A phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid response data encryption material and its preparation method and application

Abstract

The present application discloses a phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material and its preparation method and application, belonging to the technical field of polymer acid responsive data encryption material preparation. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material comprises a phenanthroline benzimidazole structure polyimide, a rare earth ion, and an organic small molecule ligand of a β-diketone structure bound by coordination. The material exhibits a rapid acid response when added with different proportions of organic acid / inorganic acid, and the function of data encryption can be realized through this acid response effect.

Description

Technical Field

[0001] The present application relates to a phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material and a preparation method and application thereof, belonging to the technical field of polymer acid responsive data encryption material preparation. Background Art

[0002] Information security has received increasing attention in daily life, and has also promoted the development of new materials and technologies for encryption, anti-counterfeiting and information security storage. By combining multiple anti-counterfeiting technologies or using multiple external stimuli (such as light, temperature, pH and humidity) to decrypt information, the encrypted information becomes difficult to interpret and copy, thereby effectively improving the security of information storage. However, integrating different types of anti-counterfeiting technologies into a system often requires complex assembly methods and it is difficult to avoid mutual interference. At the same time, complex decryption operations usually require expensive and clumsy decryption equipment. Therefore, how to achieve secure storage of information through simple encryption / decryption methods is a challenging problem.

[0003] Furthermore, rewritable materials, which enable reversible writing and erasing of information in the presence or absence of specific stimuli (such as light, solvents, ions, acids / bases, or competing guest molecules), have attracted significant attention in the field of information storage. However, most reported rewritable materials are chemically reactive or based on gel systems. These are susceptible to chemical residues / accumulation or volume changes associated with solvent evaporation, limiting their rewritability and sensitivity. Therefore, there is a need to develop rewritable materials that are fast in response, rewritable, simple to prepare, and require mild conditions.

[0004] Fluorescent materials are materials that absorb external energy (such as temperature, light, and electricity) and emit fluorescent light. Because they can emit a variety of bright colors visible to the naked eye, fluorescent materials play an indispensable role in coatings, lamps, fluorescent signs, and other fields. These fluorescent materials are combined with acid-responsive molecules. Acid-responsive refers to a type of intelligent responsive material in which the fluorescent color and intensity of the material molecules undergo significant changes in response to the pH of the environment. Most acid-chromic materials contain groups that can interact with acids or bases, such as amino, pyridyl, carboxyl, phenolic hydroxyl, or other nitrogen-containing heterocycles. Under the action of acid or base, the molecular structure receives protons and undergoes a protonation effect, which in turn changes the compound's electron cloud distribution or molecular stacking pattern, triggering a significant change in the material's fluorescence or absorption spectrum. Such acid-responsive materials have broad applications and prospects in fields such as pH sensors, acid-base switches, and optoelectronic devices.

[0005] Currently, the introduction of lanthanide ions into HOFs framework materials not only improves the stability of HOFs, but also provides unique luminescence centers, promotes fluorescence resonance energy transfer between the HOFs framework and guest molecules, provides efficient photoresponsiveness, and enriches the color changes of color-changing materials. However, the inherent stability of HOFs materials limits their application range.

[0006] Polyimide (PI) is widely recognized for its excellent thermal stability, chemical resistance, dimensional stability, and mechanical strength. However, in the field of optoelectronics, rare earth metals can be introduced into PI through a post-polymerization coordination strategy, theoretically producing coordinated PI with superior performance. Introducing acid-responsive groups into the polyimide molecular structure can achieve acid-induced color change, thereby achieving the purpose of data encryption.

[0007] With the advancement of science and technology and the development of information, material molecules with a single stimulus-responsive characteristic can no longer meet people's diverse needs. In order to achieve the diversity and diversification of materials that respond to multiple stimuli, we explore the integration of multiple stimulus-responsive principles and the construction of multi-stimulus-responsive materials. By modifying the materials to have multiple response characteristics, we can solve the single function of the material and obtain functional materials with multifunctional application potential, which is more conducive to further expanding the application range of such materials. Summary of the Invention

[0008] In order to solve the problems of relatively poor solubility, thermal performance, and luminescence that still exist in the existing technology of materials with stimulus-responsive properties, this application provides a phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material and its preparation method and application. By introducing the phenanthroline benzimidazole structure, it has excellent rare earth metal ion coordination ability. On this basis, the β-diketone small molecule ligand with sensitization properties for rare earth ions reacts with the polyimide molecule phenanthroline benzimidazole ligand to generate PI-Ln 3+ Coordinated polyimide. The phenanthroline benzimidazole structure has a strong response to proton acid. When different amounts of proton acid are added, Ln 3+ Under organic ligand sensitization, the luminescence efficiency undergoes significant changes. This results in changes in the fluorescence emission wavelength and intensity, enabling acid-responsive data encryption. The rigid structure of phenanthroline benzimidazole imparts excellent thermal and chemical stability to the material, while the twisted structure increases the free volume of the polymer material, enhancing its solubility and improving its processability. Compared to currently studied organic luminescent materials, the solubility, thermal properties, and luminescence performance of this polymer material are significantly improved, demonstrating its potential commercial value and low production cost, enabling large-scale production and application.

