A data encryption and anti-counterfeiting method based on polymer free volume change

Abstract

The application discloses a data encryption and anti-counterfeiting method based on polymer free volume change. The data encryption method comprises the following steps: preparing a polymer film containing encrypted information through photopolymerization, using a reverse rigidochromic fluorescent molecular probe as a developer to decrypt the polymer film containing encrypted information, and reading information. Compared with existing encryption and anti-counterfeiting technologies, the data encryption and anti-counterfeiting technology based on polymer free volume change has the same element composition and elastic modulus in the information area and the background area, greatly reduces the risk of cracking data by using advanced instruments, and the multidimensional change of the pattern is not easy to be tampered with, and the method is suitable for the field of encryption and anti-counterfeiting technologies.

Description

TECHNICAL FIELD

[0001] The application relates to a data encryption and anti-counterfeiting method based on polymer free volume change, and belongs to the technical field of encryption and anti-counterfeiting. BACKGROUND

[0002] With the rapid development of big data, cloud computing, blockchain and other technologies, it is increasingly important to protect information security during transmission and storage, especially in the fields of finance and military. Although existing data encryption technologies are very effective, most of them are heavily dependent on mathematical algorithms or software engineering, and there is a risk of "algorithm counteracting algorithm, program cracking program". Counterfeiting and attacks can still occur. Developing new data encryption and anti-counterfeiting technologies is of great significance to national and enterprise security and personal privacy. Data encryption and protection methods based on chemistry or material science are expected to fundamentally eliminate the possibility of remote counterfeiting and hacker attacks, and can complement existing algorithmic encryption methods. Luminescent materials have good optical sensitivity and spatial resolution and are easy to control, and have shown considerable development prospects in the field of information encryption and anti-counterfeiting. However, traditional data encryption and anti-counterfeiting technologies based on fluorescent materials have relatively single signal changes, high predictability, easy information reading and decryption, and patterns are easy to counterfeit. How to use fluorescent materials to improve the security level of encryption and anti-counterfeiting technology and more effectively protect information is still an important challenge in this field. SUMMARY

[0003] In view of the above problems, the application provides a class of anti-rigid photochromic fluorescent molecular probes, and develops an information encryption and anti-counterfeiting technology based on polymer free volume change using the molecular probes. The anti-rigid photochromic fluorescent molecular probe has a significant red shift in fluorescence emission with the decrease of polymer free volume. The change of polymer free volume is mainly realized by changing the polymer chain length, conformation, crosslinking density and hierarchical structure at the nanometer and micrometer levels. The application can control the chain length and crosslinking density of the polymer in the exposed area and the non-exposed area through a patterning process to control the free volume distribution of the polymer, thereby realizing information storage and encryption. The element composition of the information area and the background area is consistent, which greatly reduces the risk of cracking the data using advanced instruments; the difference in elastic modulus is almost negligible, and no detectable anisotropic swelling occurs in common solvents, so it is impossible to decrypt the information by solvent swelling or etching; the information can only be cracked under the development of the anti-rigid photochromic fluorescent molecules, which greatly improves the security of data encryption. In addition, further optimization of the hierarchical / topological structure of the polymer, together with the anti-rigid photochromic fluorescent molecular probe as an "embedded fluorescent sensor", can controllably regulate the fluorescence emission wavelength and circularly polarized light emission polarity of the pattern, realizing the multiple anti-counterfeiting capability of the pattern. The information encryption and anti-counterfeiting technology based on polymer free volume change provided by the application has great application potential in the field of encryption and anti-counterfeiting technology.

[0004] According to one aspect of the present application, a method for data encryption based on polymer free volume change is provided, a pattern is written by changing the free volume of the polymer, and the pattern is displayed by using the sensitivity of the fluorescent molecular probe to the free volume change of the polymer.

[0005] The method comprises:

[0006] A polymer film containing encrypted information is prepared by a photopolymerization process, and the polymer film containing encrypted information is decrypted by using a reverse rigidochromic fluorescent molecular probe as a developer to read the information.

[0007] The present method realizes data encryption and decryption by using a reverse rigidochromic fluorescent molecular probe as a developer to sense the free volume change of the polymer during polymerization or degradation. The matrix formula for photopolymerization of the polymer is monomer molecules, a photoinitiator, and a fluorescent probe molecule, or monomer molecules, a photoinitiator, a fluorescent probe molecule, and a crosslinking agent, preferably monomer molecules, a photoinitiator, a fluorescent probe molecule, and a crosslinking agent. The photoinitiator is preferably phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, and the crosslinking agent is preferably 1,6-hexanediol diacrylate. The loading of the probe molecule is as low as 2 ppm. The fluorescent molecular probe is preferably a reverse rigidochromic fluorescent molecular probe, which has the reverse rigidochromic property that the fluorescence emission red shifts as the free volume of the polymer decreases (i.e., the rigidity increases).

[0008] In the present method, the difference between the information area and the background area comes from the different free volumes of the polymer. The free volume change of the polymer is mainly realized by changing the polymer chain length, conformation, crosslinking density, and hierarchical structure at the nanometer and micrometer levels.

[0009] Optionally, the method comprises the following steps:

[0010] (1) A pre-polymer solution containing polymer monomer molecules and a photoinitiator I is injected into a mold, and photoinitiated polymerization is performed under the condition of using a mask plate to obtain a thin film containing encrypted information;

[0011] (2) The thin film obtained in step (1) is soaked in a solution I containing a reverse rigidochromic fluorescent molecular probe, and information is read under ultraviolet light I.

[0012] Optionally, the polymer monomer molecules are selected from at least one of methyl acrylate, methyl acrylate derivatives, phenolic acrylate, phenolic acrylate derivatives, pentafluorophenol acrylate, and pentafluorophenol acrylate derivatives.

[0013] Optionally, the polymer monomer molecule is selected from at least one of pentafluorophenyl acrylate, p-trifluoromethylphenyl acrylate, 2-methyl-1,4-phenylene bis(4-(3-(acryloyloxy)propoxy)benzoate), 4-[[6-[(1-oxo-2-propenyl)oxy]hexyl]oxy]benzoic acid 4-methoxyphenyl ester.

[0014] Optionally, the photoinitiator I is selected from at least one of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, α,α-dimethoxy-α-phenylacetophenone.

[0015] Optionally, the pre-polymer solution further comprises a solvent I, and the solvent I is selected from at least one of toluene, 1,4-dioxane, tetrahydrofuran, dichloromethane, trichloromethane, ethyl acetate, acetone, chlorobenzene, o-dichlorobenzene, acetonitrile.

[0016] Optionally, the pre-polymer solution further comprises a cross-linking agent.

[0017] Optionally, the cross-linking agent is a condensate of one of a C2-12 diol, a C5-20 tetrol, a C2-12 diamine, or a C5-20 tetramine derivative with acrylic acid.

[0018] Optionally, the cross-linking agent is selected from at least one of 1,6-hexanediol diacrylate, 1,5-pentanediol diacrylate, hexamethylene bisacrylamide.

[0019] Optionally, the solution I containing the reverse thermochromic fluorescent molecular probe further comprises a solvent II, and the solvent II is selected from at least one of toluene, dichloromethane, trichloromethane, tetrahydrofuran, acetone, ethyl acetate, n-hexane, diethyl ether, chlorobenzene, o-dichlorobenzene, 1,4-dioxane.

[0020] Optionally, the mass ratio of the polymer monomer molecule to the photoinitiator I is 600:1 to 1600:1, the mass of the polymer monomer molecule being the mass of the polymer monomer molecule itself, and the mass of the photoinitiator I being the mass of the photoinitiator I itself.

[0021] Optionally, the mass ratio of the polymer monomer molecule to the photoinitiator I is independently selected from any value of 600:1, 800:1, 1000:1, 1200:1, 1400:1, 1600:1, or any value between any two of the above values.

[0022] Optionally, the mass ratio of the polymer monomer molecule to the cross-linking agent is 50:1 to 150:1, the mass of the polymer monomer molecule being the mass of the polymer monomer molecule itself, and the mass of the cross-linking agent being the mass of the cross-linking agent itself.

[0023] Optionally, the molar ratio of the polymer monomer molecules, the crosslinking agent is independently selected from any value or any value between any two points of the following: 50:1, 70:1, 90:1, 100:1, 120:1, 150:1.

[0024] Optionally, the light-induced polymerization conditions are: light power is 8-200W, light wavelength is 250-420nm, light exposure time is 5-60 minutes.

[0025] Optionally, the light power is independently selected from any value or any value between any two points of the following: 8W, 18W, 40W, 80W, 100W, 120W, 160W, 200W.

[0026] Optionally, the light wavelength is independently selected from any value or any value between any two points of the following: 250nm, 365nm, 420nm.

[0027] Optionally, the light exposure time is independently selected from any value or any value between any two points of the following: 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes.

[0028] Optionally, the light-induced polymerization conditions are: light power is 18W, light wavelength is 365nm, light exposure time is 40-50 minutes.

[0029] Optionally, in the solution I containing the reverse thermochromic fluorescent molecular probe, the concentration of the reverse thermochromic fluorescent molecular probe is 2.5×10 -5 mol / L-7.5×10 -4 mol / L.

[0030] Optionally, the concentration of the reverse thermochromic fluorescent molecular probe is 2.5×10 -4 mol / L.

[0031] Optionally, the concentration of the reverse thermochromic fluorescent molecular probe is independently selected from any value or any value between any two points of the following: 2.5×10 -5 mol / L, 5.0×10 -5 mol / L, 7.5×10 -5 mol / L, 2.5×10 -4 mol / L, 5.0×10 -4 mol / L, 7.5×10 -4 mol / L.

[0032] Optionally, the molar ratio of the anti-archichromic fluorescent molecular probe to the polymer monomer molecule is 1:1000-1:1000000, the number of moles of the anti-archichromic fluorescent molecular probe is based on the number of moles of the anti-archichromic fluorescent molecular probe itself, and the number of moles of the polymer monomer molecule is based on the number of moles of the polymer monomer molecule itself.

