LU504033B1 - Structural color multi-responsive hydrogel and preparation method and application thereof - Google Patents
Structural color multi-responsive hydrogel and preparation method and application thereof Download PDFInfo
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- LU504033B1 LU504033B1 LU504033A LU504033A LU504033B1 LU 504033 B1 LU504033 B1 LU 504033B1 LU 504033 A LU504033 A LU 504033A LU 504033 A LU504033 A LU 504033A LU 504033 B1 LU504033 B1 LU 504033B1
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 239000004038 photonic crystal Substances 0.000 claims abstract description 57
- 230000004044 response Effects 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
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- 239000000178 monomer Substances 0.000 claims abstract description 9
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
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- 229920001155 polypropylene Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- BLSAPDZWVFWUTL-UHFFFAOYSA-N 2,5-dioxopyrrolidine-3-sulfonic acid Chemical compound OS(=O)(=O)C1CC(=O)NC1=O BLSAPDZWVFWUTL-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 36
- 239000002904 solvent Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 20
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- CWKAIKSGLZIWGO-UHFFFAOYSA-N CCC(O)=O.OS(=O)(=O)C1CC(=O)NC1=O Chemical compound CCC(O)=O.OS(=O)(=O)C1CC(=O)NC1=O CWKAIKSGLZIWGO-UHFFFAOYSA-N 0.000 description 5
- 229930182555 Penicillin Natural products 0.000 description 5
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229940049954 penicillin Drugs 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000004043 responsiveness Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 2
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- 239000007787 solid Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—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 aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/06—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
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method for structural color multi-responsive hydrogel. According to the method, firstly, monodisperse polymer microspheres are self- assembled into three-dimensional photonic crystals, then hydrophilic monomers acrylamide and carboxymethyl chitosan are filled into the inter-spherical gaps in the photonic crystals, and structural color composite hydrogel with specific pictures and texts information is prepared by photo-initiated polymerization and controlling the illumination intensity of different areas through mask technology. The invention also discloses the structural color multi-responsive hydrogel prepared by the method and the application of the structural color multi-responsive hydrogel in anti-counterfeiting and encryption. The structural color hydrogel in the invention has multiple effects such as solvent response, gas response, mechanical force response, color angle dependence, etc., and is difficult to forge, and has a good application prospect in anti- counterfeiting of tobacco and alcohol commodities, anti-counterfeiting of high-end luxury goods, anti-counterfeiting of electronic science and technology products, etc.
Description
DESCRIPTION 1006008
STRUCTURAL COLOR MULTI-RESPONSIVE HYDROGEL AND
PREPARATION METHOD AND APPLICATION THEREOF
The invention belongs to the technical field of optical anti-counterfeiting materials, and particularly relates to a structural color multi-responsive hydrogel and a preparation method and application thereof.
Responsive photonic crystal material is a kind of optical functional material by combining photonic crystals with stimulus-responsive intelligent material.
At present, most of the responsive photonic crystal materials are in a single response mode and the technology is mature. According to the response characteristics, the existing responsive photonic crystal materials can be divided into ion response type, temperature response type, liquid/gas response type, mechano response type and light response type, etc., which are low in technical content, the structural combination is easy to be deciphered and poor in anti- counterfeiting effect. Therefore, the application and development of the responsive photonic crystal materials in anti-counterfeiting functions are limited greatly.
Therefore, in the field of optical anti-counterfeiting, it will be one of the future trends to prepare the multi-responsive anti-counterfeiting labels. They can improve the complexity of anti-counterfeiting effectively, increase the difficulty of counterfeiting and deciphering greatly, break through the bottleneck of low applicability, low added value and low performance of traditional anti-counterfeiting materials, and open up a new way for anti-counterfeiting technology. It is necessary to realize multiple responses on anti-counterfeiting materials to increase the cost of deciphering and counterfeiting.
The purpose of the present invention is to provide a preparation method for structural color multi-responsive hydrogel. In this method, hydrophilic monomers acrylamide and carboxymethyl chitosan are filled into the inter-spherical gaps in photonic crystals, and the light intensity in different areas is controlled by photo-initiated polymerization and mask technology,
? LU504033 so as to prepare structural color composite hydrogel with specific graphic information, which can realize multiple responses on anti-counterfeiting materials, and the cost of deciphering and counterfeiting is high.
The purpose of the present invention is also to provide a structural color multi-responsive hydrogel prepared by the method, and the structural color multi-responsive hydrogel has multi- responsive characteristics such as solvent response, angular response, gas response and mechanical force response.
The last purpose of the present invention is to provide the application of the structural color multi-responsive hydrogel in encryption and anti-counterfeiting.
