Preparation method and application of supramolecular polymer with adjustable optical switch fluorescence and 3D structure
By preparing the super molecular polymer with the fluorescence and 3D structured structure, combined with the 3D spatial structure anti -counterfeiting and photoretic fluorescence and anti -counterfeiting, the positive control of the light, thermal, and force stimulus solves the anti -counterfeiting safety in existing technologies. Insufficient problems achieved high security dual -modal anti -counterfeiting effects.
Patent Information
- Application Number
- CN202411331030.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-24
- Publication Date
- 2025-01-21
AI Technical Summary
In the prior art, the security of a single anti-counterfeiting method is insufficient, and the dual-mode anti-counterfeiting system cannot achieve mutual coupling and independent response, making it difficult to effectively prevent unauthorized imitation or copying.
By preparing a super molecular polymer that can adjust the fluorescence and 3D structured 3D structures, combined with the 3D space structure anti -counterfeiting and photoretic fluorescent anti -counterfeiting, realize the orthogonal of fluorescence signals and 3D space structure information in specific areas. Regulate.
It achieves improved anti-counterfeiting safety while being simple to prepare, stimulating means do not affect each other, and has excellent tensile properties, anti-fouling properties and stability in strong acid or alkali environments.
Smart Images
Figure CN119331175A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of chemical material preparation and application, and in particular, relates to a preparation method and application of a supramolecular polymer with adjustable optical switch fluorescence and 3D structure. Background Art
[0002] The market demand for anti-counterfeiting technology is expanding, and scientific researchers are investing more and more in the research and development of the anti-counterfeiting field. Researchers have explored various anti-counterfeiting strategies, such as traditional watermarks, optical switch fluorescence, barcodes and QR codes, etc., as well as emerging 3D structural anti-counterfeiting methods including apparent wrinkles, three-dimensional coding, lens anti-counterfeiting and three-dimensional holographic anti-counterfeiting, etc. However, as far as the current situation is concerned, the anti-counterfeiting of a single method has problems such as simple encryption and low security, and the degree of crackdown is still not strong enough. Therefore, in order to prevent imitation or copying without the owner's permission and avoid unnecessary economic losses, it is very necessary to create anti-counterfeiting technology with high security.
[0003] Based on this, coupling traditional anti-counterfeiting technology and 3D spatial structure anti-counterfeiting technology on the same material to achieve dual-modal anti-counterfeiting is an ideal way to improve security. In general, there are some reports on dual-modal anti-counterfeiting (ACSMacro Lett., 2018, 7, 540-545, Nat. Commun., 2023, 14, 7131). Systems that respond independently to each other cannot achieve mutual coupling, and mutually coupled systems cannot achieve independent responses to each other.
[0004] In view of this, the present invention is proposed. Summary of the invention
[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art, provide a preparation method and application of supramolecular polymers with adjustable photoswitch fluorescence and 3D structure, couple 3D spatial structure anti-counterfeiting and photoswitch fluorescence anti-counterfeiting, and realize anti-counterfeiting materials with orthogonal regulation of fluorescence signals and 3D spatial structure information in a specific area under light, heat and force stimulation. While improving anti-counterfeiting security, the preparation is simple and the stimulation means will not affect each other, which has quite important practical significance and application prospects. The optical switch molecule is prepared according to the existing technology (Sci. China Mater., 2023, 66,1949-1958. CN202210548000.X, Angew. Chem. Int. Ed. 2024, e202414846,CN202311833788.X). The anti-counterfeiting label prepared by the optical switch supramolecular fluorescent polymer not only has multiple reversible fluorescence switching performance under alternating irradiation of ultraviolet light and visible light, but also its 3D structure can also achieve multiple reversible switching under the action of temperature and pressure, showing excellent tensile properties, anti-fouling properties and excellent stability in strong acid or strong alkali environments.
