Preparation method of polyarylether phosphine oxide intrinsic type room temperature phosphorescent material

Abstract

The invention relates to the technical field of photoelectric functional polymer materials, in particular to a preparation method of a polyarylether phosphine oxide intrinsic type room-temperature phosphorescent material, which comprises the following steps: step 1, reacting a Grignard reagent 4-fluorophenyl magnesium bromide with phenyl phosphoric acid diacyl chloride, and performing column chromatography and recrystallization to obtain a polyarylether phosphine oxide intrinsic type room-temperature phosphorescent material; a di (4-fluorophenyl) phenyl phosphine oxide monomer is obtained; and 2, weighing the obtained di (4-fluorophenyl) phenylphosphine oxide and bisphenol monomers, dissolving the di (4-fluorophenyl) phenylphosphine oxide and bisphenol monomers in an organic solvent, adding a catalyst and a water-carrying agent, then heating to 140-160 DEG C, carrying out a stirring reaction and dehydration for 3 h, then heating to 190-200 DEG C, carrying out a polymerization reaction for 5 h, and then carrying out purification treatment to obtain the polyarylether phosphine oxide intrinsic room temperature phosphorescent material. The polymer material obtained by the invention has excellent mechanical properties, heat resistance, environmental resistance and longer phosphorescence emission life and service life.

Description

Technical Field

[0001] The invention relates to the technical field of optoelectronic functional polymer materials, and in particular to a method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material. Background Art

[0002] Pure organic room temperature phosphorescent materials have shown broad application potential in many fields such as encryption and anti-counterfeiting, optoelectronic display and biosensing due to their simple processing, low cost, high design flexibility, good biocompatibility and strong stability. However, current research focuses on organic phosphorescent small molecules, which have significant deficiencies in processability, repeatability and stability. Relatively speaking, polymer materials have become ideal substrates for the preparation of room temperature phosphorescent materials due to their excellent solubility, processability, ductility, heat resistance, transparency, repeatability, mechanical properties and cost-effectiveness.

[0003] Using fatty chain polymers as the matrix, through covalent bonds, hydrogen bonds, electrostatic potential and other effects, to construct room temperature phosphorescent materials is a common method with low cost and mature processes. However, due to the alkyl structure of the main chain of this type of polymer, its glass transition temperature is generally low. At higher temperatures (≥60°C), the movement within the molecule intensifies, resulting in an increase in the non-radiative transitions of triplet excitons, and the quenching of its phosphorescence. For example, commonly used polymer matrix materials such as polyvinyl alcohol and polymethyl methacrylate can construct a rigid environment through weak intramolecular and intermolecular interactions, but the triplet excitons excited in this environment are easily affected by water vapor and thermal effects and are quickly quenched.

[0004] In recent years, the application research of special engineering plastic polyarylether phosphine oxide in the field of optoelectronics has gradually attracted attention. The structural characteristics of polyarylether phosphine oxide, including excellent mechanical properties, heat resistance, thermal stability, repeatability, anti-aging and chemical resistance, make its triplet excitons less susceptible to quenching by water and heat. Its strong electron-withdrawing phosphonyl group and rigid aromatic ring structure make it possible to achieve room temperature phosphorescence emission. In the prior art, the common synthesis method is to construct an intrinsic organic room temperature phosphorescent material based on an alkane chain. The intrinsic organic room temperature phosphorescent material synthesized by this synthesis method is more sensitive to harsh environments. In high temperature, high humidity, acid and alkali and high radiation environments, its phosphorescence lifetime, luminescence intensity, mechanical strength and other properties will be greatly reduced.

[0005] In summary, how to solve the problem that the existing intrinsic organic room temperature phosphorescent materials constructed based on alkane chains are sensitive to harsh environments and their phosphorescence lifetime, luminous intensity, mechanical strength and other properties are significantly reduced under high temperature, high humidity, acid and alkali and high radiation environments has become a difficult problem that needs to be solved urgently in this field. Therefore, it is necessary to propose a method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material. Summary of the invention

[0006] In order to solve the problem that the existing intrinsic organic room temperature phosphorescent materials constructed based on alkane chains are more sensitive to harsh environments and their phosphorescence lifetime, luminous intensity, mechanical strength and other properties are significantly reduced under high temperature, high humidity, acid and alkali and high radiation environments, the present invention provides a method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material, and the obtained polymer material has excellent mechanical properties, heat resistance, environmental resistance and long phosphorescence emission lifetime and service life.

