Polyimide single rare earth ion coordination full-spectrum luminescent material with phenanthroline benzimidazole structure as well as preparation method and application of polyimide single rare earth ion coordination full-spectrum luminescent material

Abstract

The invention discloses a phenanthroline benzimidazole structure polyimide single rare earth ion coordination full-spectrum luminescent material as well as a preparation method and application thereof, and belongs to the technical field of preparation of polymer luminescent materials. The phenanthroline and benzimidazole structure polyimide single rare earth ion coordination full-spectrum luminescent material comprises phenanthroline and benzimidazole structure polyimide, rare earth ions and an organic small molecule ligand of a beta-diketone structure which are combined through coordination. The polymer single rare earth coordination material not only retains the advantages of polyimide, but also shows special optical properties brought by addition of rare earth ions (Ln < 3 + >), PI-Tb < 3 + > formed after coordination of the coordination polymer and the rare earth ions Tb < 3 + > can emit full-spectrum white light (CIE = (0.31, 0.35)), and shows excellent thermal stability and solubility.

Description

Technical Field

[0001] The present application relates to a phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material and a preparation method and application thereof, belonging to the technical field of preparation of polymer luminescent materials. Background Art

[0002] Polymer light-emitting diodes (PLEDs) are a class of polymer-based devices that utilize polymers as light-emitting materials. In contrast to the inefficient vacuum thermal evaporation process used for organic light-emitting diodes (OLEDs), PLEDs are manufactured using cost-effective techniques such as spin coating or inkjet printing. Currently, polymers used in PLEDs, including poly(p-phenylene), polystyrene, and polyfluorene, are known for their low production costs and excellent processability. However, these polymers exhibit poor thermomechanical properties and are prone to photodegradation and oxidation reactions, especially under harsh environmental conditions. These factors greatly limit the service life and reliability of PLEDs devices. In addition, achieving white light emission (full light emission) with polymers remains a challenge.

[0003] Polyimides (PIs) are widely recognized for their superior thermal stability, chemical resistance, dimensional stability, and mechanical strength. However, in the field of optoelectronics, they are usually used as transport layers, substrates, or supporting materials for luminescence, and are rarely used directly as luminescent materials. Due to the strong intramolecular and intermolecular charge transfer (CT) interactions of polyimide (PI), the CT (π-π*) state is the lowest excited state, and the CT state oscillation intensity is low, resulting in a low fluorescence quantum yield of the polymer, so traditional aromatic PIs usually do not emit light. Current research on the luminescence properties of aromatic PIs generally involves the introduction of luminophores into the polymer chain structure. Other studies incorporate rare earth metal complexes into PIs. Rare earth elements are known for their unique electronic transitions, which produce unique emission spectra with high color purity, high luminescence efficiency, and extended fluorescence lifetime. However, this pre-coordinated polymerization method is not conducive to obtaining high molecular weight PIs, and the subsequent film formation process becomes more challenging. Rare earth metals can be introduced into PIs through a post-polymerization coordination strategy, which can theoretically produce coordinated PIs with superior properties, while also obtaining pure and tunable color emission from the polymer.

[0004] To date, there are still many difficulties and bottlenecks in the research of luminescent rare earth coordination polymers: (1) In terms of synthesis, due to the large radius and strong charge of rare earth ions, the large coordination number and relatively flexible coordination configuration during the coordination reaction, it is difficult to control the synthesis of rare earth coordination polymers with specific structural characteristics during the synthesis process, which is far from the goal of targeted synthesis; (2) In terms of performance, the luminescence properties of rare earth coordination polymers largely depend on the process of organic ligand sensitization of rare earth ions. External environmental factors, such as the vibration of water molecules, also have a great influence on the luminescence of rare earth coordination polymers. Therefore, how to select suitable organic ligands, control reaction conditions, or use post-modification treatment methods to prepare rare earth coordination polymers with good luminescence performance still needs further research. (3) In terms of application, due to the relatively poor stability, solubility and mechanical properties of rare earth coordination polymers, how to prepare rare earth coordination polymers into devices through process means to meet the needs of practical applications still needs further exploration. Summary of the invention