[0006] In order to solve the above technical problems, the basic concept of the technical solution adopted by the present invention is: Preparation of a supramolecular polymer with photoswitchable fluorescence and 3D structure tunable: (1) Trifluoroethyl methacrylate, hexafluorobutyl acrylate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator I-819) and 1,6-hexanediol diacrylate were mixed and dissolved by ultrasonication in a mass ratio of 1:0-2.0:0.01-0.05:0-0.01.
[0007] (2) injecting the solution prepared in step (1) into a reaction cell consisting of a pair of glass plates with a spacing of 2 mm and polymerizing under visible light (460 nm) for 1 hour; (3) After the reaction in step (2) is completed, the polymerized sample is placed in a solution containing trifluoroethyl methacrylate, hexafluorobutyl acrylate, 1,6-hexanediol diacrylate, fluorescent dye molecule 2-(6-(dimethylamino)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl acrylate (MNEA), 4-(acryloyloxy)butyl-4-(2-methyl-3-(2-(2-methylbenzo[b]thiophen-3-yl)-4-oxy-5,6-2H-4H-thiopyran[2,3-)b]thiopyran-3-yl)benzo[b]thiophen-6-yl)-4-oxobutyrate (BTBA) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator) and immersed for 40 minutes to allow the sample to swell; (4) Place the mask 1 (attached Figure 5 ) is placed above the above polymer, and irradiated with 460 nm visible light for 15 minutes to allow self-growth in the hollowed-out mask area to obtain a film material with a 3D structure in the shape of "7". At the same time, due to the presence of fluorescent dye, the material also has corresponding optical switch fluorescence; (5) soaking and dialyzing the polymer obtained in step (4) in a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 10:1 to 5:1); (6) The surface of the polymer in step (5) was brushed with an ethanol solution containing p-toluenesulfonic acid (20 mg / mL). The sample was then placed in an oven at 40°C for 6 hours. Subsequently, the temperature was raised to 120°C and heated for 4 hours. After the sample was cooled, it was immersed in a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 10:1 to 5:1) for 48 hours, and the sample was taken out and dried to obtain supramolecular polymer 1.
[0008] (7) Repeat steps (3-6), but when repeating step (3), remove the fluorescent dye MNEA, and keep the content of other molecules unchanged; when repeating step (4), replace the mask plate with mask plate 2 (attached Figure 6 As shown), the prepared 3D structure is improved from "7" to "3", obtaining a supramolecular polymer that can achieve optical switching fluorescence changes and 3D structural changes.
[0009] The optically switchable fluorescence and 3D structure-adjustable supramolecular polymer of the present invention contains green fluorescent dye MNEA and optically switchable red fluorescent dye BTBA. The system is green fluorescent in the initial state, turns into red fluorescence after irradiation with 365 nm ultraviolet light, and further turns into the initial green fluorescence after irradiation with 525 nm visible light. And this process is reversible under alternating irradiation with 365 nm ultraviolet light and 525 nm visible light.
[0010] The surface 3D structure of the supramolecular polymer with adjustable optical switch fluorescence and 3D structure described in the present invention disappears after low-temperature treatment under thermal and mechanical stimulation. This state exists stably at low temperatures, and the 3D structure gradually recovers as the system temperature increases.
[0011] The present invention discloses a supramolecular polymer with adjustable optical switch fluorescence and 3D structure, which is prepared according to a self-growth strategy. In the self-growth preparation process, the grown 3D structure contains the corresponding fluorescent dye, and its optical switch fluorescence and the 3D structure are coupled to each other in the same space, and the two anti-counterfeiting methods are cleverly combined (see attached Figure 4 Schematic diagram).
[0012] In the optically switchable fluorescence and 3D structure adjustable supramolecular polymer described in the present invention, fluorescence changes are regulated by light, and 3D spatial structure is regulated by heat and force. The stimulation means are different, and the two anti-counterfeiting methods respond independently to each other. The hidden state of the anti-counterfeiting label will not be disturbed during verification.
[0013] Compared with the currently available responsive fluorescent polymers, the polymer prepared by the present invention cleverly couples the optical switch fluorescence and the 3D spatial structure, thereby showing higher safety.