[0007] In order to achieve the above object, the technical solution of the present invention is as follows: A method for preparing a polyaryletherphosphine oxide intrinsic room temperature phosphorescent material comprises the following steps:

[0008] Step 1, synthesizing bis(4-fluorophenyl)phenylphosphine oxide: dripping a mixed solution of phenylphosphoric acid dichloride and tetrahydrofuran into a solution containing 4-fluorophenylmagnesium bromide, stirring at room temperature for 15 hours to obtain a mixed solution; adding dilute sulfuric acid and deionized water to the mixed solution, and then adding ether to extract an organic phase, adding anhydrous magnesium sulfate to the extracted organic phase for drying, filtering the dried organic phase and rotary evaporating to remove the solvent to obtain a product after the solvent is removed, and then purifying the product after the solvent is removed by column chromatography according to a mass ratio of petroleum ether: ethyl acetate = 5:1 to obtain a target product, and recrystallizing the target product from ethyl acetate to obtain a bis(4-fluorophenyl)phenylphosphine oxide monomer;

[0009] Step 2, synthesizing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material: dissolving a di(4-fluorophenyl)phenylphosphine oxide monomer and a bisphenol monomer in an organic solvent, adding a catalyst and a water-carrying agent, mixing and stirring to obtain a mixed solution, heating the mixed solution to 140-160° C., stirring and reacting and dehydrating for 3 hours, then heating the mixed solution to 190-200° C., performing a polymerization reaction for 5 hours, until the viscosity of the mixed solution no longer increases, to obtain a solution after the polymerization reaction, adding the solution after the polymerization reaction into a dilute hydrochloric acid solution, mixing and stirring until a white precipitate is precipitated, filtering and collecting the white precipitate, purifying the white precipitate, and obtaining a polyarylether phosphine oxide intrinsic room temperature phosphorescent material.

[0010] Further, in step 2, the bisphenol monomer includes one or more of bisphenol A, bisphenol AF, bisphenol F, bisphenol S, hydroquinone, resorcinol, biphenol, phenolphthalein, phenolphthalein and bisphenolfluorene.

[0011] Furthermore, in step 2, the organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and cyclopentane sulfone, the catalyst is one or more of potassium carbonate, sodium carbonate and sodium hydroxide, and the water-carrying agent is one or more of molecular sieves and toluene.

[0012] Furthermore, in step 2, the purification treatment includes acid boiling, Soxhlet extraction and drying.

[0013] Further, in step 2, the reaction equation of the synthesis route of bis(4-fluorophenyl)phenylphosphine oxide is:

[0014]

[0015] Further, in step 2, the reaction equation for the synthesis route of polyaryletherphosphine oxide is:

[0016]

[0017] Furthermore, the polyarylether phosphine oxide prepared by the preparation method of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material has the following general structural formula:

[0018]

[0019] Among them, HO-Ar 1 -OH and HO-Ar 2 -OH is a bisphenol monomer, and the bisphenol monomer includes one or more of bisphenol A, bisphenol AF, bisphenol F, bisphenol S, hydroquinone, resorcinol, biphenol, phenolphthalein, phenolphthalein and bisphenolfluorene;

[0020] n is a percentage ranging from 0 to 100%.

[0021] Further, a method for preparing a polyarylether phosphine oxide thick film prepared based on the above-mentioned method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material comprises the following steps:

[0022] S1: dissolving 1 g of poly(arylene ether phosphine oxide) in 2 mL of N,N-dimethylacetamide solvent to obtain a mixed solution, placing the mixed solution on a constant temperature heated magnetic stirrer, heating and stirring at 80° C. for 2 hours to obtain a completely dissolved poly(arylene ether phosphine oxide) concentrated solution;

[0023] S2: Put the cleaned and dried glass plate into a vacuum oven and preheat it at 60°C for 30 minutes. Take out the glass plate and place it on the coating machine. Adjust the scraper height to 1000 μm, the coating speed to 50 cm / min, the coating stroke to 30 cm, and perform the coating operation.