[0009] This application adopts the following technical solutions:

[0010] According to one aspect of the present application, a phenanthroline benzimidazole structure polyimide single rare earth ion coordinated acid responsive data encryption material is provided, comprising a phenanthroline benzimidazole structure polyimide, a rare earth ion, and an organic small molecule ligand of a β-diketone structure bound by coordination;

[0011] The phenanthroline benzimidazole structure polyimide has a structure of the general formula shown in Formula I:

[0012]

[0013] wherein Ar is the residue of a dianhydride monomer;

[0014] M is selected from C6-C 40 At least one of the arylene groups;

[0015] 0.5<n≤1,n+m=1;

[0016] The organic small molecule ligand of the β-diketone structure has a structure of the general formula shown in Formula Ia:

[0017]

[0018] Optionally, the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material has a structure of the general formula shown in Formula II:

[0019]

[0020] Among them, Ln represents rare earth ions, and Ligand represents organic small molecule ligands;

[0021] Ar is the residue of a dianhydride monomer;

[0022] M is selected from C6-C 40 At least one of the arylene groups;

[0023] 0.5<n≤1,n+m=1.

[0024] Optionally, the rare earth ion is at least one element ion selected from Tb, Eu, Ce, Yb, Sm, and Gd;

[0025] Optionally, the molar ratio of the rare earth ions to the N atoms in the phenanthroline benzimidazole structure polyimide is 0.025 to 0.5:1;

[0026] Optionally, the organic small molecule ligand of the β-diketone structure is selected from at least one of α-thienyltrifluoroacetone (TTA), acetylacetone (acac), dibenzoylmethane (DBM), benzoylacetone (BA), benzoyltrifluoroacetone (BFA), and β-naphthoyltrifluoroacetone (β-NTA).

[0027] Optionally, the organic small molecule ligand with a β-diketone structure is selected from compounds of at least one of the following structural formulas:

[0028]

[0029] Optionally, Ar is selected from any one of the groups represented by the structure of formula III;

[0030]

[0031] Optionally, M is selected from any one of the groups represented by the structure of formula IV;

[0032]

[0033] Optionally, the glass transition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 290°C.

[0034] Optionally, the initial decomposition temperature (T d5％ ) is greater than or equal to 504℃.

[0035] Optionally, the residual carbon rate of the phenanthroline benzimidazole structure polyimide is greater than or equal to 50%.

[0036] Optionally, the molecular weight of the phenanthroline benzimidazole structure polyimide is greater than or equal to 20,000 g / mol.

[0037] Optionally, the glass transition temperature of the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material is greater than or equal to 250°C.

[0038] Optionally, the initial decomposition temperature (T d5％ ) is greater than or equal to 350℃.

[0039] Optionally, the residual carbon rate of the phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material is greater than or equal to 55%.

[0040] Optionally, the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid-responsive data encryption material realizes acid-responsive data encryption under the action of proton acid, and controls the interaction between the proton acid and the imidazole group in phenanthroline imidazole and the small molecule ligand Ligand, thereby affecting the sensitization characteristics of the ligand to the rare earth ion Ln, thereby realizing the fluorescence intensity of the rare earth ion Ln, and further realizing the adjustment of its fluorescence emission spectrum.

[0041] According to another aspect of the present application, a method for preparing the above-mentioned phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material is provided, firstly, 1,10-phenanthroline-2,9-diacid and o-phenylenediamine are used as raw materials to prepare 2,9-bis(1-hydrogen-benzimidazole-2-yl)-1,10-phenanthroline, and then the 2,9-bis(1-hydrogen-benzimidazole-2-yl)-1,10-phenanthroline and 1-fluoro- 4-nitro-2-trifluoromethylbenzene is used as a monomer to prepare a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline through a nucleophilic substitution reaction in the presence of a catalyst, and then the dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline is reacted with a catalyst and a reducing agent. A reduction reaction is carried out in the presence of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline) to prepare a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline), and then the 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline is polymerized with an aromatic diamine and an aromatic dianhydride to prepare a phenanthroline benzimidazole structure polyimide. Then, under an inactive atmosphere, a rare earth metal chloride salt and a small molecule ligand with a β-diketone structure are reacted in an alkaline mixed solution to prepare an organic small molecule rare earth complex. Finally, under an inactive atmosphere, the small molecule rare earth metal complex and a polyimide polymer containing a phenanthroline benzimidazole structure are coordinated in an organic solvent to prepare a phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material.