[0014] Compared with ordinary anti-counterfeiting labels, the present invention is not only irreversible in the process of use, but also has an irreversible deformation state after being deformed by external force, which will shorten the service life of the label. However, our invention has a dynamic-covalent double cross-linking effect in the polymer system, which ultimately makes the 3D spatial structure have excellent switching performance. Even if it is twisted, folded or even squeezed and deformed by external force during use, the label can still be restored to its original state.
[0015] Due to its sensitive temperature responsiveness, the present invention can deform at different temperatures. Based on this, the present invention also prepares an anti-counterfeiting label with temperature response. For example, we use a customized mold to process the prepared polymer into a designed pattern, control the monomer ratio to adjust the glass transition temperature of the polymer, and make it respond to different temperatures, and finally achieve the purpose of controlling the temperature to achieve orderly deformation of the polymer, so that it has excellent anti-counterfeiting performance of the 3D structure.
[0016] After adopting the above technical scheme, the present invention has the following beneficial effects compared with the prior art.
[0017] (1) Compared with previously reported materials, the supramolecular polymer prepared in the present invention has two anti-counterfeiting measures that are coupled to each other but respond independently, with a simple stimulation method, higher security, and higher practical application value.
[0018] (2) The present invention uses a self-growth strategy to couple the light-switch molecules with cross-linking, so that the prepared polymer can achieve dual-mode anti-counterfeiting by combining light-switch fluorescence and 3D structure. Compared with the current polymer anti-counterfeiting materials, it improves its anti-counterfeiting security, making it more difficult to imitate, and expands the anti-counterfeiting application concept of fluorescent polymers.
[0019] (3) Compared with previous fluorescent polymers, the supramolecular polymer prepared by the present invention has excellent stability and switching performance. After being twisted, folded or even squeezed and deformed by external forces, its optical switching ability and 3D structure are not affected, showing excellent optical recycling and 3D recycling performance, which has great advantages in actual production applications.
[0020] 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
[0021] 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: Figure 1 This is a fluorescence test diagram of the self-growth cross section of the supramolecular polymer of the present invention.
[0022] Figure 2 It is the fluorescence emission spectrum of the supramolecular polymer of the present invention in the fluorescence resonance energy transfer process under the action of different external lights.
[0023] Figure 3 The figure is a glass transition temperature diagram of the polymer prepared by regulating different ratios of rigid and flexible monomers in the supramolecular polymer of the present invention.
[0024] Figure 4 This is an application diagram of the supramolecular polymer of the present invention made into an anti-counterfeit label.
[0025] Figure 5 It is a schematic diagram of the mask 1 of the present invention.
[0026] Figure 6 It is a schematic diagram of the mask 2 of the present invention.
[0027] 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
[0028] 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.
[0029] Example 1: Preparation of a supramolecular polymer 1: 1.680 g of trifluoroethyl methacrylate, 2.360 g of hexafluorobutyl acrylate, 0.084 g of photoinitiator, and 0.023 g of 1,6-hexanediol diacrylate were ultrasonically mixed and uniformly dissolved, and then injected into a reaction cell consisting of a pair of glass plates with a spacing of 2 mm. The glass plates were clamped with clips to prevent air leakage. Under irradiation with visible light (460 nm, 40 mW / min), polymerization was carried out for 1 hour to obtain supramolecular polymer 1.
[0030] Example 2: Swelling of a photoswitchable supramolecular red fluorescent polymer 2: 16.800 g of trifluoroethyl methacrylate, 11.800 g of hexafluorobutyl acrylate, 0.627 g of photoinitiator, 0.170 g of crosslinker and 0.309 g of BTBA were uniformly mixed by ultrasonication, and the supramolecular polymer 1 was immersed in the above nutrient solution for 40 minutes to swell.