[0033] Optionally, the molar ratio of the anti-archichromic fluorescent molecular probe to the polymer monomer molecule is independently selected from any value in 1:1000, 1:10000, 1:100000, 1:1000000 or any value between any two of the above.

[0034] Optionally, the soaking I time is 3-10 min.

[0035] Optionally, the soaking I time is independently selected from any value in 3 min, 5 min, 8 min, 10 min or any value between any two of the above.

[0036] Optionally, the light wavelength of the ultraviolet light I is 250-420 nm.

[0037] Optionally, the light wavelength of the ultraviolet light I is 365 nm.

[0038] Optionally, the light wavelength of the ultraviolet light I is independently selected from any value in 250 nm, 365 nm, 420 nm or any value between any two of the above.

[0039] As a specific embodiment, the encryption specific steps of the photopolymerization process are as follows:

[0040] First, configure the pre-polymerization liquid, and the pre-polymerization liquid composition is polymer monomer molecule (594 mg), 1,6-hexanediol diacrylate (6 mg), and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (9 mg / mL, 74 μL, and the solvent is preferably toluene). Inject the pre-polymerization liquid into the mold, exclude air, and then use a mask plate with a pre-designed pattern to perform light-induced polymerization, thereby writing information and encrypting the thin film. The light power is preferably 18 W, the light wavelength is preferably 365 nm, the light irradiation time is 30-60 min, and preferably 40-50 min.

[0041] Although different doses of light are applied to the written and unwritten areas, the entire film is well crosslinked, with no difference in surface roughness and film transparency, and no information can be read under natural light or ultraviolet light. Tensile tests show that the elastic modulus of the polymer film is 4.0-5.0 MPa. The difference in elastic modulus between the information area and the background area is almost negligible, and no detectable anisotropic swelling occurs in common organic solvents, and it is impossible to decrypt information by solvent swelling or etching. Elemental analysis tests show that the elemental composition of the polymer information area and the background area is almost the same, and it is difficult to crack by advanced instrument analysis composition method. The only difference between the information area and the background area comes from the different crosslinking densities of the polymer. Only by immersing the film in a solution of a reverse-rigidochromic fluorescent molecular probe (2.5×10 -4 M, and the solvent is preferably toluene), and then taking out and reading under an ultraviolet lamp to achieve information decryption. The immersion time is preferably 5-10 minutes, and the light wavelength is preferably 365 nm.

[0042] Because the polymer in the area with a large light dose has a large crosslinking density, a small free volume, a strong rigidity, and a strong interaction with the fluorescent molecule, it mainly presents a red shift emission after the interaction of the fluorescent molecule and the polymer; the polymer in the area with a small light dose has a small crosslinking density, a relatively large free volume, a relatively weak rigidity, and a weakened interaction with the fluorescent molecule, and mainly presents the emission of the fluorescent molecule itself. Under ultraviolet light, the different fluorescent emissions of the two areas can make the encrypted information appear.

[0043] In another aspect of the present application, a method for preventing counterfeiting based on the change of the free volume of a polymer is provided, and the method for preventing counterfeiting is achieved by using a patterned liquid crystal film I to prevent counterfeiting under visible light;

[0044] The preparation method of the patterned liquid crystal film I includes:

[0045] (1) preparing a polymer film layer;

[0046] (2) loading a solution II containing a liquid crystal monomer, a chiral inducer, a photoinitiator II, and a reverse-rigidochromic fluorescent molecular probe II on a single side surface of the polymer film layer I to obtain a liquid crystal film layer II;

[0047] (3) under the condition of using a mask plate, forming a patterned liquid crystal film I under the irradiation of ultraviolet light II.

[0048] Optionally, the liquid crystal monomer is selected from acrylate derivatives containing a phenyl ester benzene functional group on the side group;

[0049] Optionally, the liquid crystal monomer is selected from at least one of RM105, RM257, RM23, RM82, and C6M.

[0050] Preferably, the chiral inducer is selected from one of S811, R811, S5011, R-1011 and S-1011;

[0051] Optionally, the photo-initiator II is selected from at least one of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphonate, a,a-dimethoxy-a-phenylacetophenone;

[0052] Optionally, the solution II further comprises an organic solvent selected from at least one of tetrahydrofuran (THF), dichloromethane, trichloromethane, acetone, ethyl acetate, n-hexane, diethyl ether, ethanol, methanol.

[0053] Optionally, the thickness of the liquid crystal film layer II is 30-80 μm,

[0054] Optionally, the thickness of the liquid crystal film layer II is 39-45 μm.

[0055] Optionally, the thickness of the liquid crystal film layer II is independently selected from any value of 30 μm, 39 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm or any value between any two of the above.

[0056] Optionally, the patterned liquid crystal film I is a cholesteric liquid crystal film;

[0057] Optionally, when the patterned liquid crystal film I is a cholesteric liquid crystal film, the liquid crystal monomers comprise RM105 and RM257, and the chiral inducer is S811, wherein the mass ratio of RM105, RM257 and S811 is 1:(1-2):(0.5-0.9);

[0058] Optionally, the mass ratio of RM105, RM257 and S811 is independently selected from any value of 1:1:0.5, 1:1.5:0.5, 1:2:0.5, 1:1:0.9, 1:1.5:0.9, 1:2:0.9 or any value between any two of the above.

[0059] Optionally, in the solution II, the mass fraction of the photo-initiator II is 0.1-5 wt%, and the mass fraction of the photochromic fluorescent molecular probe is 0.005-0.5 wt%;

[0060] Optionally, the mass fraction of the photo-initiator II is independently selected from any value of 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or any value between any two of the above.

[0061] Optionally, the mass fraction of the anti-photoclastochromic fluorescent molecular probe is independently selected from any value or any value between any two of 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%.

[0062] Optionally, in the solution II, the mass ratio of the liquid crystal monomer, the chiral inducer, the photoinitiator II and the anti-photoclastochromic fluorescent molecular probe is 1:0.2-0.3:0.001-0.01:0.0005-0.001.

[0063] Optionally, the mass ratio of the liquid crystal monomer, the photoinitiator II and the anti-photoclastochromic fluorescent molecular probe is independently selected from any value or any value between any two of 1:0.2:0.001:0.0005, 1:0.2:0.01:0.001, 1:0.3:0.001:0.0005, 1:0.3:0.01:0.001.

[0064] Optionally, the temperature of the heating I is 60-85°C.

[0065] Optionally, the temperature of the heating I is 72-78°C, and the time of the heating I is 6-8h.

[0066] Optionally, the temperature of the heating I is independently selected from any value or any value between any two of 60°C, 70°C, 72°C, 75°C, 78°C, 80°C, 85°C.

[0067] Optionally, the time of the heating I is independently selected from any value or any value between any two of 6h, 7h, 8h.

[0068] Optionally, in the step (3), the power of the ultraviolet light II is 8-50W.

[0069] Optionally, the power of the ultraviolet light II is 15-25W.

[0070] Optionally, the power of the ultraviolet light II is independently selected from any value or any value between any two of 8W, 10W, 15W, 18W, 20W, 25W, 35W, 45W, 50W.

[0071] Optionally, the light wavelength of the ultraviolet light II is 250-420nm.

[0072] Optionally, the light wavelength of the ultraviolet light II is 365nm.

[0073] Optionally, the light wavelength of the ultraviolet light is independently selected from any value in 250 nm, 365 nm, 420 nm or any value between any two of the above.

[0074] Optionally, the irradiation time of the ultraviolet light II is 30 minutes to 60 minutes.

[0075] Optionally, the irradiation time of the ultraviolet light II is 50 minutes.

[0076] Optionally, the irradiation time of the ultraviolet light II is independently selected from any value in 30 minutes, 40 minutes, 50 minutes, 60 minutes or any value between any two of the above.

[0077] Optionally, the anti-counterfeiting method comprises the following steps:

[0078] (1) spin coating a water solution containing a polymer on a glass slide I, heating II, to form a polymer thin film layer on the glass slide I;

[0079] (2) covering a glass slide II on the polymer thin film layer, to form a unit of glass slide II, polymer thin film layer, glass slide I;

[0080] (3) filling a solution II containing liquid crystal monomers, photoinitiator II, and reverse thermochromic fluorescent molecular probe into the gap between the glass slide II and the polymer thin film layer after heating I;

[0081] (4) attaching a patterned photomask plate on the side of the glass slide II away from the polymer thin film layer, and forming a patterned liquid crystal thin film I under the irradiation of ultraviolet light II;

[0082] Optionally, in step (1), the polymer is selected from at least one of polyvinyl alcohol, polyimide, and polyvinylpyrrolidone solution.

[0083] Optionally, in the water solution containing a polymer, the mass fraction of the polymer is 0.5-10 wt%.

[0084] Optionally, the mass fraction of the polymer is 1 wt%.

[0085] Optionally, the mass fraction of the polymer is independently selected from any value in 0.5 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt% or any value between any two of the above.

[0086] Optionally, the rotation speed of the spin coating is 1500-2000 rpm.

[0087] Optionally, the rotation speed of the spin coating is 1600 rpm.

[0088] Optionally, the spin-coating speed is independently selected from any value or any value between any two points of 1500 rpm, 1600 rpm, 1700 rpm, 1800 rpm, 1900 rpm, 2000 rpm.

[0089] Optionally, the heating II time is 60-180 minutes.

[0090] Optionally, the heating II time is 120 minutes.

[0091] Optionally, the heating II time is independently selected from any value or any value between any two points of 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes.

[0092] Optionally, the heating II temperature is 100-130℃,

[0093] Optionally, the heating II temperature is 110℃.

[0094] Optionally, the heating II temperature is independently selected from any value or any value between any two points of 100℃, 110℃, 120℃, 130℃.

