3g of stearyl methacrylate, 5g of absolute ethyl alcohol, 50mg of 2, 2-diethoxyacetophenone and 5mg of ethylene glycol dimethacrylate, soaking for 6 hours, taking out the dehydrated hydrogel, irradiating for 2 minutes in a 60 ℃ environment by using a 365nm ultraviolet lamp, and then putting the dehydrated hydrogel into dimethyl sulfoxide to obtain oil-water gel;
(3) And (3) loading information: placing a "sakura" pattern mold on the surface of the oil-water gel in the step (2), adding water drops on the mold, and allowing water molecules to permeate into the oil-water gel to replace solvents, so as to realize information loading under visible light;
(4) Information encryption: cooling the oil-water gel carrying information prepared in the step (3) at 0 ℃ for 10min to hide patterns on the oil-water gel, so as to encrypt the information under visible light;
(5) Decrypting information: heating the oil-water gel encrypted in the step (4) at 40 ℃ for 10min to make the hidden pattern information show again, so as to realize information decryption under visible light;
(6) And (3) information erasure: soaking the oil-water gel loaded with information in dimethyl sulfoxide at 25 ℃ for 20min, and eliminating pattern information on the oil-water gel to realize information erasure under visible light;
(7) And (3) circularly storing information: the oil-water gel with the information erased in the step (6) is subjected to the cyclic operation from the step (3) to the step (6), and experiments show that 50 times of cyclic information storage can be realized.
Example 4
(1) Preparation of hydrogels: 2.5g of N, N '-dimethylacrylamide, 25mg of ammonium persulfate and 2.5mg of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 30 ℃ and the reaction time is 5 hours, so that hydrogel is obtained; soaking the hydrogel in acetone for 4 hours, taking out, and drying in a ventilation place for 5 hours at a drying temperature of 25 ℃;
(2) Preparation of the oil-water gel: adding the dehydrated hydrogel into a mixed solution of 2.5g of stearyl methacrylate, 5g of absolute ethyl alcohol, 40mg of 2, 2-diethoxyacetophenone and 4mg of ethylene glycol dimethacrylate, soaking for 6 hours, taking out the dehydrated hydrogel, irradiating the dehydrated hydrogel for 6 minutes in a 30 ℃ environment by using a 365nm ultraviolet lamp, and then putting the dehydrated hydrogel into dimethyl sulfoxide to obtain an oil-water gel, wherein a scanning electron microscope diagram of the oil-water gel is shown in figure 3;
(3) And (3) loading information: placing a "sakura" pattern mold on the surface of the oil-water gel in the step (2), adding water drops on the mold, and allowing water molecules to permeate into the oil-water gel to replace solvents, so as to realize information loading under visible light;
(4) Information encryption: cooling the oil-water gel carrying information prepared in the step (3) at 0 ℃ for 10min to hide patterns on the oil-water gel, so as to encrypt the information under visible light;
(5) Decrypting information: heating the oil-water gel encrypted in the step (4) at 40 ℃ for 8min to make the hidden pattern information show again, so as to realize information decryption under visible light;
(6) And (3) information erasure: soaking the oil-water gel loaded with information in dimethyl sulfoxide at 25 ℃ for 20min, and eliminating pattern information on the oil-water gel to realize information erasure under visible light;
(7) And (3) circularly storing information: the oil-water gel for erasing information in the step (6) is subjected to the cyclic operation in the steps (3) to (6), and experiments show that 55 times of cyclic information storage can be realized, and the erasing of information and the repeated use process of materials in the embodiment are shown in fig. 4.
Comparative example 1 comparative pure water gel
(1) Preparation of hydrogels: 2.5g of N, N '-dimethylacrylamide, 25mg of ammonium persulfate and 2.5mg of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 30 ℃ and the reaction time is 5 hours, so that hydrogel is obtained; soaking the hydrogel in acetone for 4 hours, taking out, drying in a ventilation place for 5 hours at a drying temperature of 25 ℃, and soaking in dimethyl sulfoxide;
(2) And (3) loading information: placing a "sakura" pattern mold on the surface of the hydrogel in the step (1), and dripping water on the mold, wherein the transparency change cannot be observed on the surface of the material, and the loading of information cannot be realized.
Comparative example 2 comparative pure oleogel
(1) Preparation of oleogel: pouring a mixed solution of 2.5g of stearyl methacrylate, 5g of absolute ethyl alcohol, 40mg of 2, 2-diethoxyacetophenone and 4mg of ethylene glycol dimethacrylate into a glass die, irradiating for 6min at 30 ℃ by using a 365nm ultraviolet lamp, and taking out the mixed solution and putting into dimethyl sulfoxide to obtain oil gel;
(2) And (3) loading information: the "sakura" pattern mold was placed on the surface of the oil gel in step (1), water was dropped onto the mold, and water molecules were infiltrated into the interior of the oil gel to displace the solvent, but the formed pattern was blurred in outline and difficult to recognize, and the loading process of information in this comparative example was as shown in fig. 5.