[0005] In order to solve the problems of poor directional synthesis ability, insufficient emission spectrum width, relatively poor application stability and solubility that still exist in the prior art of luminescent rare earth coordination polymers, the present application provides a phenanthroline benzimidazole structure polyimide single rare earth ion coordination full spectrum luminescent material and its preparation method and application, which introduces a phenanthroline benzimidazole structure to make it have excellent rare earth metal ion coordination ability. On this basis, PI-Tb is generated by reacting a β-diketone small molecule ligand with a sensitizing property for rare earth ions with a polyimide molecule phenanthroline benzimidazole ligand. 3+ Coordinated polyimide. Tb 3+ Emitting red light under organic ligand sensitization (Tb 3+ Ionic 5D 0 →7F 5 Electronic transition) and Tb 3+ The polymer blue light red shift (550-615nm) occurs due to the charge transfer formed by the coordination with the phenanthroline structure in the polymer. Since there is cross-linking in the molecular structure of the coordinated polyimide, the cross-linking effect strengthens the charge transfer between molecules, thereby widening the emission spectrum, covering a wide band of 470-700nm (full spectrum emission). The rigid structure of phenanthroline benzimidazole gives the material good thermal stability and chemical stability, while the twisted structure increases the free volume of the polymer material, enhances the solubility of the polymer material, and improves the processability tolerance of the material.

[0006] This application adopts the following technical solutions:

[0007] According to one aspect of the present application, a phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is provided, comprising a phenanthroline benzimidazole structure polyimide, a rare earth ion, and an organic small molecule ligand of a β-diketone structure combined by coordination;

[0008] The phenanthroline benzimidazole structure polyimide has a general structure shown in Formula I:

[0009]

[0010] wherein Ar is the residue of a dianhydride monomer;

[0011] M is selected from C 6 -C 40 At least one of the arylene groups;

[0012] 0.5<n≤1,n+m=1;

[0013] The rare earth ions are selected from Tb ions;

[0014] The organic small molecule ligand of the β-diketone structure is selected from α-thienyl trifluoroacetone.

[0015] Optionally, the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material has a general structure shown in Formula II:

[0016]

[0017] Among them, Ln represents rare earth ions, and Ligand represents small molecule ligands with β-diketone structure;

[0018] Ar is the residue of a dianhydride monomer;

[0019] M is selected from C 6 -C 40 At least one of the arylene groups;

[0020] 0.5<n≤1,n+m=1;

[0021] The rare earth ions are selected from Tb ions;

[0022] The organic small molecule ligand of the β-diketone structure is selected from α-thienyl trifluoroacetone.

[0023] The applicant has found that in the full-spectrum luminescence, only Tb can achieve full-spectrum emission (so-called white light emission) while Eu, Ce, Yb, Sm, Gd and other rare earth ions cannot achieve the full-spectrum emission characteristics of the present application. At the same time, the organic small molecules with β-diketone structure can only achieve full-spectrum emission (so-called white light emission) with α-thienyl trifluoroacetone.

[0024] 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;

[0025] Optionally, the organic small molecule ligand of the β-diketone structure is selected from α-thienyltrifluoroacetone.

[0026] Optionally, Ar is selected from any one of the groups of the structure shown in formula III;

[0027]

[0028] Optionally, M is selected from any one of the groups of the structure shown in formula IV;

[0029]

[0030] Optionally, the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material has a fluorescence emission peak in the wavelength range of 490 to 630 nm under 393 nm light excitation.

[0031] Optionally, the glass transition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 294°C.

[0032] Optionally, the initial decomposition temperature (T d5％ ) is greater than or equal to 504℃.

[0033] Optionally, the residual carbon rate of the phenanthroline benzimidazole structure polyimide is greater than or equal to 50%.

[0034] Optionally, the molecular weight of the phenanthroline benzimidazole structure polyimide is greater than or equal to 20,000 g / mol.

[0035] Optionally, the glass transition temperature of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is greater than or equal to 250°C.

[0036] Optionally, the initial decomposition temperature (T d5％ ) is greater than or equal to 380℃.

[0037] Optionally, the residual carbon rate of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is greater than or equal to 55%.