The first purpose of the present invention can be achieved by the following technical scheme: a preparation method for structural color multi-responsive hydrogel comprises the following steps: (S1) disperse polymer monodisperse nanospheres in water to obtain polymer monodisperse nanospheres dispersion, insert a hydrophilic glass sheet vertically into the polymer monodisperse nanospheres dispersion, evaporate water in a constant temperature and humidity environment, and self-assemble the polymer monodisperse nanospheres on the surface of the hydrophilic glass sheet by a vertical sedimentation method to obtain polymer photonic crystals; (S2) dissolve carboxymethyl chitosan in water for ultrasonic dispersion, add acrylamide and crosslinking agent in turn when it is transparent and uniform, and perform ultrasonic dispersion until uniform to obtain a multi-responsive polymer monomer solution, add photoinitiator aqueous solution into the multi-responsive polymer monomer solution, and mix uniformly to obtain the polymer precursor mixed solution; (S3) add the polymer precursor mixed solution in step (S2) into the polymer photonic crystals in step (S1), and stand in the dark until the polymer precursor mixed solution completely fills the inter-spherical gaps in the photonic crystals; (S4) arrange a photomask with pictures and texts above the photonic crystals filled with the polymer precursor mixed solution obtained in step (S3), and irradiate under ultraviolet light to initiate polymerization, and (S5) after the polymerization in step (S4) is finished, embed the polymer photonic crystals into the polymer precursor mixed solution, take it off the hydrophilic glass, and clean it to remove impurities, so as to obtain the structural color multi-responsive hydrogel.
In the preparation method for structural color multi-responsive hydrogel:
> LU504033 preferably, the polymer monodisperse nanospheres in step (S1) are polystyrene monodisperse nanospheres or polymethylmethacrylate monodisperse nanospheres, and the particle size is 160~350 nm.
The polymer monodisperse nanospheres in this application have not been removed, but have been embedded in the hydrogel, as shown by the electron microscope image in Fig. 1.
Preferably, the mass percentage content of the polymer monodisperse nanospheres in the polymer monodisperse nanospheres dispersion in step (S1) is 0.15~0.25wt%
Preferably, in the constant temperature and humidity environment in step (S1), the temperature is 50~65°C and relative humidity is 55~70%.
Preferably, the crosslinking agent in step (S2) is N-N'- methylene bisacrylamide, divinylbenzene, diisocyanate or 3,3'-dithiobis (sulfosuccinimide propionate).
Preferably, in step (S2), the mass ratio of methyl chitosan, acrylamide, crosslinking agent and water is 0.1~0.5:1.5~2.5, 0.03~0.07:3.5~5.
Preferably, the crosslinking agent in step (S2) is N-N'- methylene bisacrylamide, divinylbenzene, diisocyanate or 3,3'-dithiobis (sulfosuccinimide propionate).
Preferably, in the step (S2), the mass percentage content of the photoinitiator in the photoinitiator aqueous solution is 10~40%, and its addition amount accounts for 1~6% of the total mass of the multi-responsive polymer monomer solution.
Preferably, in the step (S2), the photoinitiator is azodiisobutylamidine hydrochloride, azodiisobutylimidazoline hydrochloride, azodicyanovaleric acid, azodiisopropylimidazoline or azobis (2-methylpropylmi) dihydrochloride.
Preferably, in step (4), the photomask with pictures and texts is arranged above the photonic crystals filled with the polymer precursor mixed solution obtained in step (S3), so that the illumination degree in different areas is different; wherein the photomask is a transparent polymer film or a quartz glass sheet, and the transparent polymer film is a transparent sheet of polypropylene, polyethylene or polyethylene glycol terephthalate, and the pictures and texts information is set on the photomask through ink-jet printing or an oily marker.
Preferably, in the step (S4), it is irradiated under the condition of 32~40 W ultraviolet light for 100~300 minutes to initiate polymerization.
Perferably, in step (S95), the thickness of the structural color multi-responsive hydrogel is 1-4 mm.
Preferably, in steps (S1) to (S2), the water used is ultrapure water, and in step (S5), it is soaked and rinsed with ultrapure water to remove residual reactants and by-products.
The second purpose of the present invention can be achieved by the following technical 95 scheme: a structural color multi-responsive hydrogel can be prepared by the method in any one of the above items.
The last purpose of the present invention can be achieved by the following technical scheme: the application of the structural color multi-responsive hydrogel in encryption and anti- counterfeiting.
