Optically switchable multi-state fluorescent supramolecular polymers for multiple data encryption

Abstract

The present invention discloses a method for applying a light-switch multi-state fluorescent supramolecular polymer to multiple data encryption. Methyl methacrylate, butyl acrylate, polymerizable photochromic diarylethene, polymerizable adamantane, and azobisisobutyronitrile are used as raw materials, and a free radical copolymerization method is adopted to prepare a light-switch guest polymer and a guest polymer; photochromic spiropyran and β-cyclodextrin are used as raw materials to prepare a light-switch main molecule. The guest polymer and the main molecule are further combined by the host and the guest to obtain three supramolecular polymers, which are respectively coated on a fan-shaped glass sheet to obtain a data encryption unit a, a data encryption unit b, and a data encryption unit c, which are arranged and combined for multiple information encryption applications. The light-switch multi-state fluorescent supramolecular polymer prepared by the present invention has high contrast, fast light responsiveness, good light reversibility and good processability, and is simple to synthesize and low in cost, and has great application prospects in the fields of anti-counterfeiting and information encryption.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical materials, and in particular relates to a method for applying optical switch multi-state fluorescent supramolecular polymer to multiple data encryption. Background Art

[0002] In recent years, stimuli-responsive fluorescent materials have been widely used in biosensors, bioimaging, anti-counterfeiting and information encryption because their luminescence is sensitive to environmental stimuli. The response of stimuli-responsive fluorescent materials to light, temperature, pressure, ions, acid, alkali and humidity has been widely studied. Compared with other types of stimuli-responsive fluorescent materials, photoswitchable fluorescent systems with light-triggered mechanisms have the advantages of remote control, no waste, and high spatial and temporal resolution.

[0003] At present, photoswitchable systems with multi-state fluorescence transitions are an important technology for realizing advanced anti-counterfeiting and multi-layer information storage. Obviously, photoswitchable multi-state fluorescence systems have greater development potential than monochromatic fluorescent materials or photoswitchable two-color fluorescence systems. Generally speaking, photoswitchable multi-state fluorescence systems can be constructed by adding fluorescent dyes and various fluorescent photochromics (such as spiropyran and diarylethene). In recent years, some photoswitchable multi-state fluorescence systems, such as organic binary molecules, doped polymer nanoparticles and copolymer films, have been reported. These photoswitchable multi-state fluorescence systems show obvious multiple fluorescence changes under different light stimuli, showing great potential in information encryption, anti-counterfeiting and optical data storage. Although these photoswitchable multi-state fluorescence systems have been developed, it is still very important to explore the preparation of high-performance photoswitchable multi-state fluorescence systems to enrich photoswitchable multi-state fluorescence systems. In addition, the current photoswitchable multi-state fluorescence systems also encounter problems such as cumbersome synthesis (organic molecules), low structural stability and poor processability (doped polymer nanoparticles), or lack of flexibility in adjusting optical properties (copolymer films) in applications.

[0004] Supramolecular polymers are widely used to construct stimuli-responsive fluorescent materials due to their excellent reversibility and sensitive response to external stimuli. Such materials are widely used in display, sensor and information encryption. In addition, supramolecular interactions include host-guest interactions, ligand-metal complexation, π-π stacking, ionic interactions and hydrogen bonding, which can not only provide flexible optical performance adjustment, but also have good self-assembly ability and potential self-healing ability. Therefore, supramolecular polymers may become an ideal material platform for constructing new photoswitchable multistate fluorescent systems with more comprehensive performance. However, the feasibility of constructing photoswitchable multistate fluorescent supramolecular polymers using supramolecular polymers and fluorescence photochromic technology has not been explored.

