Cellulose-based membrane with temperature and pH stimulation response as well as preparation method and application of cellulose-based membrane

Abstract

The invention belongs to the technical field of anti-counterfeiting films, and particularly discloses a cellulose-based film with temperature and pH stimulation response as well as a preparation method and application of the cellulose-based film with temperature and pH stimulation response. A stimuli-responsive chain segment, an aggregation-induced emission chain segment and a color-controllable fluorescent polymer chain segment are synchronously introduced, so that the cellulose-based membrane with temperature and pH stimuli-responsive can be rapidly prepared in one step, and the cellulose-based membrane can be used for preparing a dynamic anti-counterfeiting membrane; the preparation method adopts biodegradable cellulose as a raw material, and has the advantages of greenness, environmental protection and low carbon.

Description

Technical Field

[0001] The invention relates to the technical field of anti-counterfeiting films, in particular to a cellulose-based film responsive to temperature and pH stimulation, and a preparation method and application thereof. Background Art

[0002] With the continuous advancement of technology and the advent of the digital age, the proliferation of counterfeit goods and information leakage has become more and more common, resulting in large economic losses every year. In order to solve these problems and protect the integrity of goods and information, a large number of anti-counterfeiting and encryption technologies have been developed, including quick response codes, holograms, color conversion, photoluminescence patterns, and stimulus response. However, these methods usually exhibit disadvantages such as easy counterfeiting, high production costs, complex manufacturing processes, and cumbersome detection procedures.

[0003] Fluorescence-based anti-counterfeiting and dynamic encryption technologies have become excellent solutions in this field because of their inherent properties of stealth, ease of design and implementation, and direct verifiability. The use of fluorescent dyes in anti-counterfeiting applications ensures product authenticity and effectively prevents substandard and counterfeit products from entering the market. On the other hand, in the field of information security, fluorescent encryption technology provides protection by encoding sensitive data during transmission and storage, thereby preventing unauthorized access and manipulation. Common fluorescent anti-counterfeiting and information encryption materials include traditional organic fluorescent materials, quantum dot materials, rare earth coordination materials, and phosphorescent materials. However, these materials often suffer from aggregation-induced detonation (ACQ) phenomena, are complex to synthesize, and simple information encryption is easy to copy.

[0004] The discovery of aggregation-induced luminescence materials solves the ACQ problem. They have excellent anti-photobleaching properties in the aggregated state, can adjust different molecular structures and chemical bonds to achieve different luminescent colors and emission wavelengths, and can introduce different functional groups to achieve multiple stimulus responses. At the same time, the fluorescent dynamic anti-counterfeiting technology that dynamically changes fluorescence with external stimuli is a more advanced anti-counterfeiting technology that is difficult to forge and crack, and has higher security and reliability.

[0005] Therefore, a simple and fast method is developed to prepare a stimulus-responsive cellulose-based dynamic anti-counterfeiting film. By regulating the external stimulus source, the emission wavelength of the anti-counterfeiting film can be changed, thereby presenting different color changes. In the field of dynamic anti-counterfeiting and dynamic information encryption, it can greatly increase the difficulty of counterfeiting and has potential application value. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a cellulose-based film responsive to temperature and pH stimulation, and a preparation method and application thereof.

[0007] To achieve the above object, the present invention is implemented according to the following technical solutions:

[0008] One of the technical solutions of the present invention is to provide a method for preparing a cellulose-based film responsive to temperature and pH stimulation, comprising the following steps:

[0009] S1. Mix cellulose and ionic liquid in a mass ratio of 1:(10-50), heat and stir to dissolve, add N,N-dimethylformamide solvent to dilute, the mass ratio of N,N-dimethylformamide to ionic liquid is (1-3):(1-3); then add 2-bromopropyl bromide in an ice water bath, the mass ratio of cellulose to 2-bromopropyl bromide is 1:(5-20), react at room temperature for 48 hours, precipitate in deionized water, centrifuge, wash, and dry to obtain a cellulose-based initiator;