Further, the preparation method of the structural color multi-responsive hydrogel provided by the invention comprises the following steps: (1) A method for preparing polymer three-dimensional photonic crystals comprises the following steps: the three-dimensional photonic crystals are self-assembled by vertical sedimentation method: clean the commercial glass sheets, then soak them in concentrated sulfuric acid/hydrogen peroxide=7:3v/v for 12~24 h, and then carry out hydrophilic treatment.
Dilute monodisperse polymer microsphere emulsion (particle size of microsphere is 160~350 nm) with water until the mass fraction is 0.15~0.25wt% and inject it into a penicillin bottle.
Subsequently, insert the glass sheet after hydrophilic treatment vertically into the diluted polymer microsphere emulsion, fix it, place it in a constant temperature and humidity box, stand it at the constant temperature and humidity environment with the relative humidity of 55-70% and the temperature of 50-65°C for 3-5 days; and after the water evaporates, the polymer microspheres are assembled on the glass sheet to obtain three-dimensional photonic crystals. (2) A preparation method for structural color multi-responsive hydrogel comprises the following steps: put 0.1~0.5 g of carboxymethyl chitosan in a centrifuge tube, add 3.5~5 mL of ultrapure water for ultrasonic dispersion, and when it is transparent and uniform, add 1.5~2.5 g of acrylamide and 0.03~0.07 g of photo-crosslinking agent (such as N-N'- methylene bisacrylamide, divinylbenzene, diisocyanate and 3,3'-dithiobis (sulfosuccinimide propionate)) in turn, and disperse ultrasonically until uniform.
Subsequently, dissolve 0.1~0.2 g of water-soluble photoinitiator (such as azodiisobutylamidine hydrochloride, azodiisobutylimidazoline hydrochloride, azodicyanovaleric acid, azodiisopropylimidazoline and azobis (2-methylpropylmi)
dihydrochloride) in 0.5~1.0 mL of ultrapure water, then add the dissolved initiator solution into 204058 the above mixed solution, and mix uniformly to obtain the polymer precursor.
Place the three-dimensional photonic crystals in a polytetrafluoroethylene mold, pour the polymer precursor into the mold, and stand in the dark for 2-5 min until the mixed solution completely fills the gap between the spheres in the photonic crystals.
Place the photomask with patterns above the mold, so that the pictures and texts information area is partially shaded, while the background area is exposed, and put it into a 36
W ultraviolet lamp for light polymerization for 100~300 min. Photonic crystals assembled by polymer microspheres have been embedded in the hydrogel. At this time, uncover the obtained structural color hydrogel from the hydrophilic glass sheet, and soak and wash it with a large amount of clean water (ultra-pure water) to remove the residual reactants and by-products, so as to obtain the multi-responsive structural color hydrogel finally.
The thickness of the obtained hydrogel is determined by the liquid level height of the polymer precursor injected into the mold. The thickness of the finally obtained hydrogel is preferably 1-4 mm.
The principle of the invention is as follows: (1) In the process of photoinitiated polymerization, the part with higher light intensity has higher polymerization degree and crosslinking degree, and the swelling degree in solvents (such as water and ethanol) is lower; However, in the area with weak light intensity, the polymerization degree and crosslinking degree are low, and the swelling degree in solvent is high. Because the swelling degree of different areas is different, the period of embedding photonic crystals in hydrogel is also different, and the wavelength of its diffracted light is also different, which eventually forms the color difference between the background part and the pattern part, so it shows different pictures and texts information. (2) Because the swelling degree of hydrogel is different in different solvents, the colors of pattern and background of the structural color multi-responsive hydrogel are also different in different solvents. (3) In the process of stretching or extrusion, due to the deformation of the structural color multi-responsive hydrogel, the internal microsphere period will also change accordingly, resulting in the overall color change of the hydrogel. (4) According to Bragg diffraction law, the wavelength of diffracted light of photonic crystal materials is related to the angle of incident light and the angle of emergent light.
° LU504033
Therefore, when the observation angle is changed, the structural color multi-response hydrogel samples will also show different colors.
Therefore, in order to overcome the defects and technical deficiencies of the existing single-responsive photonic crystal material technology, the method of the invention provides a structural color multi-responsive hydrogel. The more response characteristics of a structural color hydrogel, the more information can be obtained; and the reliability of its response signal can be enhanced through the mutual comparison and reference of different signals, and the possibility of interference by other factors can be reduced, thereby improving its anti- counterfeiting level. According to the preparation method for the structural color multi- responsive hydrogel provided by the invention, the structural color hydrogel with solvent response, angle response, gas response and mechanical force response can be obtain.