[0024] S3: Pour the concentrated solution of polyarylether phosphine oxide evenly on the glass plate and start scraping. After scraping, put the glass plate together with the coating into a vacuum oven and slowly heat it at a rate of 80°C for 2 hours), 100°C for 2 hours, 120°C for 2 hours, and 150°C for 6 hours. After the solvent is basically evaporated, evacuate the vacuum oven and continue drying for 12 hours. After the solvent is completely evaporated, stop heating, take out the glass plate from the vacuum oven after natural cooling, cut the area with a film thickness of 175±5μm, and seal it for use.

[0025] Furthermore, the preparation method of the polyarylether phosphine oxide thin film is basically the same as the preparation method of the above-mentioned thick film, wherein the solution is prepared by dissolving 1 g of polyarylether phosphine oxide in 10 mL of N,N-dimethylacetamide solvent and stirring to obtain a mixed dilute solution, and the dilute solution is naturally cast on a glass plate, and then taken out after drying in a vacuum oven. The thickness of the polyarylether phosphine oxide film is between 80 and 100 μm.

[0026] The above scheme has the following beneficial effects:

[0027] 1. In the present invention, the polyarylether phosphine oxide intrinsic room temperature phosphorescent material has a simple preparation process, excellent mechanical properties, good processability, good environmental stability, the initial performance of the material is not easily destroyed, and it is easy to prepare on an enlarged basis. The polyarylether phosphine oxide intrinsic room temperature phosphorescent material has important application prospects in the fields of information display, encryption, and sensing.

[0028] 2. In the present invention, the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material has a phosphonyl group with strong electron-withdrawing properties and a rigid aromatic ring structure, which makes it easy to form a charge separation state inside the molecule, thereby exhibiting a long emission lifetime and strong luminescence intensity. Even at a high temperature of 100°C, it still has a long phosphorescence lifetime, and after the effects of acid, alkali, water, radiation aging, etc., it still has stable room temperature phosphorescence emission.

[0029] 3. In the present invention, a series of poly(arylether) phosphine oxide thin films and thick films are obtained by film casting and blade coating. The polymer has good heat resistance, thermal stability and mechanical properties. g All above 180℃, T 5％ The temperature of the ternary copolymer polyarylether phosphine oxide is around 500°C, and the tensile strength of the ternary copolymer polyarylether phosphine oxide is above 40MPa. The ternary copolymer polyarylether phosphine oxide has excellent room temperature phosphorescence performance, and its room temperature phosphorescence lifetime can reach up to 479ms, and the room temperature afterglow can reach 5s. Even at a high temperature of 100°C, it still has a long phosphorescence lifetime. After being exposed to acid, alkali, water, radiation aging, etc., it still has stable room temperature phosphorescence emission.

[0030] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is an infrared spectrum of the intrinsic room temperature phosphorescent material of polyaryletherphosphine oxide obtained in the example of the present invention.

[0032] Figure 2 This is a hydrogen nuclear magnetic resonance spectrum of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in an example of the present invention.

[0033] Figure 3 This is a thermal performance diagram of the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material obtained in an example of the present invention.

[0034] Figure 4 This is a diagram showing the mechanical properties of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in an embodiment of the present invention.

[0035] Figure 5 This is a room temperature afterglow photograph of the binary homopolymeric polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in the example of the present invention after being irradiated with 365nm ultraviolet light.

[0036] Figure 6 This is a room temperature afterglow photograph of the ternary copolymer polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in the example of the present invention after irradiation with 365nm ultraviolet light.

[0037] Figure 7 The phosphorescence spectrum and phosphorescence lifetime decay diagram of the poly(arylether phosphine oxide) intrinsic room temperature phosphorescent material obtained in the embodiment of the present invention are shown.

[0038] Figure 8 This is an electron spin resonance signal diagram of the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material obtained in an example of the present invention.

[0039] Fig. 9 This is a temperature-dependent afterglow photograph of the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material obtained in an example of the present invention after being irradiated with 365nm ultraviolet light.