[0010] S2. A cellulose-based initiator and a dimethyl sulfoxide solvent in a mass ratio of 1:(15-30) are mixed at 30°C-60°C to obtain a reaction solution A; benzyl mercaptan and triethylamine in a mass ratio of (1-3):1 are mixed and reacted for 30 minutes, and carbon disulfide is added, the mass ratio of benzyl mercaptan and carbon disulfide is 1:(1-5), and stirring is continued for 30 minutes to obtain a reaction solution B; reaction solution A and reaction solution B are mixed, heated at 30°C-80°C and stirred for 24 hours, precipitated with deionized water, centrifuged, washed, and dried to obtain a cellulose-based macromolecular RAFT agent;

[0011] S3. After dissolving a cellulose-based macromolecular RAFT agent in dioxane, add a phenylboronic acid derivative, wherein the molar ratio of the cellulose-based macromolecular RAFT agent to the phenylboronic acid derivative is 1:(1-5), and heat the reaction for 8-12 hours to obtain a modified cellulose-based macromolecular RAFT agent; take a stimulus-responsive monomer, an aggregation-induced emission fluorescent polymerization monomer, a fluorescent polymer segment with controllable color change, a modified cellulose-based macromolecular RAFT agent, and an initiator in a mass ratio of (200-600):(0.1-24):(0.02-6):(2-60):(0.2-12) and add them to an organic solvent. After nitrogen bubbling for 30 minutes, place the mixture in an oil bath and react for 12-24 hours. After the reaction is completed, add the reaction solution dropwise into a n-hexane solvent for precipitation three times, and vacuum dry to obtain a cellulose-based graft copolymer;

[0012] S4. Dissolve the cellulose-based graft copolymer in an organic solvent, add a cross-linking agent, stir and react for 1-5 hours, and then coat it on the surface of filter paper to obtain a cellulose-based membrane that responds to temperature and pH stimuli.

[0013] Furthermore, the cellulose is one or more of microcrystalline cellulose, ethyl cellulose, and carboxymethyl cellulose.

[0014] Further, the ionic liquid is one or more of 1-allyl-3-methylimidazolium chloride (AMIMCl), 1-butyl-3-methylimidazolium chloride (BMIMCl), 1-ethyl-3-methylimidazolium chloride (EMIMCl), 1-methyl-3-butylimidazolium chloride (MMIMCl), 1-butyl-3-methylimidazolium propionamide (BMIMAc) and 1-butyl-3-methylimidazolium acetate (BMIMOAc).

[0015] Furthermore, the stimulus responsive monomer is one or more of acrylic acid, methacrylic acid, N-isopropyl acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-ethyl methacrylamide, N-pyrrolidinoacrylamide, N-cyclopropyl methacrylamide, 2-methoxyethyl acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol methyl ether acrylate, and methacryloylethyl sulfobetaine.

[0016] Furthermore, the aggregation-induced luminescence fluorescent polymer monomer is a tetraphenylethylene derivative, and its structural formula is as follows:

[0017]

[0018] Wherein, the group R is one of vinyl, propenyl, acrylate, methacrylate, and acrylamide; more preferably, the group R in the tetraphenylethylene derivative is vinyl.

[0019] The color-controllable fluorescent polymer chain segment is a spiropyran derivative, and its structural formula is as follows:

[0020]

[0021] Wherein, the group R is one of vinyl, propenyl, acrylate, methacrylate, and acryloyl chloride. More preferably, the group R in the spiropyran derivative is acrylate.

[0022] The boric acid derivative is one or more of 4-formylphenylboronic acid, 4-hydroxyphenylboronic acid, 4-carboxymethylphenylboronic acid and 4-aminophenylboronic acid.

[0023] Furthermore, the initiator is any one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, etc.

[0024] Furthermore, the organic solvent is one or more of toluene, acetone, dioxane, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide.

[0025] Furthermore, the cross-linking agent is one or more of 1,4-butanediamine, ethylenediamine, 1,5-pentanediamine, and 1,6-hexamethylenediisocyanate.

[0026] The second technical solution of the present invention is to provide a cellulose-based membrane responsive to temperature and pH stimulation prepared by the above method.