[0095] As a specific embodiment, the specific steps of realizing multiple anti-counterfeiting by using the reversible photochromic fluorescent molecular probe as the "built-in fluorescent sensor" to visualize the polymer free volume change are as follows:

[0096] A polyvinyl alcohol (PVA) aqueous solution (mass fraction preferably 1 wt%) is spin-coated on a clean glass slide (50 x 50 mm2) at a speed of 1500-2000 rpm, preferably 1600 rpm. Subsequently, heating is performed at a preferred temperature of 110℃ for a heating time of 60-180 minutes, preferably 120 minutes. In order to promote the arrangement of liquid crystal molecules, the PVA layer is rubbed in one direction using a velvet cloth. A blank glass slide is placed on the rubbed PVA layer, and a liquid crystal cell is injected between the PVA layer and the blank glass slide to prepare a CLC film, and the gap between the two layers is preferably 39 μm.

[0097] Liquid crystal monomers RM105 (2 g), RM257 (3 g), S811 (1 g), a photoinitiator (1 wt%) and an inverse-guest-host fluorescent molecular probe (0.05 wt%) are dissolved in an organic solvent, preferably THF; the solution is heated to 75 °C, and THF is completely evaporated after about 6 hours. The uniform liquid crystal mixed solution is then filled into the cell gap by capillary action, and a patterned photomask is attached to the top of the cell. A patterned CLC film is then formed under UV irradiation. The light power is preferably 18 W, the light wavelength is preferably 365 nm, and the light irradiation time is 40-60 minutes, preferably 50 minutes.

[0098] The prepared CLC film is a left-handed cholesteric liquid crystal film that can transmit right-circularly polarized light (R-CPL), reflect left-circularly polarized light (L-CPL), and emit L-CPL. Under visible light, the patterned CLC film exhibits different effects when observed with a left polarizing filter, a right polarizing filter, and no polarizing filter; under 365 nm light, the pattern exhibits different visual effects when observed with a left polarizing filter, a right polarizing filter, and no polarizing filter. The pattern written in the liquid crystal film has at least 6 different views, enhancing the anti-counterfeiting ability of the pattern.

[0099] By adjusting the ratio of RM105, RM257 and S811, the optical band gap (PBG) and the pitch of the liquid crystal film can be further adjusted. After the topological structure of the polymer is coupled with the inverse-guest-host fluorescent molecular probe, the CPL chirality, the CPL wavelength and the glum value of the pattern can be adjusted, and the pattern has multiple anti-counterfeiting capabilities.

[0100] It should be noted that the amount of each reactant in the above preparation process of the patent is a proportion obtained by converting a certain reactant as a basis. In actual operation, the amounts of all reactants and solvents can be changed accordingly.

[0101] As a specific embodiment, the inverse-guest-host fluorescent molecular probe as an "embedded fluorescent sensor" can visualize the change in the free volume of the polymer to achieve the following specific steps for multiple anti-counterfeiting:

[0102] (3a) Preparation of a liquid crystal film: the inverse-guest-host fluorescent molecular probe is doped into a liquid crystal component, and a liquid crystal film is prepared by photopolymerizing the liquid crystal component with a mask plate; the liquid crystal film is preferably a cholesteric liquid crystal (CLC) polymer film, and RM105, RM257 and S811 are more preferably used as the liquid crystal component;

[0103] (3b) Under visible light, the liquid crystal film is observed with a left polarizing filter, a right polarizing filter, and no polarizing filter, respectively;

[0104] (3c) UV light, preferably 365 nm, respectively, under left polarized filter, right polarized filter and no polarized filter, the liquid crystal film is observed.

[0105] In step (3a), the liquid crystal film has typical chiral characteristics. Preferably, the CLC film prepared by RM105, RM257 and S811 is a left-handed cholesteric liquid crystal film, which can transmit right circularly polarized light (R-CPL) and reflect left circularly polarized light (L-CPL).

[0106] In step (3a), compared with the non-exposed area, the free volume of the exposed area of the liquid crystal film is reduced, the rigidity is increased, the interaction between the exposed area and the fluorescent molecules is stronger than that between the non-exposed area and the fluorescent molecules, the exposed area mainly presents red shift emission after the interaction between the fluorescent molecules and the liquid crystal, and the non-exposed area mainly presents the emission of the fluorescent molecules itself. With the continuous extension of the light time, the fluorescent emission of the non-exposed area will also be red shifted. By controlling the light time, the fluorescent emission wavelengths of the exposed area and the non-exposed area can be adjusted, and the pattern writing can be realized.

[0107] In step (3a), the liquid crystal film has circularly polarized light emission characteristics, and the optical band gap (PBG) and the pitch of the film can be adjusted. Preferably, the CLC film pattern prepared by RM105, RM257 and S811 has the ability to emit left circularly polarized light (L-CPL); by adjusting the proportion of RM105, RM257 and S811, the adjustable PBG is coupled with the anti-rigid photochromic characteristics of the fluorescent molecules, so that the reversible CPL chirality, the adjustable CPL wavelength and the high glum value can be realized.

[0108] In steps (3b) and (3c), the pattern written in the liquid crystal film has at least six different views, and the CPL chirality, the CPL wavelength and the glum value of the pattern can be adjusted, and the pattern has multiple anti-counterfeiting capabilities.

[0109] Optionally, the anti-rigid photochromic fluorescent molecule probe is selected from compounds having at least one of the structural formulas of formulas M1 to M20;

[0110]

[0111] wherein the R1 substituent group is selected from at least one of H, C1-20 alkyl, C1-6 alkylhalide, C1-6 alkyl primary amine, C1-6 alkyl secondary amine, C1-6 alkyl tertiary amine, C1-6 quaternary amine salt;

[0112] According to the present application, R1 is preferably C1-20 alkyl;

[0113] R2 substituent group is selected from at least one of H, C1-12 alkyl, cyano, halogen, amino, methylamino, C0-4 alkyl secondary amine, C0-4 alkyl tertiary amine, C0-4 quaternary amine salt.

[0114] According to the application, R2 is preferably a C1-12 alkyl group;

[0115] In formula M2, X is at least one selected from N, P, As, and Y is at least one selected from H, halogen atoms; according to the application, X is preferably N, and Y is preferably H;

[0116] In formulae M10-M17, X is N or C; when X is N, R2 is a monosubstituted group; when X is C, R2 is a disubstituted group; according to the application, X is preferably N;

[0117] In formulae M15-M17, R is at least one selected from H, halogen atoms, a benzene ring and its derivatives, thiophene and its derivatives, furan and its derivatives, cyclohexane, pyridine, pyrrole.

[0118] Optionally, the reverse rigidochromic fluorescent molecular probe can be the following specific compound:

[0119]

[0120] The application adopts a fluorescent molecule with a phenanthridine unit introduced to construct a π conjugated system, precisely regulates polar-π interaction and charge transfer path between a probe molecule and a polymer to construct a design strategy of a reverse rigidochromic fluorescent molecular probe. On one hand, the phenanthridine unit is introduced, and the lone pair of electrons on the sp2 hybridized "N" is conducive to inducing dipole-dipole interaction between the fluorescent probe and the polymer, thereby promoting the formation of a charge transfer complex (CTC) between the probe molecule and the polymer. On the other hand, the construction of the π conjugated system can adjust the frontier molecular orbital energy level and further enhance the π-π interaction between the fluorophore and the polymer; at the same time, the π fused ring is conducive to locking the conformation of the fluorescent molecule, limiting intramolecular rotation, inhibiting the emission blue shift induced by twisted intramolecular charge transfer (TICT), and reducing the energy loss of non-radiative transition, thereby enhancing the quantum yield of the fluorescent molecule.

[0121] Optionally, the preparation method of the reverse rigidochromic fluorescent molecular probe comprises the following steps:

[0122] (1) mixing raw materials containing compound 1, compound 2, a weak base and a solvent III, contacting with a catalyst I under a non-active atmosphere, performing Suzuki coupling reaction, passivation I, and obtaining compound 3;

[0123] (2) mixing a mixed solution containing compound 3 and POCl3, contacting with P2O5 under a non-active atmosphere, performing Bischler-Napieralski reaction, passivation II, and obtaining the reverse rigidochromic fluorescent molecular probe;

[0124] Optionally, in step (1), the weak base is selected from at least one of K2CO3, NaHCO3, Cs2CO3;

[0125] The compound 1 has a structure shown in formula I;

[0126] The compound 2 has a structure shown in formula II;

[0127] The compound 3 has a structure shown in formula III;

[0128]

[0129] wherein AryI is at least one of anthracene, diphenylamine, triphenylamine, indole, tri- carbazole, tri-fluorene compound;

[0130] The R' substituent group is selected from at least one of halogen, boronic acid pinacol ester group;

[0131] The R1 substituent group is selected from at least one of H, C1-20 alkyl, C1-6 alkylhalide, C1-6 alkyl primary amine, C1-6 alkyl secondary amine, C1-6 alkyl tertiary amine, C1-6 quaternary amine salt;

[0132] The R2 substituent group is selected from at least one of H, C1-12 alkyl, cyano, halogen, amino, methylamino, C0-4 alkyl secondary amine, C0-4 alkyl tertiary amine, C0-4 quaternary amine salt;

[0133] Optionally, wherein when the reverse rigidochromic fluorescent molecular probe is a compound of the structure shown in formula M1, the compound 1 has a structure shown in formula N1;

[0134] When the reverse rigidochromic fluorescent molecular probe is a compound of the structure shown in formula M2, the compound 1 has a structure shown in formula N2, wherein X is selected from at least one of N, P, As, and Y is selected from at least one of H, F, Cl, Br, I;

[0135] When the reverse rigidochromic fluorescent molecular probe is a compound of the structure shown in formula M3, the compound 1 has a structure shown in formula N3;

[0136]

[0137] When the reverse rigidochromic fluorescent molecular probe is a compound of the structure shown in any one of formulas M4 to M9, the compound 1 has a structure shown in formula N4, wherein one of Y1, Y2, Y3, Y4 is Br, and the other three are H;

[0138] When the anti-irradiation color change fluorescent molecular probe is a compound of the structure according to any one of formulae M10-M20, the compound 1 has a structure according to formula N5, wherein X is selected from one of N or C, one of Y1, Y2, Y3, Y4 is Br, and the other three are H;

[0139]

[0140] Optionally, the solvent III is a mixed solvent of tetrahydrofuran and water; wherein the volume ratio of tetrahydrofuran to water in the mixed solvent of tetrahydrofuran and water is 5-12:1;

[0141] Optionally, the non-reactive atmosphere is selected from one of nitrogen and argon;

[0142] Optionally, the catalyst I is selected from at least one of Pd(PPh3)4, Pd(PPh3)2Cl2, PdCl2, PPh3, n-Bu3P, (MeO)3P, (o-tol)3P, AsPh3, Ph2P(CH2)2PPh2(dppe), Ph2P(CH2)3PPh2(dppp);

[0143] Optionally, the temperature of the Suzuki coupling reaction is 80-90°C, and the time of the Suzuki coupling reaction is 24-72h.