[0038] According to another aspect of the present application, a method for preparing the above-mentioned phenanthroline benzimidazole structure polyimide single rare earth ion coordination full-spectrum luminescent 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 as a monomer is used to prepare a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline by 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. The invention relates to a method for preparing a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline by a reduction reaction in the presence of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline, and then using the 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline to polymerize with aromatic diamine and 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 of 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 coordinated full spectrum luminescent material.

[0039] The preparation method of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material of the present application comprises the following steps:

[0040] S1, adding a monomer mixture containing 1,10-phenanthroline-2,9-dicarboxylic acid and o-phenylenediamine to polyphosphorus, reacting I, to obtain 2,9-bis(1H-benzimidazol-2-yl)-1,10-phenanthroline;

[0041] 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 subjected to a nucleophilic substitution reaction under the action of the catalyst to prepare a product;

[0042] S3, under an inert atmosphere, reacting a mixture containing a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazole-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-benzimidazole-yl))bis(3-(trifluoromethyl)aniline (4,4'-((1,10-phenanthroline-2,9-diyl)-bis(1H-benzo[d]imidazole-2,1-diyl))-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;

[0043] S4, under an inert atmosphere, reacting 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 (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, performing a reaction IV-a, then adding a catalyst III to the product, continuing the reaction IV-b, and then adding ethanol to the product to form a precipitate to obtain the phenanthroline benzimidazole structure polyimide;

[0044] S5, adding rare earth metal chloride and an organic small molecule ligand with a β-diketone structure to the alkaline mixed solution, reacting IV, and obtaining a small molecule rare earth complex;

[0045] 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 coordinated full spectrum luminescent material.

[0046] Optionally, in step S1, the molar ratio of 1,10-phenanthroline-2,9-diacid to o-phenylenediamine is 1:2.0-2.2.

[0047] Optionally, in step S1, the conditions of reaction I include: reaction temperature of 200-240° C., and reaction time of 5-8 h.

[0048] 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.

[0049] Optionally, in step S1, the process schematic diagram of reaction I is as follows:

[0050]

[0051] 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.

[0052] Optionally, in step S2, the conditions of reaction II include: reaction temperature of 80 to 120° C., and reaction time of 12 to 24 h.

[0053] Optionally, step S2 further comprises, after reaction II, pouring the reaction solution into water to form a precipitate, and washing and drying the precipitate.

[0054] Optionally, in step S2, the process schematic diagram of reaction II is as follows:

[0055]

[0056] Optionally, in step S2, catalyst I is selected from at least one of potassium carbonate, cesium carbonate and calcium carbonate.

[0057] Optionally, in step S2, solvent I is selected from at least one of N-methylpyrrolidone, NN-dimethylformamide, and NN-dimethylacetamide.

[0058] Optionally, in step S3, catalyst II is a 5% dry palladium carbon catalyst (Pb / C catalyst, Pd loading is 5%).

[0059] Optionally, in step S3, the amount of catalyst II used is 8-12% by weight of the dinitro compound.

[0060] Optionally, in step S3, the reducing agent is 85% hydrazine hydrate (85% N 2 H 4 ·H 2 O).

[0061] Optionally, in step S3, the amount of the reducing agent used is 5 to 10 times the weight of the dinitro compound.

[0062] Optionally, in step S3, the conditions of reaction III include: reaction temperature of 80 to 120° C., and reaction time of 12 to 24 h.

[0063] 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.

[0064] 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.

[0065] Optionally, in step S3, solvent II is selected from at least one of ethanol, NN-dimethylformamide, and NN-dimethylacetamide.

[0066] 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.

[0067] Optionally, in step S4, catalyst III is selected from isoquinoline.

[0068] Optionally, in step S4, the conditions of reaction IV-a include: reaction time at 80°C to 90°C for 1 to 2 hours.

[0069] 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 to 100° C. in an inert atmosphere for 0.5 to 2 h, and then a dianhydride monomer containing an Ar structure is added to obtain the mixture.

[0070] 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.

[0071] Optionally, step S4 further includes 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.

[0072] Optionally, in step S4, solvent III is selected from at least one of m-cresol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0073] 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.

[0074] 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.

[0075] Optionally, step S5 further comprises filtering the precipitate after reaction V, dissolving the precipitate with benzene, adding n-hexane to mix, standing for 8 to 16 hours, filtering, and drying the solid product.