[0027] The third technical solution of the present invention is to provide a cellulose-based film responsive to temperature and pH stimulation for use in preparing a dynamic anti-counterfeiting film.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The present invention prepares a cellulose-based macromolecular RAFT agent, initiates RAFT polymerization on the surface in situ, and simultaneously introduces a stimulus-responsive segment, an aggregation-induced luminescent segment, and a color-controllable fluorescent polymer segment, thereby preparing a cellulose-based film that responds to temperature and pH stimuli in one step and quickly, and can be used to prepare a dynamic anti-counterfeiting film. The preparation method uses biodegradable cellulose as a raw material and has good advantages of being green, environmentally friendly, and low-carbon.

[0030] (2) The cellulose-based film with temperature and pH stimulus response prepared by the present invention has rapid stimulus response to temperature, pH and ultraviolet light. At the same time, it has good adhesion on the surfaces of different substrates and has good universality.

[0031] (3) The cellulose-based film prepared by the present invention that responds to temperature and pH stimulation can change the luminescence spectrum of the fluorescent film by adjusting parameters such as temperature, pH, and ultraviolet light exposure time. It has obvious dynamic and controllable photoluminescence performance and can be used for dynamic anti-counterfeiting applications. Utilizing this characteristic, it can be applied in the fields of dynamic anti-counterfeiting and dynamic information encryption, which can greatly increase the difficulty of counterfeiting. The preparation method of this material is simple, green and environmentally friendly, and has potential application value in the field of dynamic anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The dynamic anti-counterfeiting film prepared by coating the stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) obtained in Example 1 on filter paper is shown in the figure after irradiation with 365nm ultraviolet light for 1s and 60s: (a) is irradiation for 1s; (b) is irradiation for 60s.

[0033] Figure 2The dynamic anti-counterfeiting film prepared by coating the stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) obtained in Example 2 on filter paper was heated to 60°C and irradiated under 365nm ultraviolet light for 1s and 60s: (a) irradiation for 1s; (b) irradiation for 60s.

[0034] Figure 3 The dynamic anti-counterfeiting film prepared by coating the stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) obtained in Example 3 on filter paper was immersed in an aqueous solution with a pH value of 8 for 60 seconds and irradiated under 365nm ultraviolet light for 1 second and 60 seconds: (a) is irradiated for 1 second; (b) is irradiated for 60 seconds. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not used to limit the invention.

[0036] Example 1

[0037] 1) Add microcrystalline cellulose Cell (10 g) and ionic liquid 1-allyl-3-methylimidazole chloride (AMIMCl) (200 g) into a 500 mL single-necked flask, heat to 100 ° C and stir to dissolve, then add N, N-dimethylformamide (100 g), continue stirring for 30 minutes, add 2-bromopropyl bromide (80 g) dropwise in an ice water bath, react at room temperature for 48 hours, precipitate in deionized water, centrifuge, wash, and vacuum dry to obtain a cellulose-based initiator.

[0038] 2) Add cellulose-based initiator (10 g) to dimethyl sulfoxide solvent, heat and stir at 40°C to dissolve to obtain reaction solution A. In another round-bottom flask, add benzyl mercaptan (2 g), triethylamine (1.6 g) and dimethyl sulfoxide (20 g), stir at room temperature for 30 min, add carbon disulfide (3.6 g), and continue stirring for 30 min to obtain reaction solution B. The above reaction solution A and reaction solution B are mixed, heated to 40°C and stirred for 24 h, precipitated with deionized water, centrifuged, washed, and dried to obtain a cellulose-based macromolecular RAFT agent (Cell-RAFT).

[0039] 3) Cell-RAFT (0.46 g containing 0.5 mmol trithio function) and 4-formylphenylboronic acid (0.225 g, 1.5 mmol) were dissolved in 20 mL of dioxane, stirred for reaction for 2 h, and then dimethylaminoethyl methacrylate (DMAEMA) (15.72 g, 100 mmol), (2-(4-vinylphenyl)ethylene-1,1,2-triyl)triphenyl (TPEE) (0.157 g, 1% wt), 1'-acryloyl chloride-3',3'-dimethyl-6-nitro(2H-1-benzopyran-2,2'-indole) (SPMA) (0.016 g, 0.1% wt) and azobisisobutyronitrile (AIBN) (10 mg, 0.06 mmol) were dissolved in 20 mL of dioxane, and nitrogen was bubbled for 30 min, and then placed in an oil bath and heated for reaction for 24 h. After the reaction is completed, the reaction solution is added dropwise into a n-hexane solvent for precipitation three times, and then vacuum dried to obtain the stimulus-responsive cross-linked cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA).