[0144] Optionally, the temperature of the Suzuki coupling reaction is independently selected from any value of 80°C, 85°C, 90°C, or any value between any two of the above.

[0145] Optionally, the time of the Suzuki coupling reaction is independently selected from any value of 24h, 48h, 72h, or any value between any two of the above.

[0146] Optionally, the molar ratio of compound 1, compound 2, catalyst I, and weak base is 1:1-6:0.01-0.05:10-50;

[0147] Optionally, the molar ratio of compound 1, compound 2, catalyst I, and weak base is independently selected from any value of 1:1:0.01:10, 1:1:0.01:50, 1:1:0.05:10, 1:1:0.05:50, 1:6:0.01:10, 1:6:0.01:50, 1:6:0.05:10, 1:6:0.05:50, or any value between any two of the above.

[0148] Optionally, in the mixed solution, the concentration of compound I is 0.01-0.05mol / L;

[0149] Optionally, the concentration of the compound I is independently selected from any value or any value between any two points of 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L.

[0150] Optionally, the parameter of the passivation I is that the reaction temperature is 80-90℃, and the reaction time is 24-72h.

[0151] The parameter of the passivation II is that the reaction temperature is 100-120℃, and the reaction time is 14-18h.

[0152] Optionally, the molar ratio of the compound 3 to P2O5 is 1:10-1:30.

[0153] Optionally, the molar ratio of the compound 3 to P2O5 is independently selected from any value or any value between any two points of 1:10, 1:20, 1:30.

[0154] Optionally, the mass ratio of the compound 3 to POCl3 is 1:20-1:160.

[0155] Optionally, the mass ratio of the compound 3 to POCl3 is independently selected from any value or any value between any two points of 1:20, 1:40, 1:80, 1:120, 1:160.

[0156] Optionally, the temperature of the Bischler-Napieralski reaction is 110-120℃, and the time of the Bischler-Napieralski reaction is 14-18h.

[0157] Optionally, the temperature of the Bischler-Napieralski reaction is independently selected from any value or any value between any two points of 110℃, 115℃, 120℃.

[0158] Optionally, the time of the Bischler-Napieralski reaction is independently selected from any value or any value between any two points of 14h, 16h, 18h.

[0159] As a specific embodiment, the preparation method of the reverse thermochromic fluorescent molecular probe comprises the following steps:

[0160]

[0161] (1) The compound of formula 1, the compound of formula 2 and weak base (K2CO3 / NaHCO3 / Cs2CO3, etc.) are dissolved in a mixed solvent of tetrahydrofuran and water, a catalyst Pd(PPh3)4 is added under nitrogen atmosphere, and then the reaction is carried out at 90°C. After the reaction is completed, purification treatment is carried out to obtain the compound of formula 3.

[0162] (2) The compound of formula 3 is dissolved in phosphorus oxychloride, P2O5 is added under nitrogen atmosphere, and then the reaction is carried out at 110°C. After the reaction is completed, purification treatment is carried out to obtain the reverse thermochromic fluorescent molecular probe M1-20.

[0163] In the above method, the Br functional group of the substrate can also be exchanged with the borate functional group to prepare M1-20.

[0164] As another specific embodiment, the preparation method of the reverse thermochromic fluorescent molecular probe comprises the following steps:

[0165] (1) The compound of formula 1 and the compound of formula 2 are subjected to Suzuki coupling reaction, and purification treatment is carried out to obtain the compound of formula 3.

[0166] According to the present application, in step (1), the reaction is preferably carried out in the presence of a palladium catalyst and a weak base; the palladium catalyst is preferably Pd(PPh3)4; the weak base is preferably K2CO3 or NaHCO3, and the second best is Cs2CO3. The reaction solvent is preferably a mixed solvent of tetrahydrofuran (THF) and water (H2O), and the amounts of THF and H2O are 30 mL and 2.5 mL, respectively; the reaction temperature is preferably 85-90°C; the reaction time is preferably 48-72 hours; and the reaction atmosphere is an inert environment, preferably a nitrogen atmosphere. In the preparation of M1, M4-M9 and M18-M20, the amounts of the compound of formula 1, the compound of formula 2, the palladium catalyst and the weak base are preferably 1 mmol, 1.5 mmol, 0.05 mmol and 20 mmol, respectively; in the preparation of M2 and M15-M17, the amounts of the compound of formula 1, the compound of formula 2, the palladium catalyst and the weak base are preferably 1 mmol, 3.0 mmol, 0.05 mmol and 20 mmol, respectively; and in the preparation of M3 and M10-M14, the amounts of the compound of formula 1, the compound of formula 2, the palladium catalyst and the weak base are preferably 1 mmol, 4.5 mmol, 0.05 mmol and 20 mmol, respectively.

[0167] (2) The compound of formula 3 is subjected to Bischler-Napieralski reaction, and purification is carried out to obtain the compound of formula I.

[0168] According to the present application, in step (2), the reaction is preferably carried out in the presence of phosphorus oxychloride (POCl3) and phosphorus pentoxide (P2O5); the reaction temperature is 100-120°C, preferably 110°C; the reaction time is preferably 14-18 hours; the reaction atmosphere is inert, preferably a nitrogen atmosphere. In the preparation of M1, M4-M9 and M18-M20, the amount of compound of formula 3 and P2O5 is preferably 0.25 mmol and 2.5 mmol, and the amount of POCl3 is preferably 5-10 mL; in the preparation of M2 and M15-M17, the amount of compound of formula 3 and P2O5 is preferably 0.25 mmol and 5.0 mmol, and the amount of POCl3 is preferably 10 mL; in the preparation of M3 and M10-M14, the amount of compound of formula 3 and P2O5 is preferably 0.25 mmol and 7.5 mmol, and the amount of POCl3 is preferably 10-15 mL.

[0169] The term "alkyl" as used herein refers to a straight chain or branched alkyl group having 1-20 (1-12, 1-6 or 0-4) carbon atoms;

[0170] In the present application, M10, M11, M12, M13 and M14 are configurational isomers, and the present application includes the above-mentioned configurational isomers and covers other configurational isomers of the same kind;

[0171] In the present application, M15, M16 and M17 are configurational isomers, and the present application includes the above-mentioned configurational isomers and covers other configurational isomers of the same kind;

[0172] In the present application, M18, M19 and M20 are configurational isomers, and the present application includes the above-mentioned configurational isomers and covers other configurational isomers of the same kind.

[0173] The beneficial effects that can be produced by the present application include:

[0174] The free volume of the polymer is mainly determined by the length of the polymer chain, the conformation, the crosslinking density, and the hierarchical structure at the nanometer and micrometer levels. The method of the present application includes: changing the free volume of the polymer by polymerization or degradation to achieve data storage and encryption, using the sensitivity of the reverse rigidochromic fluorescent molecular probe to the change in the free volume of the polymer as a developer, thereby achieving safe decryption under specific conditions; in addition, the hierarchical / topological structure of the polymer is further optimized, and the reverse rigidochromic fluorescent molecular probe is used as a "built-in fluorescent sensor" to achieve controllable regulation of the fluorescence emission wavelength and the polarity of circularly polarized light emission, thereby improving the multi-prevention capability of the pattern. The method provided by the present application greatly reduces the risk of cracking the data using advanced instruments, and the multi-dimensional change of the pattern is also difficult to tamper with, which is suitable for the field of encryption and anti-counterfeiting technology. Attached Figure Description

[0175] Figure 1 This is an illustration of the effect of using the anti-rigid-chromic fluorescent molecular probe F-2 as a developer to sense the free volume change of polymers during photopolymerization in Example 9, thereby achieving data encryption and decryption (scale bar: 1 cm).

[0176] Figure 2 The image shows a view of the CLC thin film with different optical bandgap obtained in Example 10, with the written pattern appearing under natural light (scale bar: 1 cm).

[0177] Figure 3 Scanning electron microscope (SEM) images of CLC films with different pitches obtained in Example 10 (scale bar: 500 nm). Detailed Implementation

[0178] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments. Unless otherwise specified, the methods described below are conventional methods.