[0076] Optionally, in step S5, the process schematic diagram of reaction V is as follows:

[0077]

[0078] 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 ethanol to water is 1:8-20.

[0079] 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 0.1-0.3:1.

[0080] Optionally, in step S6, the conditions of reaction VI include: reaction temperature of 50 to 120° C., reaction time of 8 to 15 h, and continuous stirring during the reaction.

[0081] Optionally, step S6 further comprises concentrating the reaction solution by rotary evaporation after reaction VI, adding the solution dropwise into ethanol to induce formation of a precipitate, and washing the precipitate with water, alcohol, and drying.

[0082] Optionally, in step S6, the process schematic diagram of reaction VI is as follows:

[0083]

[0084] Optionally, solvent IV is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0085] 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 coordinated full-spectrum luminescent material or the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material prepared by the above-mentioned method in a polymer luminescent material.

[0086] The beneficial effects of this application include:

[0087] The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material provided in the present application has a fluorescence emission peak in the wavelength range of 490 to 630 nm under 393 nm light excitation. 3+ PI-Tb formed after coordination 3+ It can emit full spectrum white light (CIE = (0.31, 0.35)); the glass transition temperature of the luminescent material is above 294°C, and the initial decomposition temperature (T d5％ ) is above 504°C, the residual carbon rate is above 50%, the glass transition temperature of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is above 250°C, the initial decomposition temperature (T d5％ ) is above 380°C, and the residual carbon rate is above 55%; wherein the molecular weight of the phenanthroline benzimidazole structure polyimide is above 20,000 g / mol. Compared with the organic light-emitting materials currently studied, the solubility, thermal properties, and luminescent properties of the polymer material prepared in this application are greatly improved, and it has potential commercial value and low production cost, and can be mass-produced and applied. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 This is the NMR spectrum of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline prepared in the examples of the present application.

[0089] 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 the present application.

[0090] Figure 3 This is the NMR spectrum of the diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazolyl))bis(3-(trifluoromethyl)aniline prepared in the examples of the present application.

[0091] Figure 4 This is the NMR spectrum of the phenanthroline benzimidazole structure polyimide polymer PI-1 prepared in the examples of the present application.

[0092] Figure 5 This is the GPC test result of the phenanthroline benzimidazole structure polyimide polymer PI-1 prepared in the examples of the present application.

[0093] Figure 6 This is the fluorescence spectrum of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material prepared in the examples of the present application. DETAILED DESCRIPTION

[0094] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0095] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0096] Unless otherwise specified, conventional methods were used for testing and instrument settings were those recommended by the manufacturer.

[0097] Data testing conditions and methods in the examples of this application:

[0098] Nuclear Magnetic Resonance Spectroscopy (NMR): 1 H NMR was measured on a Bruker AVANCE III 400 MHz NMR instrument, with tetramethylsilane (TMS) as the internal standard and DMS Od 6 As solvent.

[0099] Fourier Transform Infrared Test (FT-IR): FT-IR spectrum was obtained using VERTEX70 at 4000cm -1 Up to 400cm -1 The wavelength range was tested.

[0100] Fluorescence spectrum test: The fluorescence spectrum was tested on a FS920 (450W xenon lamp) fluorescence spectrum instrument.

[0101] Gel Permeation Chromatography (GPC): GPC was tested on a Waters 1515 gel permeation chromatograph with tetrahydrofuran (THF) as the mobile phase.

[0102] Differential Scanning Calorimetry (DSC): The measurements were performed using a Q20 in a nitrogen atmosphere at a heating rate of 10 K / min.

[0103] Thermogravimetric (TG) loss was measured using a STA449C analyzer in a nitrogen atmosphere at a heating rate of 10 K / min.

[0104] According to one embodiment of the present application, a method for preparing a phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material comprises:

[0105] (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-phenanthro line;

[0106] (2) 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 are used as monomers to prepare a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1H-benzo[d]imidazol-2-yl)-1,10-phenanthroline by a nucleophilic substitution reaction in the presence of a catalyst;

[0107] (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-benzimidazole-yl))bis(3-(trifluoromethyl)aniline);

[0108] (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;

[0109] (5) Under an inactive atmosphere, reacting a rare earth metal chloride salt and a small molecule ligand of a β-diketone structure in an alkaline mixed solution to prepare a small molecule rare earth complex;

[0110] (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 polyimide rare earth ion coordinated luminescent polymer.