The result color multi-responsive hydrogel in this application has the following characteristics: (1) Concealment: in the dry state, because the refractive index difference between the dried gel matrix and polymer microspheres is small, the diffraction effect is small, and the structural color pattern is difficult to observe with naked eyes; after solvent soaking and gel swelling, the refractive index difference between the swollen polymer and polymer microspheres becomes larger, and the diffraction effect becomes stronger, showing a structural color pattern visible to the naked eye. (2) Solvent responsiveness: because the swelling degree of gel polymer is different in different solvents, the period of microspheres in the gel after swelling is different, the wavelength of diffracted light is different, and their patterns are different. Due to the solvent responsiveness of structural color hydrogel, it is difficult to forge, and it is also endowed with the ability to indicate different solutions (such as different alcohols, different degrees of alcohol, etc.). (3) Mechano-color-changing ability: stretching or extruding the hydrogel can make it deform in different degrees, which can change the wavelength of diffracted light, change the color of its pattern, enhance the anti-counterfeiting effect, and endow it with mechanical sensing ability. (4) Dependence of color angle: according to Bragg diffraction law, the wavelength of diffracted light of structural color hydrogel is related to the angle of incident light and the angle of emergent light, so the samples of structural color multi-responsive hydrogel will show
’ LU504033 different colors when the observation angle is changed, which will increase its anti- counterfeiting effect.
Compared with the existing technology, the invention has the following advantages: (1) according to the invention, firstly, monodisperse polymer microspheres are self- assembled into three-dimensional photonic crystals, then hydrophilic monomers acrylamide and carboxymethyl chitosan are filled into the inter-spherical gaps in the photonic crystals, and structural color composite hydrogel with specific pictures and texts information is prepared by photo-initiated polymerization and controlling the illumination intensity of different areas through mask technology. (2) According to the invention, the polymers in different areas in the hydrogel have different cross-linking degrees through the mask technology, so that it can obtain different swelling properties under solvent infiltration and finally display different colors; moreover, due to the different swelling degrees of the polymer in different solvents, it can obtain solvent responsiveness, that is, the colors of pictures and texts information are different under different solvent infiltration; in addition, the lattice constant of the photonic crystals in the hydrogel changes during the stretching deformation process, which will also lead to the red shift/blue shift of the color of the anti-counterfeiting pattern, so that it has a mechanochromic effect. (3) Therefore, the structural color hydrogel in the invention has multiple effects such as solvent response, gas response, mechanical force response, color angle dependence, etc., and is difficult to forge, and has a good application prospect in anti-counterfeiting of tobacco and alcohol commodities, anti-counterfeiting of high-end luxury goods, anti-counterfeiting of electronic science and technology products, etc.
Fig. 1 is a scanning electron microscope image of structural color multi-responsive hydrogel in Embodiment 1;
Fig. 2 shows the structural color multi-responsive hydrogel in Embodiment 1 in a dry state;
Fig. 3 is a photograph of the structural color multi-responsive hydrogel in Embodiment 1 in the state of water immersion and ethanol immersion, with the top picture showing the response effect of the hydrogel in water and the bottom picture showing the response effect of the hydrogel in ethanol;
; LU504033
Fig. 4 is a photograph of the structural color multi-responsive hydrogel in Embodiment 1 at different observation angles, with the top picture showing the response effect of the hydrogel at 90° and the bottom picture showing the response effect of the hydrogel at 30°;
Fig. 5 shows the color change of the structural color multi-responsive hydrogel in
Embodiment 1 during stretching;
Fig. 6 1s shows the change of the dry structural color multi-responsive hydrogel fumigated in water vapor gas in Embodiment 1.
The raw materials used in the following embodiments are all commercially available products or made according to conventional methods or references unless otherwise specified.
Embodiment 1
The preparation method for structural color multi-responsive hydrogel provided by this embodiment includes the following steps: (1) Preparation of polystyrene three-dimensional photonic crystals: (S1) the three-dimensional photonic crystals are self-assembled by vertical sedimentation method: clean the commercial glass sheets, then soak them in concentrated sulfuric acid/hydrogen peroxide=7:3v/v for 24 h, and then carry out hydrophilic treatment.
Dilute monodisperse polystyrene microsphere emulsion (particle size of microsphere is 180 nm) with water until the mass fraction is 0.2wt% and inject it into a penicillin bottle.
Subsequently, insert the glass sheet after hydrophilic treatment vertically into the diluted polystyrene microsphere emulsion, fix it, place it in a constant temperature and humidity box, stand it at the constant temperature and humidity environment with the relative humidity of 55% and the temperature of 55°C for 5 days; and after the water evaporates, the microspheres are assembled on the glass sheet to obtain three-dimensional photonic crystals (They can also be called polymer photonic crystals). (2) A preparation method for structural color multi-responsive hydrogel comprises the following steps: (S2) put 0.12 g of carboxymethyl chitosan in a centrifuge tube, add 4 mL of ultrapure water for ultrasonic dispersion, and when it is transparent and uniform, add 1.6 g of acrylamide and 0.04 g of photo-crosslinking agent N-N'- methylene bisacrylamide in turn, and disperse ultrasonically until uniform.