[0040] Fig.10 The temperature-dependent phosphorescence spectrum and temperature-dependent phosphorescence lifetime decay diagram of the poly(arylether phosphine oxide) intrinsic room temperature phosphorescent material obtained in the embodiment of the present invention are shown.

[0041] Fig.11 The normalized phosphorescence spectrum of the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material obtained in the embodiment of the present invention after being aged by acid, alkali, deionized water and Xe lamp irradiation.

[0042] Fig.12 In the embodiment of the present invention, by adjusting the molar ratio of bisphenol A and biphenol, the reaction equation diagram of biphenyl-containing polyarylether phosphine oxide with different molecular structures is obtained. DETAILED DESCRIPTION

[0043] The following is further described in detail through specific implementation methods:

[0044] Embodiment 1:

[0045] A method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material comprises the following steps:

[0046] Step 1, preparation of bis(4-fluorophenyl)phenylphosphine oxide: drip a mixed solution of 30 g (150 mmol) phenylphosphonic acid dichloride and 85 mL tetrahydrofuran into a constant pressure dropping funnel containing a 4-fluorophenylmagnesium bromide solution, and slowly drip it into a three-necked flask, accompanied by the generation of bubbles. The solution changes from turbid gray to clear dark brown. After stirring at room temperature for 15 hours, a transparent light yellow mixed solution is obtained. Add 100 mL of dilute H 2 SO 4 The solution and 100 mL of deionized water were added with 50 mL of ether to separate the organic phase by extraction, dried with anhydrous magnesium sulfate, filtered, and rotary evaporated. The phase was eluted by column chromatography using a ratio of petroleum ether: ethyl acetate = 5:1 eluent and recrystallized from ethyl acetate to obtain a white crystalline di(4-fluorophenyl)phenylphosphine oxide monomer. The crystals were dried in a vacuum oven at 60 ° C for 48 h, weighed to 31.8 g, and the calculated yield was 67.5%. The crystals were sealed and stored at low temperature for later use.

[0047] The above reaction equation is:

[0048]

[0049] Step 2, synthesize polyarylether phosphine oxide intrinsic room temperature phosphorescent material: use a 100mL three-necked flask equipped with a constant temperature electric heating jacket, a stirring rod, a stirrer, a water separator, a spherical condenser, a temperature sensor and an argon flow as a reaction container, add di(4-fluorophenyl)phenylphosphine oxide (3.14g, 10mmol), bisphenol A (2.33g, 10mmol), anhydrous potassium carbonate (2.79g, 20mmol), toluene (15mL), and N-methylpyrrolidone (25mL) in sequence. After the addition is complete, add toluene to the water separator until it just refluxes.

[0050] Turn on the stirrer to mechanically stir the mixed solution in the three-necked flask (300 rad / min), and wait until the mixed solution in the three-necked flask is gradually heated to the solution azeotropic, the azeotropic temperature is 140-160°C, and in this embodiment, the azeotropic temperature is 150°C; at this time, bisphenol A reacts with the catalyst potassium carbonate to form potassium phenolate, and then the toluene in the three-necked flask is refluxed and dehydrated for 3 hours until no new water droplets are generated in the water separator, the toluene and water are released together, and the residual toluene in the solution is evaporated.

[0051] Continue to heat the mixed solution in the three-necked flask to 190°C. The potassium phenolate formed in the three-necked flask reacts with (4-fluorophenyl)phenylphosphine oxide to undergo nucleophilic substitution reaction at high temperature to generate ether bonds, which gradually increases the viscosity of the solution. Continue the reaction at this temperature for 5 hours. When the viscosity of the system no longer increases, stop heating and terminate the reaction.