[0042] The preparation method of the present invention for a phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material comprises the following steps:

[0043] S1. Adding a monomer mixture containing 1,10-phenanthroline-2,9-dicarboxylicacid and o-phenylenediamine to polyphosphorus, and performing reaction I to obtain 2,9-bis(1H-benzimidazol-2-yl)-1,10-phenanthroline;

[0044] S2, reacting a mixture containing 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline and 1-fluoro-4-nitro-2-trifluoromethylbenzene (1-fluoro-4-nitro-2-(trifluoromethyl)-benzene), catalyst I, and solvent I with II to obtain a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1H-benzo[d]imidazol-2-yl)-1,10-phenanthroline; in step S2, the monomer is reacted with the catalyst to prepare a product through a nucleophilic substitution reaction;

[0045] S3, under an inert atmosphere, reacting a mixture containing a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline, a catalyst II, a reducing agent, and a solvent II with III to obtain a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline); step S3 is to carry out a reduction reaction in the presence of a catalyst and a reducing agent to prepare a product;

[0046] S4. Under an inert atmosphere, a mixture containing a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1H-benzo[d]imidazole-2,1-diyl))-bis(3-(trifluoromethyl)-aniline)), a dianhydride monomer containing an Ar structure, a diamine monomer containing an M structure, and a solvent III is reacted IV-a, and then a catalyst III is added to the product, and the reaction is continued IV-b. Then, ethanol is added to the product to form a precipitate to obtain the phenanthroline benzimidazole structure polyimide;

[0047] S5, adding a rare earth metal chloride and an organic small molecule ligand with a β-diketone structure to the alkaline mixed solution, and performing reaction IV to obtain a small molecule rare earth complex;

[0048] S6. Mixing the phenanthroline benzimidazole structure polyimide and the small molecule rare earth complex in solvent IV, and coordinating them to obtain the phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material.

[0049] Optionally, in step S1, the molar ratio of 1,10-phenanthroline-2,9-diacid to o-phenylenediamine is 1:2.0-2.2.

[0050] Optionally, in step S1, the conditions of reaction I include: reaction temperature of 200-240° C., and reaction time of 5-8 h.

[0051] Optionally, step S1 further comprises pouring the reaction solution into an ice-water mixture after reaction I, adjusting the pH to 8.5-9.5 with aqueous ammonia to form a precipitate, and washing and drying the precipitate.

[0052] Optionally, in step S1, the process diagram of reaction I is as follows:

[0053]

[0054] Optionally, in step S2, the molar ratio of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline to 1-fluoro-4-nitro-2-trifluoromethylbenzene is 1:2.0-2.2.

[0055] Optionally, in step S2, the conditions of reaction II include: reaction temperature of 80-120° C., and reaction time of 12-24 h.

[0056] Optionally, step S2 further comprises pouring the reaction solution into water after reaction II to form a precipitate, and washing and drying the precipitate.

[0057] Optionally, in step S2, the process diagram of reaction II is as follows:

[0058]

[0059] Optionally, in step S2, catalyst I is selected from at least one of potassium carbonate, cesium carbonate, and calcium carbonate.

[0060] Optionally, in step S2, solvent I is selected from at least one of N-methylpyrrolidone, NN-dimethylformamide, and NN-dimethylacetamide.

[0061] Optionally, in step S3, catalyst II is a 5% dry basis palladium carbon catalyst (Pb / C catalyst, Pd loading is 5%).

[0062] Optionally, in step S3, the amount of catalyst II used is 8-12% by weight of the dinitro compound.

[0063] Optionally, in step S3, the reducing agent is 85% hydrazine hydrate (85% content of N2H4·H2O).

[0064] Optionally, in step S3, the amount of the reducing agent used is 5 to 10 times the weight of the dinitro compound.

[0065] Optionally, in step S3, the conditions of reaction III include: reaction temperature of 80-120° C., and reaction time of 12-24 h.

[0066] Optionally, in step S3, the mixture containing the dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1 hydrogen-benzimidazol-2-yl-1,10-phenanthroline, catalyst II, reducing agent, and solvent II is obtained by adding the reducing agent dropwise to the mixture containing the dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1 hydrogen-benzimidazol-2-yl-1,10-phenanthroline, catalyst II, and solvent II.

[0067] Optionally, step S3 further comprises filtering to remove catalyst II after reaction III, removing solvent I by rotary evaporation, and drying the obtained solid powder.

[0068] Optionally, in step S3, solvent II is selected from at least one of ethanol, NN-dimethylformamide, and NN-dimethylacetamide.

[0069] Optionally, in step S4, the ratio of the diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline), the dianhydride monomer containing the Ar structure, and the diamine monomer containing the M structure is 1:1:1.

[0070] Optionally, in step S4, catalyst III is selected from isoquinoline.

[0071] Optionally, in step S4, the conditions of reaction IV-a include: reaction at 80°C to 90°C for 1 to 2 hours.

[0072] Optionally, in step S4, a reaction material liquid containing a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1H-benzo[d]imidazole-2,1-diyl))-bis(3-(trifluoromethyl)-aniline)), a diamine monomer containing an M structure, and a solvent III is stirred and dissolved at 80-100° C. in an inert atmosphere for 0.5-2 h, and then a dianhydride monomer containing an Ar structure is added to obtain the mixture.

[0073] Optionally, in step S4, the conditions of reaction IV-b include: reaction time at 150°C to 160°C for 2 to 4 hours, then heating to 190°C to 200°C for 12 to 18 hours.

[0074] Optionally, step S4 further comprises gradually adding ethanol to the reaction solution after reaction IV-b to form a Dalian fibrous precipitate, filtering, washing with water, washing with alcohol, and drying.