[0031] Example 3: Preparation of a photoswitchable supramolecular red fluorescent polymer 2: A mask plate 2 was placed on top of the swollen sample and polymerized for 15 minutes under visible light (460 nm, 40 mW / min). The sample was then immersed in a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 10 / 1 for 48 hours to remove the monomers that were not photopolymerized, thereby obtaining a photoswitchable supramolecular red fluorescent polymer 2 with a corresponding raised pattern. The polymer was alternately irradiated between 365 nm and 525 nm to achieve reversible conversion between the non-fluorescent and red fluorescent states.
[0032] Example 4: Transesterification of a photoswitchable supramolecular red fluorescent polymer 2: The surface of the prepared optical switch supramolecular red fluorescent polymer 2 was evenly brushed with an ethanol solution (20 mg / ml) containing p-toluenesulfonic acid, and then placed in an oven at 40°C for 6 hours. Subsequently, the temperature was raised to 120°C and heated for 4 hours. After cooling, the polymer was immersed in a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 10:1 to 5:1) for 48 hours, taken out and dried, and the optical switch supramolecular red fluorescent polymer 2 after ester exchange was obtained.
[0033] Example 5: Swelling of a photoswitchable supramolecular red fluorescent polymer 2: 12.600 g of trifluoroethyl methacrylate, 11.800 g of hexafluorobutyl acrylate, 0.523 g of photoinitiator, 0.141 g of cross-linker, 0.003 g of MNEA, and 0.258 g of BTBA were uniformly mixed by ultrasonication, and the photoswitchable supramolecular red fluorescent polymer 2 was immersed in the above nutrient solution for 40 minutes to swell.
[0034] Example 6: Preparation of a photoswitchable supramolecular dual-color fluorescent polymer 3: A mask plate 1 was placed on the swollen photoswitch supramolecular red fluorescent polymer 2, and polymerized for 15 minutes under visible light (460 nm, 40 mW / min). Then, it was immersed and dialyzed in a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 10 / 1 for 48 hours, and the monomers of the unphotopolymerized part were removed to obtain a photoswitch supramolecular two-color fluorescent polymer 3 with a "3" convex pattern, in which the "7" part was alternately irradiated between 365 nm and 525 nm to achieve reversible conversion between green fluorescence and red fluorescence states; and the remaining part was alternately irradiated between 365 nm and 525 nm to achieve reversible conversion between no fluorescence and red fluorescence states.
[0035] Example 7: Transesterification of a photoswitchable supramolecular dual-color fluorescent polymer 3: The surface of the prepared optical switch supramolecular dual-color fluorescent polymer 3 with a "3" convex pattern was evenly brushed with an ethanol solution (20 mg / ml) containing p-toluenesulfonic acid, and then placed in an oven at 40°C for 6 hours. Subsequently, the temperature was raised to 120°C and heated for 4 hours. After cooling, it was immersed in a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 10:1~5:1) for 48 hours, taken out and dried, and the optical switch supramolecular dual-color fluorescent polymer 3 with a "3" convex pattern after ester exchange was obtained, in which the "7" part was alternately irradiated between 365 nanometers and 525 nanometers, and the reversible conversion between the green fluorescence and red fluorescence states could be achieved; and the remaining part was alternately irradiated between 365 nanometers and 525 nanometers, and the reversible conversion between the non-fluorescence and red fluorescence states could be achieved.
[0036] Example 8: A cross-sectional fluorescence test image of the self-growth process of a polymer containing green fluorescent dye molecules under 460 nm visible light irradiation.
[0037] Figure 1 When the polymer containing the green fluorescent molecule MNEA is irradiated with visible light (460 nanometers, 40 milliwatts per minute), the nutrient solution components absorbed inside the polymer continue to polymerize, and a regular structure gradually grows in the irradiated area of the originally flat surface of the sample. Compared with the dark environment, obvious green fluorescence can be observed in the growing part, indicating that the monomers and cross-linkers in the nutrient solution have been integrated into the growing structure. The unique color extends to the bottom area of the seed, indicating that the growth starts from the inside of the sample, rather than a simple polymerization on the surface of the sample, which shows that it is feasible to prepare light-switchable supramolecular fluorescent polymer materials using a self-growth strategy.