[0052] The reaction solution in the three-necked flask was slowly poured into a magnetically stirred dilute hydrochloric acid solution to precipitate a white long strip crude product, which was immersed in a dilute hydrochloric acid solution and stirred for 12 hours. After preliminary washing and drying, the crude product was redissolved in NMP to prepare a dilute solution of 1g / 10mL, and precipitated again in a dilute hydrochloric acid solution to form a flocculent precipitate. The flocculent precipitate was broken and immersed in a dilute hydrochloric acid solution and deionized water and boiled repeatedly for 3 times to remove the residual potassium carbonate, N-methylpyrrolidone, unreacted small molecules and oligomers, etc. After washing to neutrality, it was placed in a blast oven again at 100°C for 24 hours and dried in a vacuum oven at 150°C for 24 hours. Finally, it was extracted with methanol Soxhlet and dried to obtain 4.83g of pure product of bisphenol A polyarylether phosphine oxide (PBPO-BPA), and the calculated yield was 91.7%.

[0053] The above reaction equation is:

[0054]

[0055] Embodiment 2:

[0056] An intrinsic polyarylether phosphine oxide room temperature phosphorescent material, the preparation method of which comprises the following steps:

[0057] The method and steps are exactly the same as those in Example 1. The bisphenol monomer is only biphenyl diphenol (1.86 g, 10 mmol). After purification, 2.82 g of pure product of biphenyl diphenol type polyarylether phosphine oxide (PBPO-PPDP) can be obtained, and the yield can be calculated to be 61.3%.

[0058] The above reaction equation is:

[0059]

[0060] Embodiment 3:

[0061] An intrinsic polyarylether phosphine oxide room temperature phosphorescent material, the preparation method of which comprises the following steps:

[0062] The method and steps are exactly the same as those in Example 1. The bisphenol monomers are bisphenol A (9.9 mmol) and biphenyl diphenol (0.1 mmol). After purification, 5.14 g of a biphenyl-containing polyphenyl ether phosphine oxide (PBPO-1% PPDP) copolymer can be obtained, and the calculated yield is 94.9%.

[0063] Embodiment 4:

[0064] An intrinsic polyarylether phosphine oxide room temperature phosphorescent material, the preparation method of which comprises the following steps:

[0065] The method and steps are exactly the same as those in Example 1. The bisphenol monomers are bisphenol A (9.7 mmol) and biphenyl diphenol (0.3 mmol). After purification, 5.07 g of a biphenyl-containing polyphenyl ether phosphine oxide (PBPO-3% PPDP) copolymer can be obtained, and the calculated yield is 93.8%.

[0066] Embodiment 5:

[0067] An intrinsic polyarylether phosphine oxide room temperature phosphorescent material, the preparation method of which comprises the following steps:

[0068] The method and steps are exactly the same as those in Example 1. The bisphenol monomers are bisphenol A (9.4 mmol) and biphenyl diphenol (0.6 mmol). After purification, 5.05 g of a biphenyl-containing polyphenyl ether phosphine oxide (PBPO-6% PPDP) copolymer can be obtained, and the calculated yield is 93.6%.

[0069] Embodiment 6:

[0070] An intrinsic polyarylether phosphine oxide room temperature phosphorescent material, the preparation method of which comprises the following steps:

[0071] The method and steps are exactly the same as those in Example 1. The bisphenol monomers are bisphenol A (9.1 mmol) and biphenyl diphenol (0.9 mmol). After purification, 4.98 g of a biphenyl-containing polyphenyl ether phosphine oxide (PBPO-9% PPDP) copolymer can be obtained, and the calculated yield is 92.4%.

[0072] It can be seen from Examples 3-6 that biphenyl-containing polyarylether phosphine oxides with different molecular structures can be obtained by adjusting the molar ratio of bisphenol A to biphenyl diphenol.

[0073] Figure 1 This is the infrared spectrum of the intrinsic room temperature phosphorescent material of poly(arylether phosphine oxide) obtained in Examples 1-6 of the present invention, 2966 cm -1 The absorption peak at 1238cm is the characteristic absorption peak of the methyl group on bisphenol A. PBPO-PPDP does not have this absorption peak. -1 The absorption peak at 1113 cm is the asymmetric stretching vibration absorption peak of the aromatic ether bond (Ar-O-Ar), indicating the formation of the polymer. -1 The absorption peak at is the characteristic absorption peak of the phosphonyl group (P=O).