[0005] Therefore, inventing a novel photoswitchable multistate fluorescent supramolecular polymer that is simple, low-cost, has convenient and adjustable luminescence properties, and has photoswitchable multistate fluorescence capabilities has considerable practical significance and application prospects. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for applying a light-switchable multi-state fluorescent supramolecular polymer to multiple data encryption. To solve the above technical problem, the basic concept of the technical solution adopted by the present invention is:

[0007] 1. The preparation of data encryption unit a includes the following steps:

[0008] (1.1) Methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl 3-(3,3,4,4,5,5-hexafluoro-2-(2-methyl-1,1-dioxybenzo[b]thiophen-3-yl)cyclopent-1-ene-1-yl)-2-methylbenzo[b]thiophene-6-carboxylate 1,1-dioxide (SDTE), 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile are dissolved in an appropriate amount of dry toluene solution at a mass ratio of 1:0.1 to 1:0.01 to 0.1:0.01 to 0.1:0.01 to 0.05;

[0009] (1.2) stirring the solution prepared in step (1.1) in an ice bath while evacuating and filling with nitrogen. This process is repeated three times until the mixed solution is finally in a nitrogen-protected state;

[0010] (1.3) The mixed solution obtained in step (1.2) was heated to 70°C and stirred for 24 hours;

[0011] (1.4) After the reaction in step (1.3) is completed, the reaction solution is rapidly cooled and then precipitated in methanol. The precipitate is vacuum dried to obtain a light-switchable green fluorescent polymer; the structure of the polymer is as follows:

[0012]

[0013] The ratio of m, n, y, and z is 1: 0.05 to 1: 0.005 to 0.1: 0.005 to 0.1;

[0014] (1.5) placing the optically switchable green fluorescent polymer and β-cyclodextrin in a mixed solution of dichloromethane and methanol at a mass ratio of 1:0.01-0.2;

[0015] (1.6) ultrasonicating the mixed solution obtained in step (1.5) for 30 minutes and stirring for 6 hours to obtain a light-switchable green fluorescent supramolecular polymer SP-1 solution;

[0016] (1.7) Apply the optically switchable green fluorescent supramolecular polymer SP-1 solution on a fan-shaped glass sheet to obtain a data encryption unit a.

[0017] 2. The preparation of the data encryption unit b includes the following steps:

[0018] (2.1) dissolving methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile in a proper amount of dry toluene solution at a mass ratio of 1:0.1 to 1:0.01 to 0.1:0.01 to 0.05;

[0019] (2.2) stirring the solution prepared in step (2.1) in an ice bath while evacuating and filling with nitrogen. This process is repeated three times until the mixed solution is finally in a nitrogen-protected state;

[0020] (2.3) The mixed solution obtained in step (2.2) was heated to 70°C and stirred for 24 hours;

[0021] (2.4) After the reaction in step (2.3) is completed, the reaction solution is rapidly cooled and then precipitated in methanol. The precipitate is vacuum dried to obtain a non-fluorescent polymer; its structure is as follows:

[0022]

[0023] The ratio of m, n, and y is 1:0.05 to 1:0.005 to 0.1;

[0024] 3-(3',3'-dimethyl-6-nitrospiro[pyran-2,2'-indoline]-1'-yl) propionic acid (SPCOOH) and β-cyclodextrin are mixed at a mass ratio of 1:0.5-5, and then esterified to obtain a light-switchable red fluorescent molecule;

[0025] (2.5) placing the non-fluorescent polymer and the photoswitchable red fluorescent molecule in a mixed solution of dichloromethane and methanol, wherein the mass ratio of the non-fluorescent polymer to the photoswitchable red fluorescent molecule is 1:0.01-0.2;

[0026] (2.6) ultrasonicating the mixed solution obtained in step (2.5) for 30 minutes and stirring for 6 hours to obtain a light-switchable red fluorescent supramolecular polymer SP-2 solution;

[0027] (2.7) Apply the optically switchable red fluorescent supramolecular polymer SP-2 solution on a fan-shaped glass sheet to obtain a data encryption unit b.

[0028] 3. The preparation of the data encryption unit c includes the following steps:

[0029] (3.1) placing the photo-switchable green fluorescent polymer and the photo-switchable red fluorescent molecule obtained in step (1.4) in a mixed solution of dichloromethane and methanol, wherein the mass ratio of the photo-switchable green fluorescent polymer to the photo-switchable red fluorescent molecule is 1:0.01-0.2;

[0030] (3.2) ultrasonicating the mixed solution obtained in step (3.1) for 30 minutes and stirring for 6 hours to obtain a light-switchable multi-state fluorescent supramolecular polymer SP-3 solution;

[0031] (3.3) Apply the optically switchable multi-state fluorescent supramolecular polymer SP-3 solution on a fan-shaped glass sheet to obtain a data encryption unit c.