[0038] Example 9: Testing the fluorescence resonance energy transfer spectrum of the prepared photoswitchable supramolecular dual-color fluorescent polymer under different external light regulation.
[0039] Figure 2The fluorescence resonance energy transfer process of the prepared optically switchable supramolecular dual-color fluorescent polymer film under the control of 254 nm and 525 nm. Figure 2 It can be seen that when the polymer film is fully irradiated with 365 nm UV light (10 minutes), a small MNEA emission peak appears at 475 nm, and a higher BTBA emission peak appears at 650 nm. Then, under 525 nm visible light irradiation, the MNEA emission signal at 475 nm continues to increase and gradually red-shifts, with the maximum emission peak at 500 nm, and its fluorescence signal value is 9.75 times the original, while the BTBA emission peak signal value at 650 nm is significantly reduced.
[0040] Example 10: Differential scanning calorimetry test diagram of the optical switch supramolecular fluorescent polymer obtained by polymerization at different ratios of rigid and flexible monomers.
[0041] Figure 3 The differential scanning calorimetry test diagram of the optical switch supramolecular fluorescent polymer obtained by polymerization at different rigid and flexible monomer ratios. Figure 3 It can be seen that as the ratio of trifluoroethyl methacrylate and hexafluorobutyl acrylate in the polymer system increases from 1:2 to 2.5:1, its glass transition temperature increases significantly, rising regularly from 4.25°C to 40.74°C. This shows that the glass transition temperatures of the polymers are significantly different, and the prepared supramolecular polymers have obvious temperature responsiveness, which provides a guarantee for their design into temperature-responsive anti-counterfeiting materials.
[0042] Example 11: The prepared photoswitchable supramolecular dual-color fluorescent polymer can be prepared into an anti-counterfeiting label of a supramolecular polymer with photoswitchable fluorescence and 3D structure adjustable.
[0043] Take the optical switch supramolecular two-color fluorescent polymer 3 with the "3" convex pattern obtained by the operation of Examples 1-7, such as Figure 4As shown in the figure, in the initial state, MNEA in the optical switch supramolecular dual-color fluorescent polymer 3 shows green fluorescence "7" under 365 nm ultraviolet light, and its 3D structure is "3". After the optical switch supramolecular dual-color fluorescent polymer 3 is heated, pressed, and cooled to room temperature (25 degrees Celsius), it is exposed to ultraviolet light and shows a "7" with green fluorescence, and its 3D structure is "1". At this time, with the irradiation of ultraviolet light, the BTBA in the optical switch supramolecular dual-color fluorescent polymer 3 undergoes molecular ring closure and shows red fluorescence. At this time, the anti-counterfeiting label shows a "3" with red fluorescence, and its 3D structure is "1"; because the optical switch supramolecular dual-color fluorescent polymer 3 has shape memory properties, when the ambient temperature is increased to a temperature greater than the glass transition temperature (28.76 degrees Celsius) at a rigid-flexible ratio of 1.5:1, a part of the original flattened "7" will rebound to the 3D state, and then show a red fluorescent "3", and its 3D structure is "7". When the ambient temperature is further increased to a temperature greater than the glass transition temperature (40.74 degrees Celsius) at a rigid-flexible ratio of 2:1, the BTBA in the optically switchable supramolecular dual-color fluorescent polymer 3 changes from red fluorescence "3" to green fluorescence "7" under 525-nanometer visible light irradiation, and the remaining flattened part rebounds to the initial 3D state, at which time the 3D structure is "3", completing a cycle. The results show that the optically switchable supramolecular dual-color fluorescent polymer 3 can be used to make a dual-modal anti-counterfeiting label of a supramolecular polymer with adjustable optical switch fluorescence and 3D structure.