[0075] Optionally, in step S4, solvent III is selected from at least one of m-cresol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0076] Optionally, in step S5, the molar ratio of the rare earth metal chloride salt to the organic small molecule ligand of the compound β-diketone structure is 1:3 to 3.1.

[0077] Optionally, in step S5, the conditions for reaction V include: heating to 60° C., reacting at this temperature for 0.5 to 4 hours, and naturally cooling under continuous stirring after the reaction until precipitation is complete.

[0078] Optionally, step S5 further comprises filtering the precipitate after reaction V, dissolving the precipitate with benzene, adding n-hexane and mixing, standing for 8 to 16 hours, filtering, and drying the solid product.

[0079] Optionally, in step S5, the process diagram of reaction V is as follows:

[0080]

[0081] Optionally, in step S5, the pH of the alkaline mixed solution is greater than or equal to 8, and the alkaline mixed solution includes a mixture of ethanol and water, and the volume ratio of the ethanol to water is 1:8-20.

[0082] Optionally, in step S6, the molar ratio of the small molecule rare earth metal complex to the phenanthroline imidazole group in the phenanthroline benzimidazole structure polyimide is 0.1 to 0.3:1.

[0083] Optionally, in step S6, the conditions of reaction VI include: reaction temperature of 50-120° C., reaction time of 8-15 h, and continuous stirring during the reaction process.

[0084] Optionally, step S6 further comprises concentrating the reaction solution by rotary evaporation after reaction VI, adding the solution dropwise to ethanol to induce formation of a precipitate, and washing the precipitate with water, washing with alcohol, and drying.

[0085] Optionally, in step S6, the process diagram of reaction VI is as follows:

[0086]

[0087] Optionally, solvent IV is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0088] According to another aspect of the present application, there is also provided an application of at least one of the above-mentioned phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material or the phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material prepared by the above method in a polymer acid responsive data encryption material.

[0089] Optionally, the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material realizes acid responsive data encryption under the action of proton acid;

[0090] By adjusting the amount of proton acid added, the interaction between the proton acid and the imidazole group and the β-diketone organic small molecule ligand in the phenanthroline benzimidazole structure polyimide is controlled to affect the sensitization properties to rare earth ions, thereby achieving different fluorescence emission spectra of the data encryption material that responds to the single rare earth ion coordination acid of the phenanthroline benzimidazole structure polyimide;

[0091] Optionally, the acid response data is encrypted as shown in Formula V:

[0092]

[0093] Among them, H + It is a protonic acid, and the protonic acid is selected from organic acids and inorganic acids.

[0094] Optionally, the organic acid is selected from at least one of formic acid, acetic acid, and propionic acid.

[0095] Optionally, the inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0096] The beneficial effects of this application include:

[0097] The present application provides a phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material that achieves acid responsive data encryption under the action of proton acid. By controlling the interaction between the proton acid and the imidazole group in the phenanthroline imidazole and the small molecule ligand Ligand, the ligand's sensitization characteristics to the rare earth ion Ln are affected to achieve the rare earth ion Ln fluorescence intensity, thereby achieving the regulation of its fluorescence emission spectrum. The glass transition temperature of the phenanthroline benzimidazole structured polyimide in the present application encryption material is above 300°C, and the initial decomposition temperature (T d5％ ) is above 500°C, the residual carbon rate is above 50%, the glass transition temperature of the phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid response data encryption material is above 250°C, the initial decomposition temperature (T d5％ ) is above 350° C., the residual carbon rate is above 55%, and the molecular weight of the phenanthroline benzimidazole structure polyimide is above 25,000 g / mol. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] Figure 1 This is the NMR spectrum of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline prepared in the examples of this application.

[0099] Figure 2 This is the NMR spectrum of the dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1 hydrogen-benzimidazol-2-yl-1,10-phenanthroline prepared in the examples of this application.

[0100] Figure 3 This is the NMR spectrum of the diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline) prepared in the examples of the present application.

[0101] Figure 4 This is the NMR spectrum of the phenanthroline benzimidazole structure polyimide polymer PI-1 prepared in the examples of this application.

[0102] Figure 5 These are the GPC test results of the phenanthroline benzimidazole structured polyimide polymer PI-1 prepared in the examples of this application.

[0103] Figure 6 This is a matrix color coding diagram of the phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material prepared in an embodiment of the present application. (a) is under sunlight, (b) is under ultraviolet light, and (c) is the decryption of the matrix color coding diagram after adding an equal amount of acetic acid.

[0104] Figure 7 For the different THF solutions in the test example of this application CH3COOH PI-Ligand-Eu content 3+ -10% of the fluorescence emission spectrum.

[0105] Figure 8 PI-Ligand-Eu with different CH3COOH contents in THF solution in the test example of this application 3+ -10% color change diagram, where (a) is PI-Ligand-Eu 3+ -10%, (b) is PI-Ligand-Eu 3+ -10% plus 5% acetic acid, (c) is PI-Ligand-Eu 3+ -10% plus 10% acetic acid. DETAILED DESCRIPTION

[0106] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0107] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0108] Unless otherwise specified, conventional methods were used for testing, and instrument settings were those recommended by the manufacturer.