Subsequently, dissolve 0.12 g of water-soluble photoinitiator azodiisobutylamidine 904099 hydrochloride in 0.5 mL of ultrapure water, then add the dissolved initiator solution into the above mixed solution, and mix uniformly to obtain the polymer precursor (i.e. mixed solution of polymer precursor). (S3) Place the three-dimensional photonic crystals in a polytetrafluoroethylene mold, pour the polymer precursor into the mold, and stand in the dark for 5 min until the mixed solution completely fills the gap between the spheres in the photonic crystals. (S4) Place the photomask with patterns above the mold, so that the pictures and texts information area is partially shaded, while the background area is exposed, and put it into a 36
W ultraviolet lamp for light polymerization for 240 min, so as to carry out polymerization. (The mask plate is a transparent PET plastic sheet with a thickness of 0.2 mm, which is made by drawing different patterns on the PET sheet with a commercial oily pen. In this embodiment, three different masks are used: (1) Arabic numeral "2" and solid circular hollow "" (corresponding to Figs 2 and 3); (2) letters "Z", "K" and rhombus (corresponding to Fig. 4); (3)
Blank mask (corresponding to Fig. 5); (4) Arabic numeral "2" (corresponding to Fig. 6)). (SS) After the polymerization, photonic crystals assembled by polymer microspheres have been embedded in the hydrogel. At this time, uncover the obtained structural color hydrogel from the hydrophilic glass sheet, and soak and wash it with a large amount of clean water to remove the residual reactants and by-products, so as to obtain the multi-responsive structural color hydrogel finally.
The thickness of the obtained hydrogel is determined by the liquid level height of the polymer precursor injected into the mold. The thickness of the finally obtained hydrogel is 2 mm.
The scanning electron microscope image of the structural color multi-responsive hydrogel in this Embodiment is shown in Fig. 1. From Fig. 1, it can be seen that polystyrene microspheres with a particle size of 170 nm have been embedded in the polymer matrix.
The structural color multi-responsive hydrogel in this Embodiment in a dry state is shown in Fig. 2. From Fig. 2, it can be seen that at this time, the structural color hydrogel is translucent and yellowish, and the pattern information is hidden and cannot be recognized by naked eyes.
Therefore, the structural multi-responsive hydrogel in the invention has concealment. In the dry state, because the refractive index difference between the dried gel matrix and polymer microspheres is small, the diffraction effect is small, and the structural color pattern is difficult to observe with naked eyes; after solvent soaking and gel swelling, the refractive index
© LU504033 difference between the swollen polymer and polymer microspheres becomes larger, and the diffraction effect becomes stronger, showing a structural color pattern visible to the naked eye.
The photograph of the structural color multi-responsive hydrogel of this Embodiment in the state of water immersion and ethanol immersion is shown in Fig. 3, in which the upper picture shows the response effect of the hydrogel in water and the lower picture shows the response effect of the hydrogel in ethanol. As can be seen from Fig. 3, in water, the pattern part is orange red, while the background part is green, which is in sharp contrast and the pictures and texts information can be read. In ethanol, the pattern part is green, while the background part is blue, which is in sharp contrast and the pictures and texts information can be read. In different solvents, the colors of display patterns are obviously different.
Therefore, the structural multi-responsive hydrogel in the invention has solvent responsiveness. Because the swelling degree of gel polymer is different in different solvents, the period of microspheres in the gel after swelling is different, the wavelength of diffracted light is different, and their patterns are different. Due to the solvent responsiveness of structural color hydrogel, it is difficult to forge, and it is also endowed with the ability to indicate different solutions (such as different alcohols, different degrees of alcohol, etc.).
The photograph of the structural color multi-responsive hydrogel of this Embodiment at different observation angles are shown in Fig. 4, in which the top picture shows the response effect of the hydrogel at 90°, and the bottom picture shows the response effect of the hydrogel at 30°. From Fig. 4, it can be seen that when observed vertically at 90°, the pattern part is green and the background part is orange red, while when observed obliquely at 30°, the pattern part is blue and the background part is green. It shows that the display color of multi-responsive structural color hydrogel changes obviously from different angles.
Therefore, the structural multi-responsive hydrogel in the invention has dependence of color angle. According to Bragg diffraction law, the wavelength of diffracted light of structural color hydrogel is related to the angle of incident light and the angle of emergent light, so the samples of structural color multi-responsive hydrogel will show different colors when the observation angle is changed, which will increase its anti-counterfeiting effect.