[0074] Figure 2This is the H NMR spectrum of the intrinsic room temperature phosphorescent material of polyarylether phosphine oxide obtained in Examples 1-6 of the present invention. In the molecular structure of PBPO-3% PPDP, the characteristic peaks of triphenylphosphine oxide, bisphenol A and biphenol can all correspond one to one in the H NMR spectrum. As can be seen from Figure b, it is proved that the BPA monomer and PPDP monomer are successfully introduced into the polymer structure.

[0075] Figure 3 The thermal performance diagram of the intrinsic room temperature phosphorescent material of poly(arylether phosphine oxide) obtained in Examples 1-6 of the present invention, the glass transition temperature (T g ), with the increase of biphenyl content in the molecular chain structure, there is an obvious enhancement phenomenon, which is 188.8, 196.3, 197.4, 199.3, 200.3 and 232.2℃, respectively, indicating that biphenyl enhances the rigidity of the polymer structure and has excellent heat resistance; From Figure b, it can be seen that the 5% thermal weight loss temperature (T 5％ ) are 492.0, 496.7, 500.7, 498.7, 498.6 and 524.3 ℃ respectively. With the increase of biphenyl content, the thermal stability of this series of polymers is significantly improved.

[0076] Figure 4 The mechanical properties of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in Examples 3-6 of the present invention are shown in Figure 1. This series of polyarylether phosphine oxide copolymers have good mechanical properties, and their tensile strength is above 40Mpa, and their Young's modulus is between 1.3 and 1.8GPa. With the increase of biphenyl content, their modulus gradually increases, and their elongation at break gradually decreases. This indicates that as the biphenyl content increases, the rigid groups increase, the rigidity of the molecular chain increases, the entanglement ability between molecular weights weakens, the movement of the chain segments is hindered, the relative slip of the molecular chain is small, and forced high elastic deformation cannot be achieved.

[0077] Figure 5 The following are room temperature afterglow photographs of the PBPO-BPA and PBPO-PPDP films (175±5 μm) obtained in Examples 1 and 2 of the present invention after being irradiated with a 365 nm ultraviolet lamp for 30 seconds in an atmospheric environment. Obvious room temperature afterglow can be observed for both PBPO-BPA and PBPO-PPDP, and the afterglow duration is close to 2 seconds. The afterglow color of PBPO-BPA is yellow-green, and the afterglow color of PBPO-PPDP is yellow, showing an obvious red shift.

[0078] Figure 6The following are room temperature afterglow photographs of the PBPO-1% PPDP, PBPO-3% PPDP, PBPO-6% PPDP, and PBPO-9% PPDP films (175±5 μm) obtained in Examples 3-6 of the present invention after irradiation with a 365 nm ultraviolet lamp for 30 seconds in an atmospheric environment. This series of polyarylether phosphine oxide films are colorless or light yellow under natural light and are blue fluorescent under irradiation with 365 nm ultraviolet light, and all have an afterglow of more than 2 seconds. Among them, the afterglow duration of PBPO-3% PPDP is the longest, which can reach 5 seconds, and the afterglow color is yellow-green, achieving ultra-long-life room temperature phosphorescence of the intrinsic polyarylether group. The results show that by controlling the content of the biphenyl structure in the polyarylether phosphine oxide, the afterglow duration of the polymer can be significantly regulated.

[0079] Figure 7 The phosphorescence spectrum and phosphorescence lifetime decay diagram of the intrinsic room temperature phosphorescent material of polyarylether phosphine oxide obtained in Examples 2-7 of the present invention after being encapsulated by epoxy resin under a 365nm excitation light source are shown. The room temperature phosphorescence emission intensity of this series of polymers first increases and then decreases with the content of biphenyl. Among them, the phosphorescence emission intensity of PBPO-3% PPDP is the strongest, which is four times that of PBPO-BPA. The luminescence center is around 510nm, while the luminescence center of PBPO-PPDP produces a large red shift, which is around 540nm. This is related to the fact that the introduction of the biphenyl structure increases the conjugation degree of PBPO-PPDP, and a large number of π→π on the benzene ring. * The electron transition causes a significant red shift in the phosphorescence emission wavelength; as shown in Figure b, the phosphorescence lifetime increases from 166ms to 479ms, a 3-fold increase.