[0179] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0180] Example 1: Preparation of fluorescent molecular probe F-1

[0181]

[0182] Synthesis of Formula 3: Formula 1 (0.15 g, 0.60 mmol), Formula 2 (0.3 g, 0.90 mmol) and K2CO3 (1.0 g, 6.0 mmol) were dissolved in THF (30 mL) and deionized water (2.5 mL), purged with nitrogen, and Pd(PPh3)4 (35 mg, 0.03 mmol) was added under nitrogen atmosphere, and purged with nitrogen again. The mixture was stirred at 90 °C for 3 days. After the reaction was completed and cooled to room temperature, 50 mL of saturated brine was added, extracted with EA (50 mL x 3), the organic phase was combined, dried over anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with eluent of petroleum ether (PE) and ethyl acetate (EA) (10:1 to 2:1) to give Formula 3 (0.298 g, yield 81%) as a yellow solid.1H NMR (400 MHz, CDCl3, δ): δ 8.59 (d, J = 3.9 Hz, 2H), 8.18 - 8.03 (m, 5H), 7.56 - 7.50 (m, 3H), 7.48 - 7.37 (m, 2H), 7.28 (t, J = 7.4 Hz, 1H), 2.23 (t, J = 7.5 Hz, 2H), 1.22 (dt, J = 7.2, 3.6 Hz, 4H), 1.58 (t, J = 7.3 Hz, 2H), 0.84 - 0.76 (m, 3H).13C NMR (100 MHz, CDCl3, δ): 160.63, 144.62, 134.31, 132.29, 131.86, 131.42, 131.34, 129.07, 128.97, 128.87, 128.20, 127.55, 127.12, 126.91, 126.44, 126.31, 126.13, 123.29, 122.70, 122.65, 120.22, 41.48, 32.30, 29.09, 22.77, 14.27.

[0183]

[0184] Synthesis of F-1: A mixture of Formula 3 (0.22 g, 0.26 mmol), POCl3(16.7 g, 10 mL) and P2O5(0.37 g, 2.6 mmol) was stirred at 110 °C for 16 h under nitrogen atmosphere. After the reaction was cooled to room temperature, the resulting mixture was poured into water (100 mL), ethyl acetate (EA, 100 mL) was added, slowly neutralized to pH = 9 with aqueous NaOH solution (8 M NaOH), then extracted with DCM (100 mL x 3), the organic phase was combined, dried with anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with PE:EA (10:1 ~ 5:1) as eluent to give yellow solid F-1 (0.29 g, yield 83%).1H NMR (400 MHz, CDCl3, δ): δ 9.29 (s, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.52 (t, J = 4.6 Hz, 2H), 8.25 - 8.18 (m, 2H), 8.17 - 8.06 (m, 2H), 7.79 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.70 - 7.59 (m, 3H), 3.86 - 3.73 (m, 2H), 2.31 - 2.13 (m, 2H), 1.64 (p, J = 7.3 Hz, 2H), 1.50 (dt, J = 14.5, 7.3 Hz, 2H), 0.99 (t, J = 7.3 Hz, 3H).13C NMR (100 MHz, CDCl3, δ): 171.24, 136.06, 135.84, 134.35, 132.11, 132.04, 131.80, 130.89, 130.26, 128.44, 128.18, 128.12, 128.09, 127.89, 127.30, 126.47, 126.04, 125.69, 125.61, 124.73, 124.46, 36.53, 31.25, 25.11, 22.20, 13.31.

[0185] Example 2: Preparation of fluorescent molecular probe F-2

[0186]

[0187] Synthesis of Formula 4: tris(4-bromophenyl)amine (434 mg, 0.90 mmol), Formula 2 (1.35 g, 4.05 mmol) and K2CO3(1.25 g, 9.0 mmol) were dissolved in THF (30 mL) and deionized water (2.5 mL), purged with nitrogen, and Pd(PPh3)4(35 mg, 0.03 mmol) was added under nitrogen atmosphere, and purged with nitrogen again. The mixture was stirred at 90 °C for 3 days. After the reaction was completed and cooled to room temperature, 50 mL of saturated brine was added, extracted with EA (50 mL x 3), the organic phases were combined, dried over anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with PE:EA (10:1 ~ 2:1) as eluent to give white solid 4 (580 mg, yield 79%).1H NMR (400 MHz, CDCl3, δ): 8.26 (d, J = 8.2 Hz, 3H), 7.40-7.31 (m, 9H), 7.29 (d, J = 8.7 Hz, 9H), 7.24 (s, 3H), 7.18 (d, J = 7.5 Hz, 3H), 2.26 (t, J = 7.6 Hz, 6H), 1.63 (t, J = 7.5 Hz, 6H), 1.32-1.27 (m, 12H), 0.89-0.84 (m, 9H).13C NMR (100 MHz, CDCl3, δ): 171.17, 146.89, 134.72, 133.08, 131.74, 130.40, 130.05, 128.42, 124.48, 121.97, 37.82, 31.43, 31.31, 30.19, 29.70, 25.19, 22.37, 13.93.

[0188]

[0189] Synthesis of F-2: A mixture of Formula 4 (200 mg, 0.25 mmol), phosphorus oxychloride (POCI3, 25.1 g, 15 mL) and phosphorus pentoxide (P2O5, 1.1 g, 7.50 mmol) was stirred at 110 °C for 16 h under nitrogen atmosphere. After cooling to room temperature, the resulting mixture was poured into water (100 mL), ethyl acetate (EA, 100 mL) was added, slowly neutralized to pH = 9 with aqueous sodium hydroxide solution (8 M NaOH), then extracted with DCM (100 mL x 3), the organic phase was combined, dried with anhydrous Na2SO4, filtered, concentrated. The crude product was purified by column chromatography with PE: Ea (5:1 ~ 2:1) as eluent to give F-2 (110 mg, yield 59%) as a light yellow solid.1H NMR (400 MHz, CDCl3, δ): 8.62 (d, J = 8.9 Hz, 3H), 8.49 (d, J = 8.0 Hz, 3H), 8.11 (d, J = 8.1 Hz, 3H), 7.99 (s, 3H), 7.80 (d, J = 8.9 Hz, 3H), 7.70 (t, J = 7.5 Hz, 3H), 7.63 (t, J = 7.5 Hz, 3H), 3.09 (t, J = 8.1 Hz, 6H), 1.71 (dd, J = 15.4, 7.7 Hz, 6H), 1.18 (t, J = 7.8 Hz, 6H), 1.04 (q, J = 7.4 Hz, 6H), 0.54 (t, J = 7.2 Hz, 9H).13C NMR (100 MHz, CDCl3, δ): 160.64, 145.05, 142.48, 128.63, 128.34, 127.29, 126.32, 125.59, 125.47, 123.26, 122.42, 120.61, 119.25, 35.33, 30.81, 28.30, 21.27, 12.68.

[0190] Example 3: Preparation of fluorescent molecular probe F-3

[0191]

[0192] Synthesis of Formula 5: 6-bromoindole (2 g, 10.2 mmol) was dissolved in 30 mL of super dry DMF under nitrogen atmosphere, and stirred vigorously at room temperature, NaH (293.8 mg, 12.24 mmol) was added to the reaction solution under nitrogen atmosphere, and stirred vigorously at room temperature for 40 min, then hexyl iodide (1.8 mL, 12.29 mmol) was injected into the reaction solution with a syringe, and then stirred at 70 °C for 24 h under reflux. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and 100 mL of saturated brine were poured into a separatory funnel, and the organic / water phase mixture was extracted with EA (100 mL x 3), the organic phase was collected, dried with Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with PE as eluent to obtain colorless oily liquid 5 (2.85 g, yield 93%).1H-NMR (400 MHz, CDCl3, δ): 7.51-7.41 (m, 2H), 7.19-7.13 (dd, 1H), 7.05-6.98 (d, 1H), 6.46-6.38 (d, 1H), 4.07-3.94 (t, 2H), 1.82-1.70 (t, 2H), 1.30-1.23 (m, 6H), 0.90-0.82 (m, 3H).

[0193]

[0194] Synthesis of Formula 6: Formula 5 (100 mg, 0.36 mmol), Formula 2 (171 mg, 0.54 mmol) and K2CO3 (497 mg, 3.60 mmol) were dissolved in THF (30 mL) and deionized water (2.5 mL), purged with nitrogen, and Pd(PPh3)4 (25 mg, 0.02 mmol) was added under a nitrogen atmosphere, and then purged with nitrogen again. The mixture was stirred at 90 °C for 3 days. After the reaction was completed and cooled to room temperature, 50 mL of saturated brine was added, extracted with EA (50 mL x 3), the organic phase was combined, dried over anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with PE:EA (10:1 ~ 8:1) as eluent to obtain brown oil liquid 6 (169.33 mg, yield 85%).1H-NMR (400 MHz, CDCl3, δ): 8.35-8.27 (d, J = 8.2 Hz, 1H), 7.64-7.57 (d, J = 8.1 Hz, 1H), 7.36-7.29 (s, 1H), 7.26-7.19 (m, 3H), 7.09-7.03 (m, 2H), 7.01-6.96 (dd, J = 8.0, 1.4 Hz, 1H), 6.47-6.42 (d, J = 3.1 Hz, 1H), 4.05-3.95 (t, J = 7.2 Hz, 2H), 2.08-1.99 (t, J = 7.5 Hz, 2H), 1.79-1.68 (m, 2H), 1.53-1.41 (m, 2H), 1.24-1.18 (m, 6H), 1.15-1.11 (m, 4H), 0.80-0.71 (m, 6H).13C (100 MHz, CDCl3, δ): 170.19, 135.24, 134.24, 131.90, 130.06, 129.38, 127.88, 127.12, 126.92, 122.76, 120.42, 119.78, 119.36, 109.28, 99.91, 45.50, 36.83, 30.38, 30.22, 29.23, 25.65, 24.13, 21.51, 21.31, 12.95, 12.81.