Comparative example 3 comparative nonresponsive oil-water gel
(1) Preparation of hydrogels: 2.5g of N, N '-dimethylacrylamide, 25mg of ammonium persulfate and 2.5mg of N, N' -methylenebisacrylamide are dissolved in 5g of deionized water, and then poured into a mold, and the reaction temperature is 30 ℃ and the reaction time is 5 hours, so that hydrogel is obtained; soaking the hydrogel in acetone for 4 hours, taking out, and drying in a ventilation place for 5 hours at a drying temperature of 25 ℃;
(2) Preparation of the oil-water gel: adding the dehydrated hydrogel into a mixed solution of 2.5g of methyl methacrylate, 5g of absolute ethyl alcohol, 40mg of 2, 2-diethoxyacetophenone and 4mg of ethylene glycol dimethacrylate, soaking for 6 hours, taking out the dehydrated hydrogel, irradiating for 6 minutes in a 30 ℃ environment by using a 365nm ultraviolet lamp, and then putting the dehydrated hydrogel into dimethyl sulfoxide to obtain oil-water gel;
(3) And (3) loading information: placing a 'phoenix' pattern mould on the surface of the oil-water gel in the step (2), dripping water on the mould, and allowing water molecules to permeate into the oil-water gel to replace a solvent so as to load information under visible light;
(4) Information encryption: the oil-water gel carrying information prepared in the step (3) is cooled for 10min at the temperature of 0 ℃, the printing and dyeing area and the non-printing and dyeing area on the oil-water gel have larger contrast difference, the pattern information is difficult to hide, the information encryption under the visible light cannot be realized, and the loading and hiding encryption process of the information in the comparative example is shown in fig. 6.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.

Claims (21)

1. The preparation method of the oil-water gel for storing the circulation information under the visible light is characterized by comprising the following steps of:
polymerizing a first mixed reaction system comprising a first monomer, a first initiator, a first crosslinking agent and a first solvent to obtain hydrogel, and then soaking and drying the hydrogel in acetone to obtain dehydrated hydrogel; wherein the first monomer is selected from any one or more than two of N, N '-dimethylacrylamide, acrylamide and acrylic acid, and the first crosslinking agent is selected from N, N' -methylenebisacrylamide;
and performing photopolymerization on a second mixed reaction system comprising a second monomer, a second initiator, a second crosslinking agent, a second solvent and the dehydrated hydrogel to prepare an oil-water gel for storing circulation information under visible light; wherein the second monomer is selected from stearyl methacrylate and/or lauryl methacrylate; the second crosslinking agent is selected from ethylene glycol dimethacrylate.
2. The preparation method according to claim 1, characterized by comprising the following steps:
mixing a first monomer, a first initiator, a first cross-linking agent and a first solvent to form hydrogel prepolymer liquid, and then carrying out polymerization reaction for 2-48 h at 4-80 ℃ to prepare hydrogel;
and placing the hydrogel in acetone for soaking for 3-8 hours, and then drying for 3-5 hours at 20-40 ℃ to obtain the dehydrated hydrogel.
3. The preparation method according to claim 2, characterized in that: the first monomer is N, N' -dimethylacrylamide.
4. The preparation method according to claim 2, characterized in that: the first initiator is selected from potassium persulfate and/or ammonium persulfate.
5. The preparation method according to claim 2, characterized in that: the first solvent is selected from water.
6. The preparation method according to claim 2, characterized in that: the mass ratio of the first monomer to the first solvent is 1-3: 5.
7. the preparation method according to claim 2, characterized in that: the mass ratio of the first initiator to the first solvent is 10-50 mg:5g.
8. The preparation method according to claim 2, characterized in that: the mass ratio of the first cross-linking agent to the first solvent is 1-5 mg:5g.
9. The preparation method according to claim 1, characterized by comprising the following steps: mixing a second monomer, a second initiator, a second cross-linking agent and a second solvent to form an oil gel pre-polymerization solution, swelling the dehydrated hydrogel in the oil gel pre-polymerization solution, and carrying out photopolymerization at 20-60 ℃ for 2-60 min to obtain the oil-water gel for circulating information storage under the visible light.
10. The method of manufacturing according to claim 9, wherein: the second initiator is selected from 2, 2-diethoxyacetophenone.
11. The method of manufacturing according to claim 9, wherein: the second solvent is selected from ethanol.
12. The method of manufacturing according to claim 9, wherein: the mass ratio of the second monomer to the second solvent is 1-3: 5.
13. the method of manufacturing according to claim 9, wherein: the mass ratio of the second initiator to the second solvent is 10-50 mg:5g.
14. The method of manufacturing according to claim 9, wherein: the mass ratio of the second crosslinking agent to the second solvent is 1-5 mg:5g.
15. The method of manufacturing according to claim 9, wherein: the mass ratio of the dehydrated hydrogel to the oleogel prepolymer is 1:2 to 7.
16. The method of manufacturing according to claim 9, wherein: the photopolymerization reaction uses a light wavelength of 365nm.
17. An oil-water gel for circulation information storage under visible light produced by the method of any one of claims 1 to 16.
18. Use of the oil-water gel of claim 17 for circulating information storage under visible light in the field of soft robots, flexible sensors, camouflage or information storage.
19. An information writing and erasing method, characterized by comprising:
providing the oil-water gel for circulating information storage under visible light according to claim 17;
loading information into the oil-water gel in a printing and dyeing mode;
and erasing the information loaded in the oil-water gel by adopting a solvent replacement mode.
20. The information writing and erasing method of claim 19, further comprising: and carrying out low-temperature treatment on the oil-water gel loaded with the information so as to realize information encryption, and then carrying out high-temperature treatment so as to realize information decryption.
21. The information writing and erasing method according to claim 20, characterized by comprising in particular:
applying a printing and dyeing agent on the surface of the oil-water gel so as to perform solvent replacement, thereby realizing information loading;
carrying out low-temperature treatment on the oil-water gel loaded with information at 0-20 ℃ for 1-10 min, so as to realize information encryption;
the oil-water gel with the encrypted information is subjected to high-temperature treatment for 2 to 20 minutes at the temperature of between 30 and 40 ℃ so as to realize information decryption;
applying an erasing agent to the surface of the oil-water gel for information decryption so as to perform solvent replacement, thereby realizing information erasure;
wherein the printing and dyeing agent is selected from any one or more than two of water, ethanol and methanol; the erasing agent is selected from dimethyl sulfoxide and/or N, N-dimethylformamide.
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