[0109] Data testing conditions and methods in the examples of this application:

[0110] Nuclear Magnetic Resonance Spectroscopy (NMR): 1 H NMR measurements were performed on a Bruker AVANCE III 400 MHz NMR instrument with tetramethylsilane (TMS) as the internal standard and DMSO-d6 as the solvent.

[0111] Fourier transform infrared (FT-IR) analysis: FT-IR spectra were obtained using a VERTEX70 at 4000 cm -1 to 400cm -1 tested within the wavelength range.

[0112] Fluorescence spectrum test: The fluorescence spectrum was tested on a FS920 (450W xenon lamp) fluorescence spectrometer.

[0113] Gel Permeation Chromatography (GPC): GPC was measured on a Waters 1515 gel permeation chromatograph using tetrahydrofuran (THF) as the mobile phase.

[0114] Differential Scanning Calorimetry (DSC) was performed using a Q20 instrument at a heating rate of 10 K / min in a nitrogen atmosphere.

[0115] Thermogravimetric (TG) analysis was performed using a STA449C analyzer at a heating rate of 10 K / min under a nitrogen atmosphere.

[0116] According to one embodiment of the present application, a method for preparing a phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material comprises:

[0117] (1) 1,10-phenanthroline-2,9-dicarboxylic acid and o-phenylenediamine are reacted in polyphosphorus to prepare 2,9-Bis(1H-benzimidazol-2-yl)-1,10-phenanthroline;

[0118] (2) 2,9-bis(1-(4-nitro-2-(trifluorometh yl)-phenyl)-1H-benzo[d]imidazol-2-yl)-1,10-phenanthroline was prepared by nucleophilic substitution reaction of 2,9-bis(1-(4-nitro-2-(trifluoromethyl)-phenyl)-1H-benzo[d]imidazol-2-yl)-1,10-phenanthroline and 1-fluoro-4-nitro-2-trifluoromethylbenzene in the presence of a catalyst;

[0119] (3) subjecting the dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1H-benzimidazole-2-yl-1,10-phenanthroline to a reduction reaction in the presence of a catalyst and a reducing agent to prepare a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1H-benzo[d]imidazole-2,1-diyl))-bis(3-(trifluoromethyl)-aniline);

[0120] (4) under an inert atmosphere, a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1H-benzo[d]imidazole-2,1-diyl))-bis(3-(trifluoromethyl)-aniline)), a dianhydride monomer containing an Ar structure, and a diamine monomer containing an M structure are mixed in an organic solvent, and a polymerization reaction is carried out under the action of a catalyst to obtain the phenanthroline benzimidazole structure polyimide;

[0121] (5) Under an inert atmosphere, reacting a rare earth metal chloride salt and a small molecule ligand with a β-diketone structure in an alkaline mixed solution to prepare a small molecule rare earth complex;

[0122] (6) Under an inert atmosphere, the small molecule rare earth metal complex obtained in step 5 and the polyimide polymer containing a phenanthroline benzimidazole structure obtained in step 4 are coordinated in an organic solvent to prepare the phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material.

[0123] Example 1

[0124] Steps S1 to S3 The synthesis of 4,4′-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline) was as follows.

[0125] Step S1: Under an inert gas atmosphere, 1.34 g of 1,10-phenanthroline-2,9-diacid and 1.135 g of o-phenylenediamine were added to 12.5 ml of polyphosphoric acid, and the mixture was reacted at 220° C. for 6 h. After the reaction was completed, the mixture was cooled to 120° C., and the reaction solution was poured into 200 ml of an ice-water mixture. The mixture was adjusted to pH 9 with aqueous ammonia, and the precipitate was filtered to obtain a precipitate. The precipitate was washed three times with hexane and dried in a vacuum drying oven at 80° C. for 6 h to obtain the product 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline, and the NMR spectrum was as follows: Figure 1 As shown;

[0126] Step S2: Under an inert gas atmosphere, 2.01 g of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline prepared in step (S1), 1.38 g of anhydrous potassium carbonate and 2.195 g of 1-fluoro-4-nitro-2-trifluoromethylbenzene were added to 20 ml of DMF, and the mixture was reacted at 95 ° C. for 15 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was poured into 150 ml of deionized water. The precipitate was filtered to obtain a precipitate, washed three times with hexane, and dried in a vacuum drying oven at 80 ° C. for 6 h to obtain a product, which is a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline, and the nuclear magnetic spectrum is as follows: Figure 2 As shown;

[0127] Step S3: Under an inert gas atmosphere, 0.50 g of a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1 hydrogen-benzimidazol-2-yl-1,10 phenanthroline and 0.05 g of a 10% Pd / C catalyst (Pd loading is 10%) are added to 20 ml of ethanol, and then 0.4 ml of hydrazine hydrate is added dropwise to the above reaction system, and the reaction is carried out at 85 ° C. for 12 h. After the reaction is completed, the reaction is cooled to room temperature, and the catalyst is removed by filtration. The resulting liquid is subjected to rotary evaporation to remove the solvent to obtain a solid powder, which is dried in a vacuum drying oven at 80 ° C. for 6 h to obtain a product, which is a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline, and the nuclear magnetic spectrum is as follows: Figure 3 shown.