[0195]

[0196] Synthesis of F-3: A mixture of Formula 6 (2 g), POCI3(83.7 g, 50 mL) and P2O5(7.0 g) was stirred at 110 °C for 16 h under nitrogen atmosphere. After cooling to room temperature, the resulting mixture was poured into water (100 mL), ethyl acetate (EA, 100 mL) was added, slowly neutralized to pH = 9 with 8 M NaOH, then extracted with DCM (100 mL x 3), the organic phase was combined, dried with anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by chromatography column with PE: Ea (7:1 ~ 5:1) as eluent to give F-3 (102 mg, yield 2.3%) as a yellowish liquid.1H-NMR (400 MHz, CDCl3, δ): 8.69-8.58 (d, 1H), 8.57-8.51 (s, 1H), 8.50-8.43 (s, 1H), 8.17-8.09 (d, 1H), 7.69-7.62 (t, 1H), 7.62-7.54 (t, 1H), 7.41-7.33 (d, 1H), 6.82-6.73 (d, 1H), 4.37-4.22 (m, 2H), 3.55-3.36 (m, 2H), 2.07-1.97 (dd, 2H), 1.96-1.88 (m, 2H), 1.62-1.52 (m, 2H), 1.50-1.40 (m, 2H), 1.39-1.29 (m, 6H), 1.00-0.93 (t, 3H), 0.92-0.83 (t, 3H).13C (100 MHz, CDCl3, δ): 162.61, 137.05, 130.81, 128.46, 128.31, 126.91, 126.43, 124.53, 123.67, 120.48, 118.68, 117.79, 100.70, 99.61, 45.64, 36.00, 31.32, 30.40, 29.16, 29.06, 28.62, 25.70, 21.66, 21.52, 13.10, 12.97.

[0197] Example 4: Preparation of fluorescent molecular probe F-4

[0198]

[0199] Synthesis of Formula 7: 6-TAT (0.5 g, 0.60 mmol), Formula 2 (0.857 g, 2.70 mmol) and K2CO3 (1.0 g) were dissolved in THF (30 mL) and deionized H2O (2.5 mL), purged with nitrogen, and Pd(PPh3)4 (35 mg, 0.03 mmol) was added under nitrogen atmosphere, and purged with nitrogen again. The mixture was stirred at 90 °C for 3 days. After the reaction was completed and cooled to room temperature, 50 mL of H2O was added, extracted with Ea (50 mL x 3), the organic phase was combined, dried over anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography with PE:Ea (10:1 ~ 2:1) as eluent to give white solid 7 (0.566 g, 81%).1H NMR (400 MHz, CDCl3, δ): 8.46 (d, J = 8.4 Hz, 3H), 8.38 (d, J = 8.3 Hz, 3H), 7.66 (s, 3H), 7.47-7.44 (m, 9H), 7.38 (d, J = 8.2 Hz, 3H), 7.29-7.25 (m, 3H), 4.98 (t, J = 7.7 Hz, 6H), 2.21 (t, J = 7.4 Hz, 6H), 2.10-2.02 (m, 6H), 1.62-1.58 (m, 6H), 1.37-1.31 (m, 6H), 1.25-1.23 (m, 24H), 0.82-0.78 (m, 18H).13C (100 MHz, CDCl3, δ): 171.26, 141.42, 139.45, 135.26, 132.93, 132.43, 130.49, 128.46, 124.14, 122.90, 121.88, 121.24, 121.00, 111.43, 103.16, 47.23, 37.94, 31.45, 31.31, 30.03, 26.39, 25.22, 22.49, 22.38, 13.92, 13.87.

[0200] Synthesis of F-4: A mixture of Formula 7 (0.3 g, 0.26 mmol), POCI3(25.1 g, 15 mL) and P2O5(1.1 g, 7.80 mmol) was stirred at 110 °C for 16 h under nitrogen atmosphere. After the reaction was cooled to room temperature, the resulting mixture was poured into water (100 mL), ethyl acetate (EA, 100 mL) was added, slowly neutralized to pH = 9 with 8 M NaOH, then extracted with DCM (100 mL x 3), the organic phase was combined, dried with anhydrous Na2SO4, filtered, and concentrated. The crude product was purified by column chromatography using PE:DCM:NEt3(50:100:1) as eluent to give yellow solid PTF1(0.236 g, 83%).1H NMR (400 MHz, CDCI3, δ): 9.09 (s, 3H), 8.66 (d, J = 8.0 Hz, 3H), 8.64 (s, 3H), 8.20 (d, J = 7.8 Hz, 3H), 7.77-7.67 (m, 6H), 5.15 (t, J = 7.0 Hz, 6H), 3.59 (t, J = 7.8 Hz, 6H), 2.18-2.10 (m, 6H), 1.85-1.85 (m, 6H), 1.70-1.63 (m, 6H), 1.56-1.46 (m, 6H), 1.06-0.95 (m, 27H), 0.60-0.57 (t, J = 7.1 Hz, 9H).13C (100 MHz, CDCI3, δ): 162.39, 143.49, 143.29, 141.81, 129.66, 129.63, 128.21, 126.02, 124.34, 123.94, 121.75, 120.16, 119.31, 103.81, 102.35, 47.11, 36.97, 32.52, 21.25, 29.64, 29.02, 26.36, 22.93, 22.25, 14.26, 13.72.

[0201] Example 5: Preparation of fluorescent molecular probe F-5

[0202]

[0203] Synthesis of Formula 8: Formula 8 was synthesized by referring to the method of Formula 7 above.1H NMR (400 MHz, CDC13, δ): 8.46 (d, J = 8.3 Hz, 3H), 8.27 (s, 3H), 7.71 (d, J = 8.3 Hz, 3H), 7.47-7.42 (m, 9H), 7.35 (s, 3H), 7.26-7.22 (m, 3H), 4.89 (t, J = 7.8 Hz, 6H), 2.14 (t, J = 7.5 Hz, 6H), 2.06 (br, 6H), 1.56-1.49 (m, 6H), 1.20-1.05 (m, 30H), 0.76-0.70 (m, 18H).13C (100 MHz, CDC13, δ): 171.20, 140.50, 139.45, 135.40, 132.78, 130.40, 129.73, 128.21, 124.05, 123.97, 123.82, 122.42, 121.00, 110.83, 103.10, 47.48, 37.93, 31.48, 31.20, 30.41, 26.44, 25.17, 22.47, 22.25, 13.89, 13.76.

[0204] Synthesis of F-5: F-5 was synthesized by referring to the method of F-4 above.1H NMR (400 MHz, CDC13, δ): 9.01 (s, 3H), 8.40 (d, J = 8.0 Hz, 3H), 8.24 (d, J = 8.0 Hz, 3H), 7.84 (s, 3H), 7.75 (t, J = 7.2 Hz, 3H), 7.60 (t, J = 7.4 Hz, 3H), 4.51 (t, J = 7.2 Hz, 6H), 3.24 (t, J = 7.9 Hz, 6H), 1.97-1.89 (m, 12H), 1.54-1.47 (m, 6H), 1.43-1.34 (m, 6H), 1.05-0.99 (m, 18H), 0.93 (t, J = 7.2 Hz, 9H), 0.64 (t, J = 7.0 Hz, 9H).13C (100 MHz, CDC13, δ): 161.93, 142.96, 142.75, 140.90, 129.97, 127.61, 126.56, 126.23, 125.98, 124.34, 121.73, 120.96, 113.73, 105.68, 102.32, 47.46, 36.88, 32.44, 31.47, 29.92, 29.44, 26.66, 22.70, 22.53, 14.17, 13.79.

[0205] Example 6: Preparation of fluorescent molecular probe F-6

[0206]

[0207] Synthesis of Formula 9: Refer to the method of synthesis of Formula 7 above for the synthesis of Formula 9.1H NMR (400 MHz, CDC13, δ): 8.44-8.33 (m, 3H), 8.23-8.16 (m, 3H), 7.59-7.48 (m, 9H), 7.45-7.30 (m, 9H), 4.77-4.48 (m, 3H), 3.96-3.80 (m, 3H), 1.94-1.78 (m, 6H), 1.31-1.12 (m, 6H), 0.97-0.74 (m, 18H), 0.70-0.60 (m, 12H), 0.55-0.49 (m, 12H), 0.42-0.32 (m, 12H).13C (100 MHz, CDC13, δ): 171.72, 172.61, 171.51, 142.24, 141.64, 141.41, 141.17, 140.30, 140.06, 139.99, 139.91, 136.14, 136.11, 135.99, 135.97, 130.94, 130.76, 130.43, 130.30, 130.19, 128.89, 127.43, 127.21, 127.14, 126.61, 126.44, 126.33, 126.25, 124.69, 124.63, 124.35, 124.22, 123.72, 123.43, 122.61, 122.52, 122.34, 122.23, 122.16, 122.07, 121.53, 107.41, 107.02, 106.90, 106.26, 49.06, 48.53, 47.91, 37.65, 37.57, 37.43, 30.95, 30.93, 30.92, 30.90, 30.86, 30.84, 28.11, 27.71, 27.54, 25.76, 25.60, 25.53, 24.71, 24.56, 24.48, 22.05, 22.03, 21.89, 21.84, 21.79, 21.76, 13.67, 13.62, 13.61, 13.49, 13.44, 13.37.

[0208] Synthesis of F-6: F-6 was synthesized according to the procedure of F-4 above.1H NMR (400 MHz, CDC13, δ): 9.37 (br, 3H), 8.86 (d, J = 8.4 Hz, 3H), 8.52 (d, J = 8.5 Hz, 3H), 8.31 (d, J = 7.9 Hz, 3H), 7.94-7.85 (m, 6H), 4.97 (br, 6H), 3.60 (br, 6H), 2.13 (br, 6H), 1.70-1.63 (m, 6H), 1.57-1.48 (m, 6H), 1.00 (t, J = 7.3 Hz, 9H), 0.54 (br, 9H), 0.42 (br, 9H), 0.33 (br, 15H).13C (100 MHz, CDC13, δ): 162.98, 144.41, 141.03, 129.00, 128.85, 128.39, 126.79, 125.85, 123.42, 122.63, 122.15, 121.56, 120.87, 110.58, 52.20, 37.39, 32.44, 30.59, 29.85, 27.12, 25.65, 22.77, 21.80, 14.20, 13.48.