[0032] 4. Take data encryption units a, b and c, arrange and combine them according to requirements, and can be used for multiple data encryption.

[0033] The preparation of the data encryption unit a described above, the 4-(acryloyloxy)butyl 3-(3,3,4,4,5,5-hexafluoro-2-(2-methyl-1,1-dioxidobenzo[b]thiophene-3-yl)cyclopent-1-ene-1-yl)-2-methylbenzo[b]thiophene-6-carboxylate 1,1-dioxide (SDTE) in the step (1.1) has the following structure:

[0034]

[0035] In the preparation of the above-mentioned data encryption unit b, the structure of the light-switchable red fluorescent molecule in step (2.5) is as follows:

[0036]

[0037] After adopting the above technical scheme, the present invention has the following beneficial effects compared with the prior art.

[0038] (1) Based on the principle of fluorescence resonance energy transfer (FRET), the present invention successfully prepared a photoswitchable multi-state fluorescent supramolecular polymer using a host-guest combination method.

[0039] (2) The optically switchable multi-state fluorescent supramolecular polymer prepared by the present invention can exhibit reversible switching between three states: none, red, and green.

[0040] (3) The three optically switchable fluorescent supramolecular polymers prepared in the present invention can exhibit fast and reversible fluorescent switching characteristics under the irradiation of ultraviolet light and visible light of different wavelengths, and have very important application prospects in high-end data encryption and anti-counterfeiting.

[0041] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The accompanying drawings are part of this application and are used to provide a further understanding of the present invention. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but do not constitute an improper limitation of the present invention. Obviously, the drawings described below are only some embodiments. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. In the drawings:

[0043] Figure 1 This is the NMR titration diagram of the prepared supramolecular polymer.

[0044] Figure 2 UV-visible absorption spectrum of the prepared supramolecular polymer solution under different external light effects.

[0045] Figure 3 This is the fluorescence emission spectrum of the prepared supramolecular polymer film under different external light effects.

[0046] Figure 4 This is the reversible response cycle diagram of the diarylethene part in the prepared supramolecular polymer film to ultraviolet light and visible light.

[0047] Figure 5 This is the reversible response cycle diagram of the spiropyran part in the prepared supramolecular polymer film to ultraviolet light and visible light.

[0048] Figure 6 The prepared supramolecular polymers are applied in data encryption graphs.

[0049] It should be noted that these drawings and textual descriptions are not intended to limit the conceptual scope of the present invention in any way, but are intended to illustrate the concept of the present invention for those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. The following embodiments are used to illustrate the present invention but are not used to limit the scope of the present invention.

[0051] Example 1: Preparation of data encryption unit a, the specific steps are as follows:

[0052] Dissolve 0.3g of methacrylic acid, 0.256g of butyl acrylate, 0.012g of SDTE, 0.015g of BAC, and 0.0082g of AIBN in 1mL of dry toluene, vacuum-fill and nitrogen-fill three times, and react at 70°C under nitrogen protection for 24h. After the reaction is completed, cool the reaction solution to room temperature, precipitate in methanol, and vacuum dry at 30°C overnight to obtain a light-switchable green fluorescent polymer. Place 0.025g of the light-switchable green fluorescent polymer and 0.0016g of β-cyclodextrin in a mixed solution of dichloromethane and methanol, ultrasonicate for 30min and stir for 6h to obtain a light-switchable green fluorescent supramolecular polymer SP-1 solution. It can be used as a data encryption unit a.