[0040] 4) The stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) (5.0 g) was dissolved in acetone to prepare a polymer solution with a mass concentration of 10%, 1,4-diaminobutane crosslinker (0.5 mL) was added, and after stirring for 1 h, it was coated on the surface of filter paper and dried at 40°C to obtain a dynamic anti-counterfeiting film with a cross-linked structure and temperature and pH stimulus response. The effect after irradiation under 365 nm ultraviolet light for 1 s and 60 s is shown in the figure below. Figure 1 As shown by Figure 1 It can be seen that after the obtained cellulose-based film was irradiated with ultraviolet light for 60 seconds, its luminescent color gradually changed to orange, showing dynamic photoluminescence characteristics.

[0041] Example 2

[0042] 1) Add microcrystalline cellulose Cell (10 g) and ionic liquid 1-allyl-3-methylimidazole chloride (AMIMCl) (200 g) into a 500 mL single-necked flask, heat to 100 ° C and stir to dissolve, then add N, N-dimethylformamide (100 g), continue stirring for 30 minutes, add 2-bromopropyl bromide (80 g) dropwise in an ice water bath, react at room temperature for 48 hours, precipitate in deionized water, centrifuge, wash, and vacuum dry to obtain a cellulose-based initiator.

[0043] 2) Add cellulose-based initiator (10 g) to dimethyl sulfoxide solvent, heat and stir at 40°C to dissolve to obtain reaction solution A. In another round-bottom flask, add benzyl mercaptan (2 g), triethylamine (1.6 g) and dimethyl sulfoxide (20 g), stir at room temperature for 30 min, add carbon disulfide (3.6 g), and continue stirring for 30 min to obtain reaction solution B. The above reaction solution A and reaction solution B are mixed, heated to 40°C and stirred for 24 h, precipitated with deionized water, centrifuged, washed, and dried to obtain a cellulose-based macromolecular RAFT agent (Cell-RAFT).

[0044] 3) Cell-RAFT (0.46 g containing 0.5 mmol trisulfide function) and 4-formylphenylboronic acid (0.225 g, 1.5 mmol) were dissolved in 20 mL of dioxane, stirred for reaction for 2 h, and then dimethylaminoethyl methacrylate (DMAEMA) (23.58 g, 150 mmol), (2-(4-vinylphenyl)ethylene-1,1,2-triyl)triphenyl (TPEE) (0.12 g, 0.5% wt), 1'-acryloyl chloride-3',3'-dimethyl-6-nitro (2H-1-benzopyran-2,2'-indole) (SPMA) (0.024 g, 0.1% wt), azobisisobutyronitrile (AIBN) (15 mg, 0.09 mmol) were dissolved in 20 mL of dioxane, and nitrogen was bubbled for 30 min, and then placed in an oil bath and heated for reaction for 24 h. After the reaction is completed, the reaction solution is added dropwise into a n-hexane solvent for precipitation three times, and then vacuum dried to obtain the stimulus-responsive cross-linked cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA).

[0045] 4) The stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) (5.0 g) was dissolved in acetone to prepare a polymer solution with a mass concentration of 10%, and 1,4-diaminobutane crosslinker (0.5 mL) was added. After stirring for 1 h, it was coated on the surface of the filter paper and dried at 40°C to obtain a dynamic anti-counterfeiting film with a cross-linked structure. The film was immersed in deionized water, heated to 60°C, and irradiated under 365 nm ultraviolet light for 1 s and 60 s. The effect is shown in the figure below. Figure 2 As shown. Figure 2It can be seen that by adjusting the temperature to 60°C, which exceeds the lowest solubility temperature (LCST) of the cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA), the solubility of the PDMAEMA segment in water decreases, aggregation occurs, and then the aggregation-induced emission segment PTPEE aggregates and emits light. Then, when irradiated with ultraviolet light for 1 second, it emits blue light, showing an obvious aggregation-induced emission (AIE) effect; at the same time, with the extension of the illumination time, the color-controllable luminescent segment PSPMA gradually changes from colorless to orange-red, and the PTPEE emission color and the PSPMA emission color are superimposed to obtain dynamic color changes, which can be used for dynamic anti-counterfeiting and information encryption.