[0209] Example 7: Elemental analysis test based on information encryption of polymer free volume change

[0210] In the method of using the anti-irradiation fluorescent molecular probe F-2 as a developer to sense the free volume change of the polymer during the photopolymerization process to realize data encryption and decryption,

[0211] The specific method is as follows: configure a prepolymer solution, and the components of the prepolymer solution are polymer monomer molecules (pentafluorophenol acrylate, 594 mg), 1,6-hexanediol diacrylate (6 mg), and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (9 mg / mL, 74 μL, toluene solvent). Inject the prepolymer solution into the mold, exclude air, and then use a mask plate with a hollow letter “Fuz” to perform photopolymerization, so as to write and encrypt the information “Fuz” into the film. The light power is 18 W, the light wavelength is 365 nm, and the light irradiation time is 50 minutes. The film is immersed in a toluene solution containing the fluorescent molecule F-2 obtained in Example 2 (2.5 x 10 -4The film containing encrypted information was taken out after 5 minutes and information was read under UV light 365 nm. The information area "Fuz" presented yellow fluorescent emission and the background area presented blue fluorescent emission. The thin film of the yellow area and the blue area was cut respectively for elemental analysis test. The film containing encrypted information obtained by elemental analysis test, the C, H, O, N element content of the information area and the background area, the results were: the C, H, O, N element percentage of the information area was 46.3±0.09, 1.60±0.07, 26.0±1.64, <0.3 respectively; the C, H, O, N element percentage of the background area was 45.9±0.45, 1.55±0.11, 26.5±0.9, <0.3 respectively. The elemental composition of the two was almost the same, which greatly reduced the risk of information decryption by advanced instrument analysis of ingredients.

[0212] Example 8: Stretching performance test of information encryption based on polymer free volume change

[0213] The film of the information area and the background area of the film containing encrypted information obtained in Example 7 was tested for stretching performance, and the results were: the elastic modulus of the information area and the background area was 4.92 MPa and 4.74 MPa respectively. The difference in elastic modulus of the two was almost negligible, and there would be no any detectable anisotropic swelling in common organic solvents, and it was impossible to decrypt the information by solvent swelling or etching.

[0214] Example 9: Information encryption technology based on polymer free volume change

[0215] The monomer pentafluorophenyl acrylate (594 mg), 1,6-hexanediol diacrylate (6 mg) and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (9 mg / mL, 74 μL, toluene) were mixed, and then the mixture was injected into the mold, air was excluded, and photopolymerization was carried out under 365 nm UV light using a mask plate pre-designed with three hollow letters of Fuz, the light power was 18 W, and the light exposure time was 50 minutes, to obtain a film B containing encrypted information. The prepared film B had no pattern under visible light and UV light. As shown in Figure 1 The film B was immersed in a solution containing the fluorescent molecule F-2 obtained in Example 2 (solvent: toluene, concentration of fluorescent molecule F-2: 2.5×10 -4 M, 5 mL) for 5 minutes, and there was still no pattern under visible light, but the three encrypted letter information of Fuz could be seen under 365 nm UV light.

[0216] Example 10: Information anti-counterfeiting technology based on polymer free volume change

[0217] A polyvinyl alcohol (PVA) aqueous solution (mass fraction preferably 1 wt%) was spin-coated on a clean glass slide (50 x 50 mm 2 ) at a rotation speed of 1600 rpm. Subsequently, it was heated at 110 °C for 120 min. The PVA layer was rubbed in one direction with a velvet cloth. A blank glass slide was placed on the PVA layer, and a liquid crystal cell was injected between the PVA layer and the blank glass slide to prepare a CLC film, with a gap of 39 pm between the two layers, i.e. a CLC film thickness of 39 pm.

[0218] Liquid crystal monomers RM105 (200 mg), RM257 (300 mg), S811 (100 mg), phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (4 mg / mL, 500 uL, THF), and the reverse thermochromic fluorescent molecular probe F-2 (2.5 x 10 -4 M, 400 uL, THF) obtained from Example 2 were dissolved in THF; the solution was heated at 75 °C for 6 hours. Then, a uniform liquid crystal mixed solution was filled into the above-mentioned 39 pm thick gap by capillary action, and a photomask with a flower hollow pattern was attached to the upper surface of the blank glass slide. Subsequently, photopolymerization was carried out under 365 nm ultraviolet light with a light power of 18 W and an irradiation time of 50 minutes. A patterned CLC film with a PBG of 700 nm was obtained.

[0219] The above-mentioned scheme was repeated by adjusting the amounts of liquid crystal monomers RM105, RM257, S811, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, and F-2 to 200 mg, 300 mg, 135 mg, 0.67 mg, and 1 mg, respectively, to obtain a patterned CLC film with a PBG of 550 nm.

[0220] In summary, by adjusting the proportions of RM105, RM257, and S811, CLC thin films with optical band gaps (PBGs) of 550 nm and 700 nm were prepared, respectively, so that the fluorescence emission of the fluorescent molecular probe F-4 fell inside and to the left of the PBG. As shown in Figure 2 Fig. 6, the written pattern under natural light showed significantly different visual effects under left polarizing filters, right polarizing filters, and no polarizing filters, demonstrating its strong anti-counterfeiting ability.

[0221] Figure 3 As shown in Fig. 7, scanning electron microscopy characterization showed that the pitch of the CLC liquid crystal thin film with a PBG of 550 nm was 378 nm, and the pitch of the CLC liquid crystal thin film with a PBG of 700 nm was 426 nm.

[0222] The above merely describes several embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical contents without departing from the scope of the technical solutions of the present application, and the equivalent embodiments are equivalent to the equivalent embodiments, which are within the scope of the technical solutions.

Claims

1. A method for data encryption based on polymer free volume change, characterized in that, The method includes the following steps: (1) A prepolymer liquid containing polymer monomer molecules and photoinitiator I is injected into a mold, and photoinitiated polymerization is carried out under the condition of using a mask to obtain a thin film containing encrypted information; (2) Immerse the thin film obtained in step (1) in solution I containing the anti-rigid color-changing fluorescent molecular probe, take it out and read the information under ultraviolet light I; The fluorescence emission of the aforementioned anti-rigid-chromic fluorescent molecular probe exhibits a significant redshift as the free volume of the polymer decreases.

2. The method according to claim 1, characterized in that, The polymer monomer molecule is selected from at least one of methyl acrylate, methyl acrylate derivatives, phenolic acrylate, phenolic acrylate derivatives, pentafluorophenolic acrylate, and pentafluorophenolic acrylate derivatives.

3. The method according to claim 1, characterized in that, The polymer monomer molecule is selected from at least one of pentafluorophenol acrylate, p-trifluoromethylphenol acrylate, 2-methyl-1,4-phenylene bis(4-(3-(acryloyloxy)propoxy))benzoate, and 4-methoxyphenyl 4-[[6-[(1-oxo-2-propenyl)oxy]hexyl]oxy]benzoate.

4. The method according to claim 1, characterized in that, The photoinitiator I is selected from at least one of 2,4,6-trimethylbenzoylphenylphosphonate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and α,α-dimethoxy-α-phenylacetophenone.

5. The method according to claim 1, characterized in that, The prepolymer liquid also contains solvent I, which is selected from at least one of toluene, 1,4-dioxane, tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, acetone, chlorobenzene, o-dichlorobenzene, and acetonitrile. The prepolymer solution also contains a crosslinking agent.

6. The method according to claim 5, characterized in that, The crosslinking agent is selected from at least one of the following: a C2-12 diol, a C5-20 tetraol, a C2-12 diamine, or a C5-20 tetraamine derivative, in combination with acrylic acid.

7. The method according to claim 5, characterized in that, The crosslinking agent is selected from at least one of 1,6-hexanediol diacrylate, 1,5-pentanediol diacrylate, and hexamethylenebisacrylamide.

8. The method according to claim 1, characterized in that, The solution I containing the anti-rigid colorimetric fluorescent molecular probe further includes solvent II, which is selected from at least one of toluene, dichloromethane, chloroform, tetrahydrofuran, acetone, ethyl acetate, n-hexane, diethyl ether, chlorobenzene, o-dichlorobenzene, and 1,4-dioxane.

9. The method according to claim 1, characterized in that, The mass ratio of the polymer monomer molecules to the photoinitiator I is 600:1 to 1600:1, wherein the mass of the polymer monomer molecules is based on the mass of the polymer monomer molecules themselves, and the mass of the photoinitiator I is based on the mass of the photoinitiator I itself.

10. The method according to claim 9, characterized in that, The mass ratio of the polymer monomer molecules to the crosslinking agent is 50:1 to 150:1, wherein the mass of the polymer monomer molecules is based on the mass of the polymer monomer molecules themselves, and the mass of the crosslinking agent is based on the mass of the crosslinking agent itself.

11. The method according to claim 1, characterized in that, The conditions for photoinitiated polymerization are: light power of 8~200W, light wavelength of 250~420nm, and light irradiation time of 5~60 minutes.

12. The method according to claim 1, characterized in that, The conditions for photoinitiated polymerization are: light power of 18W, light wavelength of 365 nm, and light irradiation time of 40-50 minutes.

13. The method according to claim 1, characterized in that, In solution I containing the anti-rigid chromogenic fluorescent molecular probe, the concentration of the anti-rigid chromogenic fluorescent molecular probe is 2.5 × 10⁻⁶. -5 mol / L ~ 7.5 × 10 -4 mol / L.

14. The method according to claim 1, characterized in that, In solution I containing the anti-rigid chromogenic fluorescent molecular probe, the concentration of the anti-rigid chromogenic fluorescent molecular probe is 2.5 × 10⁻⁶. -4 mol / L.

15. The method according to claim 1, characterized in that, The molar ratio of the anti-rigid-chromic fluorescent molecular probe to the polymer monomer molecules is 1:1000 to 1:1000000, wherein the number of moles of the anti-rigid-chromic fluorescent molecular probe is calculated based on the number of moles of the anti-rigid-chromic fluorescent molecular probe, and the number of moles of the polymer monomer molecules is calculated based on the number of moles of the polymer monomer molecules themselves. The soaking time for I is 3-10 minutes; The wavelength of the ultraviolet light I is 250~420 nm.