[0053] Embodiment 2: Preparation of data encryption unit b, the specific steps are as follows:

[0054] Dissolve 0.3g of methacrylic acid, 0.256g of butyl acrylate, 0.015g of BAC, and 0.0082g of AIBN in 1mL of dry toluene, evacuate and fill with nitrogen three times, and react under nitrogen protection at 70°C for 24h. After the reaction is completed, cool the reaction solution to room temperature, precipitate in methanol, and vacuum dry overnight at 30°C to obtain a non-fluorescent polymer. Place 0.025g of non-fluorescent polymer and 0.0023g of light-switch red molecule in a mixed solution of dichloromethane and methanol, ultrasonicate for 30min and stir for 6h to obtain a light-switch red fluorescent supramolecular polymer SP-2 solution. It can be used as data encryption unit b.

[0055] Embodiment 3: Preparation of data encryption unit c, the specific steps are as follows:

[0056] Dissolve 0.3g of methacrylic acid, 0.256g of butyl acrylate, 0.012g of SDTE, 0.015g of BAC, and 0.0082g of AIBN in 1mL of dry toluene, evacuate and fill with nitrogen three times, and react at 70°C under nitrogen protection for 24h. After the reaction is completed, cool the reaction solution to room temperature, precipitate in methanol, and vacuum dry overnight at 30°C to obtain a light-switchable green fluorescent polymer. Place 0.025g of the light-switchable green fluorescent polymer and 0.0022g of the light-switchable red molecule in a mixed solution of dichloromethane and methanol, ultrasonicate for 30min and stir for 6h to obtain a light-switchable multi-state fluorescent supramolecular polymer SP-3 solution. It can be used as a data encryption unit c.

[0057] Example 4: Preparation of a light-switchable green fluorescent polymer film, the specific steps are as follows:

[0058] The photoswitchable green fluorescent supramolecular polymer SP-1 solution obtained in Example 1 is coated on a fan-shaped glass sheet to obtain a photoswitchable green fluorescent polymer film.

[0059] Example 5: Preparation of a light-switchable red fluorescent polymer film, the specific steps are as follows:

[0060] The light-switchable red fluorescent supramolecular polymer SP-2 solution obtained in Example 2 is coated on a fan-shaped glass sheet to obtain a light-switchable red fluorescent polymer film.

[0061] Example 6: Preparation of a light-switchable multi-state fluorescent polymer film, the specific steps are as follows:

[0062] The optically switchable multi-state fluorescent supramolecular polymer SP-3 solution obtained in Example 3 is coated on a fan-shaped glass sheet to obtain an optically switchable multi-state fluorescent polymer film.

[0063] Example 7: Testing supramolecular polymer nuclear magnetic titration diagram

[0064] Figure 1 This is the NMR titration diagram of the optically switchable multi-state fluorescent supramolecular polymer prepared in Example 3. Figure 1 It can be seen that with the increase of the main β-cyclodextrin, the chemical shift of adamantane will change. A linear fit is performed on it, showing a good linear effect. From the linear relationship diagram of the two, it can be seen that the binding constant of the supramolecular polymer is 95M -1 .

[0065] Example 8: Testing the UV-visible absorption spectrum of the prepared supramolecular polymer solution under different external light effects.

[0066] Figure 2 The UV-visible absorption spectra of the optically switchable multi-state fluorescent supramolecular polymer prepared in Example 3 under different external light effects. Figure 2 It can be seen that in the initial state, there is no absorption peak between 350-450nm. Under 365nm ultraviolet light irradiation, the absorption peak of spiropyran appears at 560nm. Then, under 254nm ultraviolet light irradiation, the obvious characteristic absorption peak of diarylethene appears at 410nm. After irradiation with 525nm visible light, the absorption characteristic peak of spiropyran disappears. Finally, under 460nm visible light irradiation, the absorption characteristic peak of diarylethene disappears.

[0067] Example 9: Testing the fluorescence emission spectra of supramolecular polymer films under different external light effects.

[0068] Figure 3 This is the fluorescence emission spectrum of the optical switchable multi-state fluorescent supramolecular polymer film prepared in Example 3 under the action of different external lights. Figure 3It can be seen that under 365nm ultraviolet light irradiation, the emission peak of spiropyran appears at 655nm. Then, under the sequential irradiation of 254nm ultraviolet light and 525nm visible light, the emission peak of diarylethene appears at 495nm. Finally, under the irradiation of 460nm visible light, the emission peak of diarylethene disappears.