[0111] Example 1

[0112] Steps S1 to S3 The synthesis of 4,4′-((1,10-phenanthroline-2,9-diyl)bis(1-hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline is as follows.

[0113] Step S1: Under an inert gas atmosphere, 2.68 g of 1,10-phenanthroline-2,9-diacid and 2.27 g of o-phenylenediamine were added to 25 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 300 ml of an ice-water mixture. The mixture was adjusted to pH 9 with ammonia water, and the precipitate was filtered to obtain a precipitate, which was washed three times with hexane and dried in a vacuum drying oven at 80° C. for 6 h to obtain a product of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline, and the NMR spectrum was as follows: Figure 1 As shown;

[0114] Step S2: Under an inert gas atmosphere, 4.12 g of 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline prepared in step 1, 2.76 g of anhydrous potassium carbonate and 4.39 g of 1-fluoro-4-nitro-2-trifluoromethylbenzene were added to 40 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 200 ml of deionized water. The precipitate was filtered to obtain a precipitate, which was washed three times with hexane and dried in a vacuum drying oven at 80° C. for 6 h to obtain a product, which was a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1-hydrogen-benzimidazol-2-yl-1,10-phenanthroline, and the NMR spectrum was as follows: Figure 2 As shown;

[0115] Step S3: Under an inert gas atmosphere, 0.99 g of a dinitro compound 2,9-bis(1-(4-nitro-2-trifluoromethyl)-phenyl)-1 hydrogen-benzimidazol-2-yl-1,10 phenanthroline and 0.10 g of a 10% Pd / C catalyst (Pd loading is 10%) are added to 35 ml of ethanol, and then 0.8 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 filtered to remove the catalyst. The solvent is removed from the obtained liquid by rotary evaporation to obtain a solid powder, which is dried in a vacuum drying oven at 80° C. for 6 h to obtain a product of a diamine monomer 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazol-yl))bis(3-(trifluoromethyl)aniline, and the NMR spectrum is as follows: Figure 3 shown.

[0116] Step S4: Synthesis of phenanthroline benzimidazole structured polyimide polymer

[0117] Under an inert gas atmosphere, 0.15 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline and 0.04 g of 4,4'-diaminodiphenyl ether (ODA) were quickly added to a three-necked flask, and then about 3 ml of m-cresol was added as a solvent. The reactants were dissolved by stirring at 80 ° C for 1 h under a nitrogen atmosphere. 0.21 g of bisphenol A diether dianhydride (BPADA) was added to the above mixture. The reaction temperature was raised to 150 ° C and stirred continuously. After 3 hours, 0.15 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 h under stirring. After cooling, the reaction solution was gradually poured into ethanol to generate a large amount of fibrous precipitates. After filtering, the dried product was washed with a large amount of water and ethanol and recorded as PI-1. The NMR spectrum is as follows Figure 4 As shown, the GPC test results are as follows Figure 5 shown.

[0118] Step S5: Synthesis of small molecule rare earth complexes

[0119] Under an inert gas atmosphere, 2-thienylcarbonyltrifluoroacetone (TTA) (1.33 g, 6 mmol) was dissolved in 30 mL of anhydrous ethanol, and then 6 mL of a 1N aqueous solution of NaOH and 10 mL of TbCl 3 6H 2 O (2mmol) anhydrous ethanol solution was added to the anhydrous ethanol solution of TTA in sequence, and then 200mL distilled water was added, the mixture was heated to 60°C, and cooled to room temperature under stirring. A precipitate was precipitated and filtered. The obtained solid was dissolved in 60mL benzene, and then 200mL n-hexane was added. The mixture was allowed to stand at room temperature overnight, filtered, and vacuum dried at 60°C for 48h to obtain a light yellow solid, which was recorded as a small molecule rare earth complex Tb (TTA). 3 ·2H 2 O.