The color change of the structural color multi-responsive hydrogel in this Embodiment at different stretching degrees is shown in Fig. 5. As can be seen from Fig. 5, with the gradual elongation of the hydrogel, its color gradually shifts to blue, from orange to green, and finally to blue.
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Therefore, the structural multi-responsive hydrogel in the invention has mechano-color- changing ability. Stretching or extruding the hydrogel can make it deform in different degrees, which can change the wavelength of diffracted light, change the color of its pattern, enhance the anti-counterfeiting effect, and endow it with mechanical sensing ability.
As shown in Fig. 6, the change of the dry structural color multi-response hydrogel in this
Embodiment after fumigation with steam gas, with the extension of fumigation time, the hidden pattern (Arabic numeral "2") in the dry hydrogel sample gradually emerges, with a light red background and a gray-green text pattern.
Therefore, the structural color multi-responsive hydrogel in the invention has gas response ability, and the dry hydrogel is fumigated by steam, and as the hydrogel absorbs water, the sample gradually swells. Because of the difference of cross-linking degree between the background area and the pattern area, the degree of swelling by absorbing water and is also different, which leads to different periods of microspheres in the gel after the swelling by absorbing water, different wavelengths of diffracted light and different colors of patterns. And the response capability of the hydrogel material is further enriched.
Embodiment 2
The preparation method for structural color multi-responsive hydrogel provided by this embodiment includes the following steps: (1) Preparation of polystyrene three-dimensional photonic crystals: (S1) the three-dimensional photonic crystals are self-assembled by vertical sedimentation method: clean the commercial glass sheets, then soak them in concentrated sulfuric acid/hydrogen peroxide=7:3v/v for 24 h, and then carry out hydrophilic treatment.
Dilute monodisperse polystyrene microsphere emulsion (particle size of microsphere is 350 nm) with water until the mass fraction is 0.15wt% and inject it into a penicillin bottle.
Subsequently, insert the glass sheet after hydrophilic treatment vertically into the diluted polystyrene microsphere emulsion, fix it, place it in a constant temperature and humidity box, stand it at the constant temperature and humidity environment with the relative humidity of 60% and the temperature of 60°C for 4 days; and after the water evaporates, the microspheres are assembled on the glass sheet to obtain three-dimensional photonic crystals. (2) A preparation method for structural color multi-responsive hydrogel comprises the following steps:
(S2) put 0.12 g of carboxymethyl chitosan in a centrifuge tube, add 4 mL of ultrapure. 204058 water for ultrasonic dispersion, and when it is transparent and uniform, add 1.6 g of acrylamide and 0.04 g of photo-crosslinking agent 3,3'-dithiobis (sulfosuccinimide propionate) in turn, and disperse ultrasonically until uniform.
Subsequently, dissolve 0.15 g of water-soluble photoinitiator azodiisobutylimidazoline hydrochloride in 1 mL of ultrapure water, then add the dissolved initiator solution into the above mixed solution, and mix uniformly to obtain the polymer precursor. (S3) Place the three-dimensional photonic crystals in a polytetrafluoroethylene mold, pour the polymer precursor into the mold, and stand in the dark for 5 min until the mixed solution completely fills the gap between the spheres in the photonic crystals. (S4) Place the photomask with patterns (For example, the pattern can be Chinese characters "Zhong Kai", and the attached drawings are not provided here) above the mold, so that the pictures and texts information area is partially shaded, while the background area is exposed, and put it into a 36 W ultraviolet lamp for light polymerization for 180 min, so as to carry out polymerization. (SS) After the polymerization, photonic crystals assembled by polymer microspheres have been embedded in the hydrogel. At this time, uncover the obtained structural color hydrogel from the hydrophilic glass sheet, and soak and wash it with a large amount of clean water to remove the residual reactants and by-products, so as to obtain the multi-responsive structural color hydrogel finally.
The thickness of the obtained hydrogel is determined by the liquid level height of the polymer precursor injected into the mold. The thickness of the finally obtained hydrogel is 1.5 mm.
Embodiment 3
The preparation method for structural color multi-responsive hydrogel provided by this embodiment includes the following steps: (1) Preparation of polystyrene three-dimensional photonic crystals: (S1) the three-dimensional photonic crystals are self-assembled by vertical sedimentation method: clean the commercial glass sheets, then soak them in concentrated sulfuric acid/hydrogen peroxide=7:3v/v for 24 h, and then carry out hydrophilic treatment.