[0046] Example 3

[0047] 1) Add microcrystalline cellulose Cell (10 g) and ionic liquid 1-allyl-3-methylimidazole chloride (AMIMCl) (200 g) into a 500 mL single-necked flask, heat to 100 ° C and stir to dissolve, then add N, N-dimethylformamide (100 g), continue stirring for 30 minutes, add 2-bromopropyl bromide (80 g) dropwise in an ice water bath, react at room temperature for 48 hours, precipitate in deionized water, centrifuge, wash, and vacuum dry to obtain a cellulose-based initiator.

[0048] 2) Add cellulose-based initiator (10 g) to dimethyl sulfoxide solvent, heat and stir at 40°C to dissolve to obtain reaction solution A. In another round-bottom flask, add benzyl mercaptan (2 g), triethylamine (1.6 g) and dimethyl sulfoxide (20 g), stir at room temperature for 30 min, add carbon disulfide (3.6 g), and continue stirring for 30 min to obtain reaction solution B. The above reaction solution A and reaction solution B are mixed, heated to 40°C and stirred for 24 h, precipitated with deionized water, centrifuged, washed, and dried to obtain a cellulose-based macromolecular RAFT agent (Cell-RAFT).

[0049] 3) Cell-RAFT (0.46 g containing 0.5 mmol trisulfide function) and 4-formylphenylboronic acid (0.225 g, 1.5 mmol) were dissolved in 20 mL of dioxane, stirred for reaction for 2 h, and then dimethylaminoethyl methacrylate (DMAEMA) (23.58 g, 150 mmol), (2-(4-vinylphenyl)ethylene-1,1,2-triyl)triphenyl (TPEE) (0.12 g, 0.5% wt), 1'-acryloyl chloride-3',3'-dimethyl-6-nitro (2H-1-benzopyran-2,2'-indole) (SPMA) (0.024 g, 0.1% wt), azobisisobutyronitrile (AIBN) (15 mg, 0.09 mmol) were dissolved in 20 mL of dioxane, and nitrogen was bubbled for 30 min, and then placed in an oil bath and heated for reaction for 24 h. After the reaction is completed, the reaction solution is added dropwise into a n-hexane solvent for precipitation three times, and then dried in vacuo to obtain the stimulus-responsive cellulose-based cross-linked graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA).

[0050] 4) The stimulus-responsive cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) (5.0 g) was dissolved in acetone to prepare a polymer solution with a mass concentration of 10%, and 1,4-diaminobutane crosslinker (0.5 mL) was added. After stirring for 1 h, it was coated on the surface of the filter paper and dried at 40°C to obtain a dynamic anti-counterfeiting film with a cross-linked structure. The film was immersed in an aqueous solution with a pH value of 8 for 60 s and irradiated under 365 nm ultraviolet light for 1 s and 60 s. The effect is shown in the figure below. Figure 3 As shown. Figure 3 It can be seen that by adjusting the pH to 8, the PDMAEMA chain segments in the cellulose-based graft copolymer Cell-gP (DMAEMA-co-TPEE-co-SPMA) are curled and aggregated, which reduces its solubility in water, causing the aggregation-induced emission segment PTPEE to aggregate and emit light, and then emit blue light when irradiated with ultraviolet light for 1 second, showing an obvious aggregation-induced emission (AIE) effect; at the same time, with the extension of the illumination time, the color-controllable luminescent segment PSPMA gradually changes from colorless to orange-red, and the PTPEE emission color and the PSPMA emission color are superimposed to obtain dynamic color changes, which can be used for dynamic anti-counterfeiting and information encryption.

[0051] In summary, the cellulose-based film prepared by the present invention with temperature and pH stimulus response can change the luminescence spectrum of the fluorescent film by regulating parameters such as temperature, pH, and ultraviolet light irradiation time. It has obvious dynamic and controllable photoluminescence performance and can be used for dynamic anti-counterfeiting applications.