16. The method according to claim 1, characterized in that, The wavelength of the ultraviolet light I is 365nm.

17. A method for preventing counterfeiting based on changes in the free volume of polymers, characterized in that, The anti-counterfeiting method achieves anti-counterfeiting by using a patterned liquid crystal film I under visible light. The method for preparing the patterned liquid crystal thin film I includes: (1) Preparation of polymer thin film layer; (2) A solution II containing liquid crystal monomer, chiral inducer, photoinitiator II, and anti-rigid color-changing fluorescent molecular probe is heated I and loaded onto one side of the polymer thin film layer to obtain liquid crystal thin film layer II; (3) Under the condition of using a photomask, a patterned liquid crystal film I is formed under the irradiation of ultraviolet light II; The fluorescence emission of the aforementioned anti-rigid-chromic fluorescent molecular probe exhibits a significant redshift as the free volume of the polymer decreases.

18. The method according to claim 17, characterized in that, The liquid crystal monomer is selected from acrylate derivatives whose side groups contain phenyl ester functional groups.

19. The method according to claim 17, characterized in that, The liquid crystal monomer is selected from at least one of RM105, RM257, RM23, RM82, and C6M.

20. The method according to claim 17, characterized in that, The chiral inducer is selected from one of S811, R811, S5011, R-1011 and S-1011.

21. The method according to claim 17, characterized in that, The photoinitiator II is selected from at least one of 2,4,6-trimethylbenzoylphenylphosphonate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and α,α-dimethoxy-α-phenylacetophenone.

22. The method according to claim 17, characterized in that, Solution II further includes an organic solvent selected from at least one of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, diethyl ether ethanol, and methanol.

23. The method according to claim 17, characterized in that, The thickness of the liquid crystal thin film layer II is 30~80μm.

24. The method according to claim 17, characterized in that, The thickness of the liquid crystal thin film layer II is 39~45 μm.

25. The method according to claim 17, characterized in that, The patterned liquid crystal film I is a cholesteric liquid crystal film.

26. The method according to claim 25, characterized in that, When the patterned liquid crystal film I is a cholesteric liquid crystal film, the liquid crystal monomers include RM105 and RM257, and the chiral inducer is S811, wherein the mass ratio of RM105, RM257 and S811 is 1:1~2:0.5~0.

9.

27. The method according to claim 17, characterized in that, In solution II, the mass fraction of photoinitiator II is 0.1~5 wt%, and the mass fraction of anti-rigid color-changing fluorescent molecular probe is 0.005~0.5 wt%.

28. The method according to claim 17, characterized in that, In solution II, the mass ratio of liquid crystal monomer, chiral inducing agent, photoinitiator II, and anti-rigid color-changing fluorescent molecular probe is 1:0.2~0.3:0.001~0.01:0.0005~0.001; The temperature of heating element I is 60 ℃~85 ℃.

29. The method according to claim 17, characterized in that, The temperature of heating I is 72~78 ℃; the heating time of heating I is 6~8h.

30. The method according to claim 17, characterized in that, In step (3), the power of the ultraviolet light II is 8~50W; The wavelength of the ultraviolet light II is 250~420 nm; The irradiation time of the ultraviolet II light is 30 to 60 minutes.

31. The method according to claim 17, characterized in that, In step (3), the power of the ultraviolet light II is 15~25 W; The wavelength of the ultraviolet light II is 365 nm; The irradiation time of the ultraviolet light II is 50 minutes.

32. The method according to claim 17, characterized in that, The anti-counterfeiting method includes the following steps: (1) Spin-coating an aqueous solution containing polymer onto glass slide I, and heating II to form a polymer thin film layer on glass slide I; (2) Cover the polymer film layer with glass slide II to form a unit consisting of glass slide II, polymer film layer, and glass slide I; (3) The solution II containing liquid crystal monomer, photoinitiator II and anti-rigid color-changing fluorescent molecular probe is heated to I and then filled into the gap between the glass slide II and the polymer film layer. (4) A patterned photomask is attached to the side of the glass slide II away from the polymer film layer, and a patterned liquid crystal film I is formed under the irradiation of ultraviolet light II.

33. The method according to claim 32, characterized in that, In step (1), the polymer is selected from one of polyvinyl alcohol, polyimide, and polyvinylpyrrolidone solution; The polymer-containing aqueous solution has a polymer mass fraction of 0.5 to 10 wt%.

34. The method according to claim 32, characterized in that, In step (1), the polymer in the aqueous solution contains 1 wt% polymer.

35. The method according to claim 32, characterized in that, The spin coating speed is 1500~2000 rpm.

36. The method according to claim 32, characterized in that, The spin coating speed is 1600 rpm.

37. The method according to claim 32, characterized in that, The heating time II is 60 minutes to 180 minutes, and the heating temperature II is 100 to 130°C.

38. The method according to claim 32, characterized in that, The heating time for heating II is 120 minutes, and the temperature of heating II is 110°C.

39. The method according to claim 1 or 17, characterized in that, The anti-rigid color-changing fluorescent molecular probe is selected from compounds having at least one of the structural formulas M1 to M20; Wherein, the R1 substituent group is selected from at least one of H, C1-20 alkyl, C1-6 alkyl halide, C1-6 alkyl primary amine, C1-6 alkyl secondary amine, C1-6 alkyl tertiary amine, and C1-6 quaternary ammonium salt; The R2 substituent group is selected from at least one of H, C1-12 alkyl, cyano, halogen, amino, methylamino, C0-4 alkyl secondary amine, C0-4 alkyl tertiary amine, and C0-4 quaternary ammonium salt; In formula M2, X is selected from at least one of N, P, and As, and Y is selected from at least one of H and halogen atoms; In formulas M10 to M17, X is N or C; when X is N, R2 is a monosubstituted group; when X is C, R2 is a disubstituted group. In formulas M15 to M17, R is selected from at least one of H, halogen atoms, benzene rings and their derivatives, thiophene and its derivatives, furan and its derivatives, cyclohexane, pyridine, and pyrrole.

40. The method according to claim 39, characterized in that, The preparation method of the inverse rigid color-changing fluorescent molecular probe includes the following steps: (1) A mixture containing compound 1, compound 2, weak base and solvent III is contacted with catalyst I under inactive atmosphere conditions, and Suzuki coupling reaction is carried out to passivate I and obtain compound 3. (2) The mixture containing compound 3 and POCl3 was contacted with P2O5 under an inactive atmosphere and subjected to Bischler-Napieralski reaction to passivate II, thus obtaining the anti-rigid color-changing fluorescent molecular probe.

41. The method according to claim 40, characterized in that, In step (1), the weak base is selected from at least one of K2CO3, NaHCO3, and Cs2CO3; The compound 1 has the structure shown in Formula I; Compound 2 has the structure shown in Formula II; Compound 3 has the structure shown in Formula III; AryI is derived from at least one of anthracene, diphenylamine, triphenylamine, indole, triaconazole, and triaconfluorene compounds; The R' substituent group is selected from at least one of halogen and pinacol borate ester group; The R1 substituent is selected from at least one of H, C1-20 alkyl, C1-6 alkyl halide, C1-6 alkyl primary amine, C1-6 alkyl secondary amine, C1-6 alkyl tertiary amine, and C1-6 quaternary ammonium salt; The R2 substituent is selected from at least one of H, C1-12 alkyl, cyano, halogen, amino, methylamino, C0-4 alkyl secondary amine, C0-4 alkyl tertiary amine, and C0-4 quaternary ammonium salt.

42. The method according to claim 40, characterized in that, in, When the anti-rigid-chromic fluorescent molecular probe is a compound with the structure of formula M1, compound 1 has the structure shown in formula N1; When the anti-rigid color-changing fluorescent molecular probe is a compound with the structure of formula M2, compound 1 has the structure shown in formula N2, wherein X is selected from at least one of N, P, and As, and Y is selected from at least one of H, F, Cl, Br, and I; When the anti-rigid-chromic fluorescent molecular probe is a compound with the structure described in formula M3, compound 1 has the structure shown in formula N3; When the anti-rigid color-changing fluorescent molecular probe is a compound with the structure of any one of formulas M4 to M9, compound 1 has the structure shown in formula N4, wherein one of Y1, Y2, Y3, and Y4 is Br, and the other three are H; When the anti-rigid color-changing fluorescent molecular probe is a compound with the structure of any one of formulas M10 to M20, compound 1 has the structure shown in formula N5, wherein X is selected from N or C, one of Y1, Y2, Y3, and Y4 is Br, and the other three are H; 。 43. The method according to claim 40, characterized in that, Solvent III is a mixed solvent of tetrahydrofuran and water, wherein the volume ratio of tetrahydrofuran to water is 5~12:1; The inactive atmosphere is selected from either nitrogen or argon. The catalyst I is selected from at least one of Pd(PPh3)4, Pd(PPh3)2Cl2, PdCl2, PPh3, n-Bu3P, (MeO)3P, (o-tol)3P, AsPh3, Ph2P(CH2)2PPh2(dppe), and Ph2P(CH2)3PPh2(dppp); The temperature of the Suzuki coupling reaction is 85~90℃, and the time of the Suzuki coupling reaction is 48~72h; The molar ratio of compound 1, compound 2, catalyst I, and weak base is 1:1~6:0.01~0.05:10~50.

44. The method according to claim 40, characterized in that, In the mixture, the concentration of compound I is 0.01~0.05 mol / L; The parameters for passivation I are: reaction temperature of 80~90 ℃ and reaction time of 24~72 h; The parameters for passivation II are: reaction temperature of 100~120℃ and reaction time of 14~18h; The molar ratio of compound 3 to P2O5 is 1:10 to 1:30; The mass ratio of compound 3 to POCl3 is 1:20 to 1:

160.

45. The method according to claim 40, characterized in that, The Bischler-Napieralski reaction was carried out at a temperature of 110-120°C for 14-18 hours.

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