[0069] Example 10: Testing the reversible response cycle diagram of the diarylethene part in the prepared supramolecular polymer film to ultraviolet light and visible light.

[0070] Figure 4 This is a reversible response cycle diagram of the diarylethene part in the optical switchable multi-state fluorescent supramolecular polymer film prepared in Example 3 to ultraviolet light and visible light. Figure 4 It can be seen that the fluorescence intensity changes of the optically switchable multi-state fluorescent supramolecular polymer film at 495nm were tested after multiple alternating irradiations of 254nm ultraviolet light, 525nm visible light and 460nm visible light. The results show that the diarylethene part in the polymer film still has good reversible fluorescence switching performance after 17 optical switching cycle tests.

[0071] Example 11: Testing the reversible response cycle diagram of the spiropyran part in the prepared supramolecular polymer film to ultraviolet light and visible light.

[0072] Figure 5 This is a reversible response cycle diagram of the spiropyran part in the optically switchable multi-state fluorescent supramolecular polymer film prepared in Example 3 to ultraviolet light and visible light. Figure 5 It can be seen that the fluorescence intensity changes of the optically switchable multi-state fluorescent supramolecular polymer film at 655nm were tested after multiple alternating irradiation with 365nm ultraviolet light and 525nm visible light. The results show that the spiropyran part in the polymer film still has good reversible fluorescence switching performance after 10 optical switching cycle tests.

[0073] Example 12: Data encryption experiment

[0074] Take the polymer films obtained in Examples 4, 5, and 6, namely, data encryption units a, b, and c, respectively, and arrange and combine them according to requirements. Figure 6As shown, the non-fluorescence state is defined as "0"; the green fluorescence state is defined as "1"; and the red fluorescence state is defined as "2". Then, according to the normal order, code book 1 (Table 1) is obtained, and code book 2 (Table 2) is obtained by random arrangement. In the absence of any ultraviolet irradiation, all sector-shaped discs are in a non-fluorescence emission state, indicating that they are in an encrypted state. Under the irradiation of 365nm ultraviolet light, encryption unit B and encryption unit C will turn into red emission. After corresponding their fluorescence emission states to different data combinations, the corresponding code books 1 and 2 are consulted to obtain the first-layer decryption information "hzb" and "boy". Then, under the sequential irradiation of 254nm ultraviolet light and 525nm visible light, encryption unit A and encryption unit C turn into green emission, and encryption unit B turns into a non-fluorescence emission state. After corresponding their fluorescence emission states to different data combinations, the corresponding code books 1 and 2 are consulted to obtain the second-layer decryption information "jam" and "man". On the other hand, it is possible to directly switch from the encryption state to the second-layer decryption state under specific light irradiation. Combined with Figure 6 ,The above results indicate that the polymer can be well applied to ,visible multiple data encryption under UV light and visible light.

[0075] Table 1 Codebook 1

[0076]

[0077]

[0078] Table 2 Codebook 2

[0079]

[0080] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this patent can make some changes or modify the technical contents suggested above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the solution of the present invention.