[0052] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A method for preparing a cellulose-based film responsive to temperature and pH stimulation, characterized in that: The following steps are involved: S1. Mix cellulose and ionic liquid in a mass ratio of 1:(10-50), heat and stir to dissolve, add N,N-dimethylformamide solvent to dilute, the mass ratio of N,N-dimethylformamide to ionic liquid is (1-3):(1-3); then add 2-bromopropyl bromide in an ice water bath, the mass ratio of cellulose to 2-bromopropyl bromide is 1:(5-20), react at room temperature for 48 hours, precipitate in deionized water, centrifuge, wash, and dry to obtain a cellulose-based initiator; S2. A cellulose-based initiator and a dimethyl sulfoxide solvent in a mass ratio of 1:(15-30) are mixed at 30°C-60°C to obtain a reaction solution A; benzyl mercaptan and triethylamine in a mass ratio of (1-3):1 are mixed and reacted for 30 minutes, and carbon disulfide is added, the mass ratio of benzyl mercaptan and carbon disulfide is 1:(1-5), and stirring is continued for 30 minutes to obtain a reaction solution B; reaction solution A and reaction solution B are mixed, heated at 30°C-80°C and stirred for 24 hours, precipitated with deionized water, centrifuged, washed, and dried to obtain a cellulose-based macromolecular RAFT agent; S3, after dissolving the cellulose-based macromolecular RAFT agent in dioxane, add phenylboronic acid derivatives, the molar ratio of the cellulose-based macromolecular RAFT agent to the phenylboronic acid derivative is 1: (1-5), and heat the reaction for 8-12 hours to obtain a modified cellulose-based macromolecular RAFT agent; take a stimulus response monomer, an aggregation-induced emission fluorescent polymerization monomer, a color-controllable fluorescent polymer segment, a modified cellulose-based macromolecular RAFT agent and an initiator in a mass ratio of (200-600): (0.1-24): (0.02-6): (2-60): (0.2-12) and add them to an organic solvent, after nitrogen bubbling for 30 minutes, place in an oil bath and add to react for 12-24 hours, after the reaction is completed, add the reaction solution dropwise into n-hexane solvent for precipitation three times, and vacuum dry to obtain a cellulose-based graft copolymer; S4. Dissolve the above cellulose-based graft copolymer in an organic solvent, add a cross-linking agent, stir and react for 1-5 hours, and then coat it on the surface of filter paper to obtain a cellulose-based membrane that responds to temperature and pH stimuli.

2. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The cellulose is one or more of microcrystalline cellulose, ethyl cellulose and carboxymethyl cellulose.

3. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The ionic liquid is one or more of 1-allyl-3-methylimidazolium chloride (AMIMCl), 1-butyl-3-methylimidazolium chloride (BMIMCl), 1-ethyl-3-methylimidazolium chloride (EMIMCl), 1-methyl-3-butylimidazolium chloride (MMIMCl), 1-butyl-3-methylimidazolium propionamide (BMIMAc) and 1-butyl-3-methylimidazolium acetate (BMIMOAc).

4. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The stimulus responsive monomer is one or more of acrylic acid, methacrylic acid, N-isopropyl acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-ethyl methacrylamide, N-pyrrolidinoacrylamide, N-cyclopropyl methacrylamide, 2-methoxyethyl acrylate, polyethylene glycol methyl ether methacrylate, polyethylene glycol methyl ether acrylate, and methacryloylethyl sulfobetaine.

5. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The aggregation-induced luminescence fluorescent polymer monomer is a tetraphenylethylene derivative; the color-controllably changeable fluorescent polymer chain segment is a spiropyran derivative; the boronic acid derivative is one or more of 4-formylphenylboronic acid, 4-hydroxyphenylboronic acid, 4-carboxymethylphenylboronic acid, and 4-aminophenylboronic acid.

6. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The initiator is any one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, etc.

7. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The organic solvent is one or more of toluene, acetone, dioxane, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide.

8. The method for preparing a cellulose-based film responsive to temperature and pH stimulation according to claim 1, characterized in that: The crosslinking agent is one or more of 1,4-butanediamine, ethylenediamine, 1,5-pentanediamine, and 1,6-hexamethylenediisocyanate.

9. A cellulose-based film responsive to temperature and pH stimuli prepared by the method according to any one of claims 1 to 8.

10. Use of the cellulose-based film responsive to temperature and pH stimulation as claimed in claim 9 in preparing a dynamic anti-counterfeiting film.

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