[0120] Step S6: Synthesis of a phenanthroline benzimidazole structured polyimide single rare earth ion coordinated full spectrum luminescent material

[0121] 0.19 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). 3 ·2H 2 The small molecule rare earth complex of O was added to the reaction mixture at a molar ratio of 10% of the phenanthroline imidazole group, and the reaction system was stirred continuously for 15 hours at a stable temperature of 60°C. 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 precipitation. The precipitate was washed with water and ethanol and the dried product was recorded as PI-Ligned-Tb 3+ -10%, fluorescence spectrum as Figure 6 shown.

[0122] Example 2

[0123] Steps S1 to S5 are the same as those in Example 1, except that step S6 is:

[0124] 0.19 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). 3 ·2H 2 The small molecule rare earth complex of O was added to the reaction mixture at a molar ratio of 20% of the phenanthroline imidazole group, and the reaction system was continuously stirred for 15 hours at a stable temperature of 60°C. 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 precipitation. The precipitate was washed with water and ethanol and the dried product was recorded as PI-Ligned-Tb 3+ -20%, fluorescence spectrum as Figure 6 shown.

[0125] Example 3

[0126] Steps S1 to S5 are the same as those in Example 1, except that step S6 is:

[0127] 0.19 g of polymer PI-1 was dissolved in 10 ml of tetrahydrofuran (THF). 3 ·2H 2 The small molecule rare earth complex of O was added to the reaction mixture at a molar ratio of 30% of the phenanthroline imidazole group, and the reaction system was continuously stirred 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 precipitation. The precipitate was washed with water and ethanol and the dried product was recorded as PI-Ligned-Tb 3+ -30%, fluorescence spectrum as Figure 6 shown.

[0128] Example 4

[0129] Steps S1-S3 and S5-S6 are the same as those in Example 1, except that step S4 is:

[0130] Under an inert gas atmosphere, 0.15 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline and 0.04 g of 4,4'-diaminodiphenyl ether (ODA) were quickly added to a three-necked flask, and then about 3 ml of m-cresol was added as a solvent. The reactants were dissolved by stirring at 80°C under a nitrogen atmosphere for 1 h. 0.18 g of hexafluoroisopropylphthalic anhydride (6FDA) was added to the above mixture. The reaction temperature was raised to 150°C and stirred continuously. After 3 hours, 0.15 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 h under stirring. After cooling, the reaction solution was gradually poured into ethanol to generate a large amount of fibrous precipitates. After filtering, the dried product was washed with a large amount of water and ethanol and recorded as PI-2.

[0131] Example 5

[0132] Steps S1-S3 and S5-S6 are the same as those in Example 1, except that step S4 is:

[0133] Under an inert gas atmosphere, 0.15 g of 4,4'-((1,10-phenanthroline-2,9-diyl)bis(1 hydrogen-benzimidazole-yl))bis(3-(trifluoromethyl)aniline and 0.037 g of 4,4'-diaminobiphenyl were quickly added to a three-necked flask, and then about 3 ml of m-cresol was added as a solvent. The reactants were dissolved by stirring at 80°C for 1 h under a nitrogen atmosphere. 0.18 g of hexafluoroisopropylphthalic anhydride (6FDA) was added to the above mixture. The reaction temperature was raised to 150°C and stirred continuously. After 3 hours, 0.15 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 h under stirring. After cooling, the reaction solution was gradually poured into ethanol to generate a large amount of fibrous precipitates. After filtering, the dried product was washed with a large amount of water and ethanol and recorded as PI-3.

[0134] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the 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 structure polyimide single rare earth ion coordinated full spectrum luminescent material, characterized in that: It includes phenanthroline benzimidazole structure polyimide, rare earth ions, and β-diketone structure organic small molecule ligands combined by coordination; The phenanthroline benzimidazole structure polyimide has a general structure shown in 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 rare earth ions are selected from Tb ions; The organic small molecule ligand of the β-diketone structure is selected from α-thienyl trifluoroacetone.

2. The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to claim 1, characterized in that: The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material has a general structure shown in Formula II: Among them, Ln represents rare earth ions, and Ligand represents small molecule ligands with β-diketone structure; 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 rare earth ions are selected from Tb ions; The organic small molecule ligand of the β-diketone structure is selected from α-thienyl trifluoroacetone.