[0128] Step S4: Synthesis of phenanthroline benzimidazole structured polyimide polymer

[0129] Under an inert gas atmosphere, 0.30 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline and 0.08 g of 4,4'-diaminodiphenyl ether (ODA) were quickly added to a three-necked flask, and then about 5.5 ml of m-cresol was added as a solvent. The reactants were dissolved by stirring at 80 ° C under a nitrogen atmosphere for 1 hour. 0.29 g of 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride was added to the above mixture. The reaction temperature was raised to 150 ° C and stirred continuously. After 3 hours, 0.30 mL of isoquinoline was added to the reaction system as a dehydrating agent and catalyst. Then, the temperature was raised to 200 ° C and the reaction was continued for 12 hours under stirring. After cooling, the reaction solution was gradually poured into ethanol to generate a large amount of fibrous precipitate. After filtration, the dried product was washed with a large amount of water and ethanol and recorded as PI-1. The nuclear magnetic spectrum is as follows Figure 4 As shown, the GPC test results are as follows Figure 5 shown.

[0130] Step S5: Synthesis of small molecule rare earth complexes

[0131] Under an inert gas atmosphere, acetylacetone (0.06 g, 6 mmol) was dissolved in 30 mL of anhydrous ethanol, and then 6 mL of an aqueous solution of NaOH (1N) and 10 mL of anhydrous ethanol solution of Eu Cl3·6H2O (2 mmol) were added to the anhydrous ethanol solution of acetylacetone in sequence, and then 200 mL of distilled water was added, the mixture was mixed and heated to 60°C, and cooled to room temperature under stirring. A precipitate was precipitated and filtered, and the obtained solid was dissolved in 60 mL of benzene. 200 mL of n-hexane was added, and the mixture was allowed to stand at room temperature overnight, filtered, and dried in vacuo at 60°C for 48 h to obtain a light yellow solid recorded as a small molecule rare earth complex Eu(acac)3·2H2O.

[0132] Step S6: Synthesis of a phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material

[0133] 0.20 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). A small molecule rare earth complex containing Ln(acac)3·2H2O was added to the reaction mixture at a molar ratio of 10% of the phenanthroline imidazole group. The reaction system was stirred continuously at a stable temperature of 60°C for 15 hours. After the reaction was completed, the reaction solution was concentrated by rotary evaporation and then slowly added dropwise to ethanol to induce the formation of a precipitate. The precipitate was washed with water and ethanol and dried, and the product was recorded as PI-Ligand-Eu 3+ -10%.

[0134] Example 2

[0135] Steps S1 to S5 are the same as those in Example 1, except that step S6 is:

[0136] 0.20 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). A small molecule rare earth complex containing Ln(acac)3·2H2O was added to the reaction mixture at a molar ratio of 20% of the phenanthroline imidazole group. The reaction system was stirred continuously at a stable temperature of 60°C for 15 hours. After the reaction was completed, the reaction solution was concentrated by rotary evaporation and then slowly added dropwise to ethanol to induce the formation of a precipitate. The precipitate was washed with water and ethanol and dried, and the product was recorded as PI-Ligand-Eu 3+ -20%.

[0137] Example 3

[0138] Steps S1 to S5 are the same as those in Example 1, except that step S6 is:

[0139] 0.20 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). A small molecule rare earth complex containing Ln(acac)3·2H2O was added to the reaction mixture at a molar ratio of 30% of the phenanthroline imidazole group. The reaction system was stirred continuously at a stable temperature of 60°C for 15 hours. After the reaction was completed, the reaction solution was concentrated by rotary evaporation and then slowly added dropwise to ethanol to induce the formation of a precipitate. The precipitate was washed with water and ethanol and dried, and the product was recorded as PI-Ligand-Eu 3+ -30%.

[0140] Example 4

[0141] Steps S1-S3 and S5-S6 are the same as those in Example 1, except that step S4 is:

[0142] Under an inert gas atmosphere, 0.30 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazolyl))bis(3-(trifluoromethyl)aniline) and 0.022 g of p-phenylenediamine were quickly added to a three-necked flask. Approximately 5 ml of m-cresol was then added as a solvent, and the mixture was stirred at 80°C under a nitrogen atmosphere for 1 hour to dissolve the reactants. 0.36 g of hexafluoroisopropylphthalic anhydride (6FDA) was added to the mixture. The reaction temperature was raised to 150°C with continuous stirring. After 3 hours, 0.30 mL of isoquinoline was added to the reaction system as a dehydrating agent and catalyst. The temperature was then raised to 200°C, and the reaction was continued with stirring for 12 hours. After cooling, the reaction solution was gradually poured into ethanol, generating a large amount of fibrous precipitate. The product was filtered, washed with copious amounts of water and ethanol, and dried, designated PI-2.