Dilute monodisperse polystyrene microsphere emulsion (particle size of microsphere is 160 nm) with water until the mass fraction is 0.25wt% and inject it into a penicillin bottle.
Subsequently, insert the glass sheet after hydrophilic treatment vertically into the diluted 904099 polystyrene microsphere emulsion, fix it, place it in a constant temperature and humidity box, stand it at the constant temperature and humidity environment with the relative humidity of 70% and the temperature of 65°C for 3 days; and after the water evaporates, the microspheres are assembled on the glass sheet to obtain three-dimensional photonic crystals. (2) A preparation method for structural color multi-responsive hydrogel comprises the following steps: (S2) put 0.3 g of carboxymethyl chitosan in a centrifuge tube, add 3.5 mL of ultrapure water for ultrasonic dispersion, and when it is transparent and uniform, add 2 g of acrylamide and 0.04 g of photo-crosslinking agent N-N'- methylene bisacrylamide in turn, subsequently, add 0.06g of photo-crosslinking agent diisocyanate and disperse ultrasonically until uniform.
Subsequently, dissolve 0.1 g of water-soluble photoinitiator azobis (2-methylpropylmi) dihydrochloride in 1.0 mL of ultrapure water, then add the dissolved initiator solution into the above mixed solution, and mix uniformly to obtain the polymer precursor. (S3) Place the three-dimensional photonic crystals in a polytetrafluoroethylene mold, pour the polymer precursor into the mold, and stand in the dark for 5 min until the mixed solution completely fills the gap between the spheres in the photonic crystals. (S4) Place the photomask with patterns (For example, the pattern can be Chinese characters "Bao Zhuang", and the attached drawings are not provided here) above the mold, so that the pictures and texts information area is partially shaded, while the background area is exposed, and put it into a 36 W ultraviolet lamp for light polymerization for 140 min, so as to carry out polymerization. (SS) After the polymerization, photonic crystals assembled by polymer microspheres have been embedded in the hydrogel. At this time, uncover the obtained structural color hydrogel from the hydrophilic glass sheet, and soak and wash it with a large amount of clean water to remove the residual reactants and by-products, so as to obtain the multi-responsive structural color hydrogel finally.
The thickness of the obtained hydrogel is determined by the liquid level height of the polymer precursor injected into the mold. The thickness of the finally obtained hydrogel is 4 mm.
Embodiment 4
The preparation method for structural color multi-responsive hydrogel provided by this embodiment includes the following steps:
a LU504033 (1) Preparation of polymethylmethacrylate three-dimensional photonic crystals: (S1) the three-dimensional photonic crystals are self-assembled by vertical sedimentation method: clean the commercial glass sheets, then soak them in concentrated sulfuric acid/hydrogen peroxide=7:3v/v for 24 h, and then carry out hydrophilic treatment.
Dilute monodisperse polymethylmethacrylate microsphere emulsion (particle size of microsphere is 220 nm) with water until the mass fraction is 0.25wt% and inject it into a penicillin bottle.
Subsequently, insert the glass sheet after hydrophilic treatment vertically into the diluted polymethylmethacrylate microsphere emulsion, fix it, place it in a constant temperature and humidity box, stand it at the constant temperature and humidity environment with the relative humidity of 60% and the temperature of 60°C for 4 days; and after the water evaporates, the microspheres are assembled on the glass sheet to obtain three-dimensional photonic crystals. (2) A preparation method for structural color multi-responsive hydrogel comprises the following steps: (S2) put 0.16 g of carboxymethyl chitosan in a centrifuge tube, add 5 mL of ultrapure water for ultrasonic dispersion, and when it is transparent and uniform, add 1.5 g of acrylamide and 0.04 g of photo-crosslinking agent 3,3'-dithiobis (sulfosuccinimide propionate) in turn, and disperse ultrasonically until uniform.
Subsequently, dissolve 0.15 g of water-soluble photoinitiator azodiisobutylimidazoline hydrochloride in 1 mL of ultrapure water, then add the dissolved initiator solution into the above mixed solution, and mix uniformly to obtain the polymer precursor. (S3) Place the three-dimensional photonic crystals in a polytetrafluoroethylene mold, pour the polymer precursor into the mold, and stand in the dark for 5 min until the mixed solution completely fills the gap between the spheres in the photonic crystals. (S4) Place the photomask with patterns (For example, the pattern can be Chinese characters "ZK Zhong Kai", and the attached drawings are not provided here) above the mold, so that the pictures and texts information area is partially shaded, while the background area is exposed, and put it into a 36 W ultraviolet lamp for light polymerization for 160 min, so as to carry out polymerization. (SS) After the polymerization, photonic crystals assembled by polymer microspheres have been embedded in the hydrogel. At this time, uncover the obtained structural color hydrogel from the hydrophilic glass sheet, and soak and wash it with a large amount of clean water to remove the residual reactants and by-products, so as to obtain the multi-responsive structural oo color hydrogel finally.