Claims

1. A method for applying a light-switchable multi-state fluorescent supramolecular polymer to multiple data encryption, characterized in that: The following steps are involved: Step 1, preparation of data encryption unit a: prepare a light-switchable green fluorescent supramolecular polymer SP-1 according to the host-guest combination method, and apply the solution on a fan-shaped glass sheet to obtain a data encryption unit a, which specifically includes: Step 1.1, methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl 3-(3,3,4,4,5,5-hexafluoro-2-(2-methyl-1,1-dioxybenzo[b]thiophen-3-yl)cyclopent-1-ene-1-yl)-2-methylbenzo[b]thiophene-6-carboxylate 1,1-dioxide (SDTE), 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile are mixed in proportion and subjected to free radical copolymerization to obtain a photoswitchable green fluorescent polymer; Step 1.2, after mixing the photoswitchable green fluorescent polymer and β-cyclodextrin in proportion, the host and the guest are combined to obtain the photoswitchable green fluorescent supramolecular polymer SP-1; Step 1.3, applying the optical switch green fluorescent supramolecular polymer SP-1 solution on the fan-shaped glass sheet to obtain the corresponding data encryption unit a; Step 2, preparation of data encryption unit b: prepare a light-switchable red fluorescent supramolecular polymer SP-2 according to the host-guest combination method, and apply the solution on a fan-shaped glass sheet to obtain a data encryption unit b, which specifically includes: Step 2.1, methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile are mixed in proportion, and free radical copolymerization is performed to obtain a non-fluorescent polymer; Step 2.2, 3-(3',3'-dimethyl-6-nitrospiro[pyran-2,2'-indoline]-1'-yl) propionic acid (SPCOOH) and β-cyclodextrin are mixed in proportion and esterified to obtain a light-switchable red fluorescent molecule, the structural formula of which is as follows: Step 2.3, after mixing the non-fluorescent polymer and the photoswitchable red fluorescent molecule in proportion, the host and the guest are combined to obtain the photoswitchable red fluorescent supramolecular polymer SP-2; Step 2.4, applying the light switch red fluorescent supramolecular polymer SP-2 solution on the fan-shaped glass sheet to obtain the corresponding data encryption unit b; Step 3, preparation of data encryption unit c: prepare the optical switch multi-state fluorescent supramolecular polymer SP-3 according to the host-guest combination method, and apply the solution on a fan-shaped glass sheet to obtain the data encryption unit c, which specifically includes: Step 3.1, mixing the photoswitchable green fluorescent polymer and the photoswitchable red fluorescent molecule at a mass ratio of 1:0.01-0.2, and combining the host and the guest to obtain the photoswitchable multi-state fluorescent supramolecular polymer SP-3; Step 3.2, applying the optical switch multi-state fluorescent supramolecular polymer SP-3 solution on the fan-shaped glass sheet to obtain the corresponding data encryption unit c; Step 4: Data encryption unit a, data encryption unit b, and data encryption unit c are arranged and combined for data encryption.

2. The method for applying the optically switchable multi-state fluorescent supramolecular polymer to multiple data encryption according to claim 1, characterized in that: The structure of the photoswitchable green fluorescent polymer in step 1.1 is as follows: Among them, the ratio of m, n, y, and z is 1:0.05~1:0.005~0.1:0.005~0.

1.

3. The method for applying the optically switchable multi-state fluorescent supramolecular polymer to multiple data encryption according to claim 1, characterized in that: In the step 1.1, the mass ratio of methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl 3-(3,3,4,4,5,5-hexafluoro-2-(2-methyl-1,1-dioxybenzo[b]thiophene-3-yl)cyclopent-1-ene-1-yl)-2-methylbenzo[b]thiophene-6-carboxylate 1,1-dioxide (SDTE), 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile is 1:0.1-1:0.01-0.1:0.01-0.1:0.01-0.05; In the step 1.2, the mass ratio of the photoswitchable green fluorescent polymer to β-cyclodextrin is 1:0.01-0.

2.

4. The method for applying the optically switchable multi-state fluorescent supramolecular polymer to multiple data encryption according to claim 1, characterized in that: The structure of the non-fluorescent polymer in step 2.1 is as follows: Among them, the ratio of m, n, and y is 1:0.05~1:0.005~0.

1.

5. The method for applying the optically switchable multi-state fluorescent supramolecular polymer to multiple data encryption according to claim 1, characterized in that: In the step 2.1, the mass ratio of methacrylic acid, butyl acrylate, 4-(acryloyloxy)butyl-adamantane-1-carboxylate (BAC), and azobisisobutyronitrile is 1:0.1-1:0.01-0.1:0.01-0.05; In the step 2.2, the mass ratio of 3-(3',3'-dimethyl-6-nitrospiro[pyran-2,2'-indoline]-1'-yl)propionic acid (SPCOOH) to β-cyclodextrin is 1:0.5-5.

6. The method for applying the optically switchable multi-state fluorescent supramolecular polymer to multiple data encryption according to claim 1, characterized in that: In the photoswitchable red fluorescent supramolecular polymer SP-2 obtained in step 2.3, the mass ratio of the non-fluorescent polymer to the photoswitchable red fluorescent molecule is 1:0.01-0.2.

Images