[0143] Example 5

[0144] Steps S1-S3 and S5-S6 are the same as those in Example 1, except that step S4 is:

[0145] Under an inert gas atmosphere, 0.30 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazolyl))bis(3-(trifluoromethyl)aniline) and 0.064 g of 4,4'-diaminobiphenyl were quickly added to a three-necked flask. Approximately 7 ml of m-cresol was then added as a solvent, and the mixture was stirred at 80°C under a nitrogen atmosphere for 1 hour to dissolve the reactants. 0.42 g of bisphenol A diether dianhydride was added to the above mixture. The reaction temperature was raised to 150°C with continuous stirring. After 3 hours, 0.30 mL of isoquinoline was added to the reaction system as a dehydrating agent and catalyst. The temperature was then raised to 200°C, and the reaction was continued with stirring for 12 hours. After cooling, the reaction solution was gradually poured into ethanol, generating a large amount of fibrous precipitate. The product was filtered, washed with copious amounts of water and ethanol, and dried, and designated PI-3.

[0146] Test Example 1 Encryption process of phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid response data encryption material

[0147] like Figure 6 As shown, PI-Ligand-Eu was prepared at a concentration of 20 mg / ml. 3+ -10% tetrahydrofuran solution and 20mg / ml tetrahydrofuran solution of Eu(acac)3·2H2O. Taking advantage of their different photoluminescence properties, we use these compounds as basic pixels, where red represents "1" and blue represents "0". Deploying this color coding strategy can perform data storage and encryption within a 3×8 matrix. Acetic acid is added during the decryption process, where the equimolar addition of acetic acid realizes the decryption of the data string "01000011,01000001,01010011", which is then translated into the ASCII representation "CAS". PI-Ligand-Eu with different acetic acid addition amounts 3+ -10% of the fluorescence emission spectrum as Figure 7 As shown, PI-Ligand-Eu with different acetic acid contents 3+ -10% color change as shown Figure 8 As shown, (a) is PI-Ligand-Eu 3+ -10%, (b) is PI-Ligand-Eu 3+ -10% plus 5% acetic acid, (c) is PI-Ligand-Eu 3+ -10% plus 10% acetic acid.

[0148] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material, characterized in that: Including phenanthroline benzimidazole structure polyimide, rare earth ions, and β-diketone structure organic small molecule ligands combined through coordination; The phenanthroline benzimidazole structure polyimide has a structure of the general formula shown in Formula I: Formula I; wherein Ar is the residue of a dianhydride monomer; M is selected from C6-C 40 At least one of the arylene groups; 0.5<n≤1,n+m=1; The organic small molecule ligand of the β-diketone structure has a structure of the general formula shown in Formula Ia: Formula Ia.

2. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material has a general structure shown in Formula II: Formula II; Among them, Ln represents rare earth ions and Ligand represents organic small molecule ligands.

3. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The rare earth ions are selected from at least one element ion of Tb, Eu, Ce, Yb, Sm, and Gd.

4. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The molar ratio of the rare earth ions to the N atoms in the phenanthroline benzimidazole structure polyimide is 0.025-0.5:

1.

5. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The organic small molecule ligand of the β-diketone structure is selected from at least one of α-thienyltrifluoroacetone, acetylacetone, dibenzoylmethane, benzoylacetone, benzoyltrifluoroacetone, and β-naphthoyltrifluoroacetone.

6. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: Ar is selected from any one of the groups represented by the structure of formula III; Formula III.

7. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: M is selected from any one of the groups represented by the structure of formula IV; Formula IV.

8. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The glass transition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 290°C.

9. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The initial decomposition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 504°C.

10. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The residual carbon rate of the phenanthroline benzimidazole structure polyimide is greater than or equal to 50%.

11. The phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material according to claim 1, characterized in that: The molecular weight of the phenanthroline benzimidazole structure polyimide is greater than or equal to 20,000 g / mol.

12. The phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material according to claim 1, characterized in that: The glass transition temperature of the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material is greater than or equal to 250°C.

13. The phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material according to claim 1, characterized in that: The initial decomposition temperature of the phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid responsive data encryption material is greater than or equal to 350°C.

14. The phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material according to claim 1, characterized in that: The residual carbon rate of the phenanthroline benzimidazole structured polyimide single rare earth ion coordination acid response data encryption material is greater than or equal to 55%.

15. The method for preparing the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material according to any one of claims 1 to 14, characterized in that: The steps include: S1, adding a monomer mixture containing 1,10-phenanthroline-2,9-diacid and o-phenylenediamine to polyphosphoric acid, reacting I to obtain 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline; S2, reacting a mixture containing 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline, 1-fluoro-4-nitro-2-trifluoromethylbenzene, catalyst I, and solvent I with II to obtain a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline; S3. Under an inert atmosphere, a mixture containing a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline, a catalyst II, a reducing agent, and a solvent II is reacted with step III to obtain a diamine monomer 4, 4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline; S4, under an inert atmosphere, reacting a mixture containing a diamine monomer 4, 4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline, a dianhydride monomer containing an Ar structure, a diamine monomer containing an M structure, and a solvent III, reacting IV-a, then adding a catalyst III to the product, continuing to react IV-b, and then adding ethanol to the product to form a precipitate to obtain the phenanthroline benzimidazole structure polyimide; S5, adding a rare earth metal chloride and an organic small molecule ligand with a β-diketone structure to the alkaline mixed solution, reacting V to obtain a small molecule rare earth complex; S6. Mixing the phenanthroline benzimidazole structure polyimide and the small molecule rare earth complex in solvent IV, and coordinating them to obtain the phenanthroline benzimidazole structure polyimide single rare earth ion coordination acid responsive data encryption material.