The thickness of the obtained hydrogel is determined by the liquid level height of the polymer precursor injected into the mold. The thickness of the finally obtained hydrogel is 2 mm.
The above is the preferred embodiment of the present invention, and it should be pointed out that for ordinary technical personnel in the technical field, the optimization, improvement, combination, substitution, etc. of the present invention made by should be regarded as within the protection scope of the present invention on the premise of the principle of the present invention.
Claims (10)
1. A preparation method for structural color multi-responsive hydrogel, wherein, it comprises the following steps: (S1) disperse polymer monodisperse nanospheres in water to obtain polymer monodisperse nanospheres dispersion, insert a hydrophilic glass sheet vertically into the polymer monodisperse nanospheres dispersion, evaporate water in a constant temperature and humidity environment, and self-assemble the polymer monodisperse nanospheres on the surface of the hydrophilic glass sheet by a vertical sedimentation method to obtain polymer photonic crystals; (S2) dissolve carboxymethyl chitosan in water for ultrasonic dispersion, add acrylamide and crosslinking agent in turn when it is transparent and uniform, and perform ultrasonic dispersion until uniform to obtain a multi-responsive polymer monomer solution, add photoinitiator aqueous solution into the multi-responsive polymer monomer solution, and mix uniformly to obtain the polymer precursor mixed solution; (S3) add the polymer precursor mixed solution in step (S2) into the polymer photonic crystals in step (S1), and stand in the dark until the polymer precursor mixed solution completely fills the inter-spherical gaps in the photonic crystals; (S4) arrange a photomask with pictures and texts above the photonic crystals filled with the polymer precursor mixed solution obtained in step (S3), and irradiate under ultraviolet light to initiate polymerization, and (S5) after the polymerization in step (S4) is finished, embed the polymer photonic crystals into the polymer precursor mixed solution, take it off the hydrophilic glass, and clean it to remove impurities, so as to obtain the structural color multi-responsive hydrogel.
2. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein the polymer monodisperse nanospheres in step (S1) are polystyrene monodisperse nanospheres or polymethylmethacrylate monodisperse nanospheres, and the particle size is 160~350 nm; the mass percentage content of the polymer monodisperse nanospheres in the polymer monodisperse nanospheres dispersion in step (S1) is
0.15~0.25wt%; in the constant temperature and humidity environment in step (S1), the temperature is 50~65°C and relative humidity is 55~70%.
3. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in step (S2), the mass ratio of methyl chitosan, acrylamide, crosslinking agent and water is 0.1~0.5:1.5~2.5, 0.03~0.07:3.5~5; the crosslinking agent in step (S2) is N-N'-
methylene bisacrylamide, divinylbenzene, diisocyanate or 3,3'-dithiobis (sulfosuccinimide 206008 propionate).
4. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in the step (S2), the mass percentage content of the photoinitiator in the photoinitiator aqueous solution is 10-40%, and its addition amount accounts for 1~6% of the total mass of the multi-responsive polymer monomer solution.
5. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in the step (S2), the photoinitiator is azodiisobutylamidine hydrochloride, azodiisobutylimidazoline hydrochloride, azodicyanovaleric acid, azodiisopropylimidazoline or azobis (2-methylpropylmi) dihydrochloride.
6. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in step (4), the photomask with pictures and texts is arranged above the photonic crystals filled with the polymer precursor mixed solution obtained in step (S3), so that the illumination degree in different areas is different; wherein the photomask is a transparent polymer film or a quartz glass sheet, and the transparent polymer film is a transparent sheet of polypropylene, polyethylene or polyethylene glycol terephthalate, and the pictures and texts information is set on the photomask through ink-jet printing or an oily marker; in the step (S4), it is irradiated under the condition of 32~40 W ultraviolet light for 100~300 minutes to initiate polymerization.
7. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in step (S5), the thickness of the structural color multi-responsive hydrogel is 1-4 mm.
8. The preparation method for structural color multi-responsive hydrogel, as claimed in claim 1, wherein, in steps (S1) to (S2), the water used is ultrapure water, and in step (S95), it is soaked and rinsed with ultrapure water to remove residual reactants and by-products.
9. The structural color multi-response hydrogel, wherein, it is prepared by the method as claimed in any one of claims 1~8.
10. The application of the structural color multi-responsive hydrogel as claimed in claim 9 in encryption and anti-counterfeiting.
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