3. The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent 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.

4. The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to claim 1, characterized in that: Ar is selected from any one of the groups of the structure shown in formula III; 5. The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to claim 1, characterized in that: M is selected from any one of the groups of the structure shown in formula IV; 6. The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to claim 1, characterized in that: The phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material has a fluorescence emission peak in the wavelength range of 490 to 630 nm under 393 nm light excitation; Preferably, the glass transition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 294° C.; Preferably, the initial decomposition temperature of the phenanthroline benzimidazole structure polyimide is greater than or equal to 504° C.; Preferably, the residual carbon rate of the phenanthroline benzimidazole structure polyimide is greater than or equal to 50%; Preferably, the molecular weight of the phenanthroline benzimidazole structure polyimide is greater than or equal to 20000 g / mol; Preferably, the glass transition temperature of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is greater than or equal to 250° C.; Preferably, the initial decomposition temperature of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is greater than or equal to 380° C.; Preferably, the residual carbon rate of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material is greater than or equal to 55%.

7. The method for preparing the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to any one of claims 1 to 6, characterized in that: The steps include: S1, adding a monomer mixture containing 1,10-phenanthroline-2,9-diacid and o-phenylenediamine to polyphosphorus, and performing reaction I to obtain 2,9-bis(1-hydrogen-benzimidazole-2-yl)-1,10-phenanthroline; S2, reacting a mixture containing 2,9-bis(1-hydrogen-benzimidazol-2-yl)-1,10-phenanthroline and 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, 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; 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, performing a reaction IV-a, then adding a catalyst III to the product, continuing the reaction IV-b, and then adding ethanol to the product to form a precipitate, to obtain the phenanthroline benzimidazole structure polyimide; S5, adding rare earth metal chloride and an organic small molecule ligand with a β-diketone structure to the alkaline mixed solution, reacting IV, and obtaining 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 coordinated full spectrum luminescent material.

8. The preparation method according to claim 7, 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; Preferably, in step S1, the conditions of reaction I include: reaction temperature of 200-240° C., reaction time of 5-8 h; Preferably, 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; Preferably, in step S2, the conditions of reaction II include: reaction temperature of 80 to 120° C., reaction time of 12 to 24 h; Preferably, in step S2, the catalyst I is selected from at least one of potassium carbonate, cesium carbonate and calcium carbonate; Preferably, in step S2, solvent I is selected from at least one of N-methylpyrrolidone, NN-dimethylformamide, and NN-dimethylacetamide; Preferably, in step S3, catalyst II is a 5% dry palladium carbon catalyst (Pb / C catalyst, Pd loading is 5%); Preferably, in step S3, the amount of catalyst II used is 8 to 12% by weight of the dinitro compound; Preferably, in step S3, the reducing agent is 85% hydrazine hydrate (85% content of N2H4·H2O); Preferably, in step S3, the amount of the reducing agent is 5 to 10 times the weight of the dinitro compound; Preferably, in step S3, the conditions of reaction III include: reaction temperature of 80 to 120° C., reaction time of 12 to 24 h; Preferably, in step S3, solvent II is selected from at least one of ethanol, NN-dimethylformamide, and NN-dimethylacetamide; Preferably, 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; Preferably, in step S4, the catalyst III is selected from isoquinoline; Preferably, in step S4, the conditions of reaction IV-a include: reaction time at 80°C to 90°C for 1 to 2 h; Preferably, 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; Preferably, in step S4, the solvent III is selected from at least one of m-cresol, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

9. The preparation method according to claim 7, characterized in that: 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; Preferably, in step S5, the conditions for reaction V include: heating to 60° C., reacting at this temperature for 0.5 to 4 hours, and cooling naturally under continuous stirring after the reaction until precipitation is complete; Preferably, in step S5, the pH of the alkaline mixed solution is greater than or equal to 8, and the alkaline mixed solution includes a mixed solution of ethanol and water, and the volume ratio of the ethanol to water is 1:8-20; Preferably, 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; Preferably, in step S6, the conditions of reaction VI include: reaction temperature of 50 to 120° C., reaction time of 8 to 15 h; Preferably, solvent IV is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

10. Use of the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material according to any one of claims 1 to 6, or the phenanthroline benzimidazole structure polyimide single rare earth ion coordinated full-spectrum luminescent material prepared according to the preparation method according to any one of claims 7 to 9 in polymer luminescent materials.

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