16. The preparation method according to claim 15, characterized in that In step S1, the molar ratio of 1,10-phenanthroline-2,9-diacid to o-phenylenediamine is 1:2.0-2.

2.

17. The preparation method according to claim 15, characterized in that In step S1, the conditions of reaction I include: reaction temperature of 200-240° C., and reaction time of 5-8 h.

18. The preparation method according to claim 15, characterized in that In step S2, the molar ratio of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline to 1-fluoro-4-nitro-2-trifluoromethylbenzene is 1:2.0-2.

2.

19. The preparation method according to claim 15, characterized in that In step S2, the conditions of reaction II include: reaction temperature of 80-120° C., and reaction time of 12-24 h.

20. The preparation method according to claim 15, characterized in that In step S2, the catalyst I is selected from at least one of potassium carbonate, cesium carbonate, and calcium carbonate.

21. The preparation method according to claim 15, characterized in that In step S2, solvent I is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

22. The preparation method according to claim 15, characterized in that In step S3, catalyst II is a 5% dry basis palladium carbon catalyst.

23. The preparation method according to claim 15, characterized in that In step S3, the amount of catalyst II used is 8-12% by weight of the dinitro compound.

24. The preparation method according to claim 15, characterized in that In step S3, the reducing agent is 85% hydrazine hydrate.

25. The preparation method according to claim 15, characterized in that In step S3, the amount of the reducing agent is 5 to 10 times the weight of the dinitro compound.

26. The preparation method according to claim 15, characterized in that In step S3, the conditions of reaction III include: reaction temperature of 80-120° C., and reaction time of 12-24 h.

27. The preparation method according to claim 15, characterized in that In step S3, the solvent II is selected from at least one of ethanol, N,N-dimethylformamide, and N,N-dimethylacetamide.

28. The preparation method according to claim 15, characterized in that In step S4, the ratio of the diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazolyl))bis(3-(trifluoromethyl)aniline), the dianhydride monomer containing an Ar structure, and the diamine monomer containing an M structure is 1:1:

1.

29. The preparation method according to claim 15, characterized in that In step S4, the catalyst III is selected from isoquinoline.

30. The preparation method according to claim 15, characterized in that In step S4, the conditions of reaction IV-a include: reaction at 80°C to 90°C for 1 to 2 hours.

31. The preparation method according to claim 15, characterized in that In step S4, the conditions of reaction IV-b include: reaction time at 150°C-160°C for 2-4 hours, then heating to 190°C-200°C for 12-18 hours.

32. The preparation method according to claim 15, characterized in that In step S4, the solvent III is selected from at least one of m-cresol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

33. The preparation method according to claim 15, characterized in that In step S5, the molar ratio of the rare earth metal chloride to the organic small molecule ligand with a β-diketone structure is 1:3 to 3.

1.

34. The preparation method according to claim 15, characterized in that In step S5, the conditions for reaction V include: heating to 60° C., reacting at this temperature for 0.5 to 4 hours, and naturally cooling under continuous stirring after the reaction until precipitation is complete.

35. The preparation method according to claim 15, characterized in that In step S5, the pH of the alkaline mixed solution is greater than or equal to 8, and the alkaline mixed solution includes a mixture of ethanol and water, and the volume ratio of the ethanol to water is 1:8-20.

36. The preparation method according to claim 15, characterized in that In step S6, the molar ratio of the small molecule rare earth complex to the phenanthroline imidazole group in the phenanthroline benzimidazole structure polyimide is 0.1-0.3:

1.

37. The preparation method according to claim 15, characterized in that In step S6, the reaction coordination conditions include: reaction temperature of 50-120° C., and reaction time of 8-15 h.

38. The preparation method according to claim 15, characterized in that The solvent IV is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

39. Use of the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material according to any one of claims 1 to 14, or the phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material prepared according to the preparation method according to any one of claims 15 to 38 in a polymer acid responsive data encryption material.

40. The use according to claim 39, characterized in that The phenanthroline benzimidazole structured polyimide single rare earth ion coordinated acid responsive data encryption material realizes acid responsive data encryption under the action of proton acid; By adjusting the amount of proton acid added, the interaction between the proton acid and the imidazole group and the β-diketone organic small molecule ligand in the phenanthroline benzimidazole structure polyimide is controlled to affect the sensitization properties to rare earth ions, thereby achieving different fluorescence emission spectra of the data encryption material that responds to the single rare earth ion coordination acid of the phenanthroline benzimidazole structure polyimide; The acid response data encryption method is shown in Formula V: Formula V; Among them, H + It is a protonic acid, and the protonic acid is selected from organic acids and inorganic acids.

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