[0044] 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 as above, 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 preparing a supramolecular polymer with optically switchable fluorescence and 3D structure tunable, characterized in that: The following steps are involved: Step (1) trifluoroethyl methacrylate, hexafluorobutyl acrylate, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator 819), and 1,6-hexanediol diacrylate are mixed and dissolved by ultrasonication in a certain proportion. Step (2) photopolymerizing the solution prepared in step (1) under irradiation with 460 nm visible light for 1 hour to obtain a cross-linked supramolecular polymer; Step (3) soaking the obtained cross-linked supramolecular polymer in a nutrient solution containing a certain proportion of trifluoroethyl methacrylate, hexafluorobutyl acrylate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), 1,6-hexanediol diacrylate, 2-(6-(dimethylamino)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl acrylate, and 4-(acryloyloxy)butyl-4-(2-methyl-3-(2-(2-methylbenzo[b]thiophen-3-yl)-4-oxy-5,6-2H-4H-thiopyran[2,3-)b]thiopyran-3-yl)benzo[b]thiophen-6-yl)-4-oxobutyrate to cause swelling; Step (4) placing the mask plate 1 above the polymer and irradiating it with 460-nanometer visible light for 15 minutes to allow self-growth to occur in the hollowed-out mask plate area, thereby obtaining a film material having a 3D structure in the shape of "7"; Step (5) soaking and dialyzing the polymer obtained in step (4) in a mixed solvent of petroleum ether and ethyl acetate; Step (6) brushing the surface of the polymer in step (5) with an ethanol solution containing p-toluenesulfonic acid (20 mg / ml), then placing the sample in an oven at 40°C for 6 hours, then heating to 120°C for 4 hours; after the sample is cooled, immersing it in a mixed solvent of petroleum ether and ethyl acetate for 48 hours, taking out the sample and drying it, thereby obtaining a supramolecular polymer 1; Step (7) repeats the operations of steps (3) to (6), and when repeating step (3), removes the fluorescent dye MNEA, and the content of other molecules remains unchanged; when repeating step (4), replaces the mask plate with mask plate 2, so that the prepared 3D structure is improved from "7" to "3", and a supramolecular polymer with target light-switch fluorescence and 3D structure adjustable is obtained.
2. The method for preparing a supramolecular polymer with optically switchable fluorescence and 3D structure tunable according to claim 1, characterized in that: In step (1), the mass ratio of trifluoroethyl methacrylate, hexafluorobutyl acrylate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator I-819) and 1,6-hexanediol diacrylate is 1:0~2.00:0~0.20:0~0.
20.
3. The method for preparing a supramolecular polymer with optically switchable fluorescence and 3D structure tunable according to claim 1, characterized in that: In step (3), the mass ratio of trifluoroethyl acrylate, hexafluorobutyl acrylate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), 1,6-hexanediol diacrylate, 2-(6-(dimethylamino)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl acrylate, and 4-(acryloyloxy)butyl-4-(2-methyl-3-(2-(2-methylbenzo[b]thiophene-3-yl)-4-oxy-5,6-2H-4H-thiopyran[2,3-)b]thiopyran-3-yl)benzo[b]thiophene-6-yl)-4-oxobutanoate is 1:0~2.00:0~0.20:0~0.20:0~0.10:0~0.
10.
4. The method for preparing a supramolecular polymer with optically switchable fluorescence and 3D structure tunable according to claim 1, characterized in that: In step (5) and step (6), the volume ratio of petroleum ether and ethyl acetate in the mixed solvent is (10:1) to (5:1).
5. Application of the optically switchable fluorescence and 3D structure-adjustable supramolecular polymer prepared by the method according to any one of claims 1 to 4 in anti-counterfeiting.
6. The use according to claim 5, characterized in that: The supramolecular polymer utilizes a self-growth strategy to couple the variable 3D spatial structure with the optical switch fluorescence signal, thereby realizing the orthogonal regulation of the fluorescence signal and the 3D spatial structure in a specific area under light, heat and force stimulation.
7. The use according to claim 5, characterized in that: The supramolecular polymer can be prepared into a dual-modal anti-counterfeiting label that couples two anti-counterfeiting means, namely, photoswitchable fluorescence and 3D spatial structure change under light, heat and force stimulation.