[0080] Figure 8 The graph is an electron spin resonance signal of the intrinsic room temperature phosphorescent material of polyarylether phosphine oxide obtained in Examples 3-6 of the present invention in an Ar environment. A strong electron spin resonance (EPR) signal can be observed for this series of polyarylether phosphine oxide films after irradiation with a 365nm ultraviolet lamp for 25s, confirming that a large number of free radicals are generated under the excitation of the ultraviolet lamp. This shows that when polyarylether phosphine oxide absorbs excitation energy, it forms a charge separation state, separates to form free radical anions and cations, and when the free radical anions and free radical cations recombine again, excitons are formed, and they return to the ground state to produce a long afterglow; it can also be seen from the figure that PBPO-3% PPDP has the highest free radical intensity, which proves that its phosphorescence emission intensity is the strongest, the life is the longest, and the afterglow is brighter and longer.

[0081] Fig. 9This is a temperature-dependent afterglow photograph of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in Example 4 of the present invention after being irradiated with 365nm ultraviolet light for 30s. Thanks to the polyarylether system, PBPO-3% PPDP has an afterglow of more than 1s under high temperature conditions of 100°C, and even at a high temperature of 125°C, it still retains a certain afterglow performance, and its phosphorescence color changes from yellow-green to light cyan.

[0082] Fig.10 The temperature-dependent phosphorescence spectrum and temperature-dependent phosphorescence lifetime decay diagram of the polyarylether phosphine oxide intrinsic room temperature phosphorescent material obtained in Example 4 of the present invention after being encapsulated by epoxy resin under a 365nm excitation light source, the phosphorescence emission center of PBPO-3% PPDP blue-shifts from 545nm to 515nm as the temperature increases; at a high temperature of 380K, it still has a phosphorescence lifetime of 47ms, which is because the polyarylether series polymers have a high glass transition temperature, so that at a high temperature of 380K, the triplet excitons of the system polymers cannot be thermally activated and thus completely converted into non-radiative relaxation.

[0083] Fig.11 This is a normalized phosphorescence spectrum of the intrinsic room temperature phosphorescent material of the polyarylether phosphine oxide obtained in Example 4 of the present invention after being subjected to the effects of acid, alkali, deionized water and Xe lamp irradiation aging. Under the effects of different pH solution treatments, deionized water infiltration and Xe lamp irradiation aging, its phosphorescence performance remains basically stable without obvious pH dependence and quenching, which indicates that its excellent structural stability enables it to maintain stable room temperature phosphorescence performance under the effects of acid and alkali solutions, water infiltration and irradiation aging. This series of intrinsic room temperature phosphorescent materials of polyarylether phosphine oxide can be widely used in harsh environments such as acid, alkali, humidity and high irradiation, greatly broadening the application range of room temperature phosphorescent materials.

[0084] Fig.12 In Examples 3-6 of the present invention, the reaction equation diagrams of biphenyl-containing polyarylether phosphine oxides with different molecular structures are obtained by adjusting the molar ratio of bisphenol A to biphenol.

[0085] The present invention, through its unique technical solution, realizes the research in the field of room temperature phosphorescence of special engineering plastic polyarylether phosphine oxide in the basic characteristic of polymer, which not only broadens the research scope in the field of room temperature phosphorescence, but also has broad application prospects, and provides new ideas and methods for the research and development of special engineering plastic polyarylether system in the field of room temperature phosphorescence. Although the specific implementation methods of the present invention are described in detail by combining examples and drawings, these descriptions should not be regarded as limiting the scope of protection of this patent. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be covered within the scope of protection of the present invention.

[0086] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material, characterized in that: The following steps are involved: Step 1, synthesizing di(4-fluorophenyl)phenylphosphine oxide: adding phenylphosphine dichloride solution to tetrahydrofuran solution and mixing and stirring to obtain a mixed solution of phenylphosphine dichloride and tetrahydrofuran, injecting the mixed solution of phenylphosphine dichloride and tetrahydrofuran dropwise into a solution containing 4-fluorophenylmagnesium bromide, stirring at room temperature for 15 hours, and obtaining a stirred mixed solution; adding dilute sulfuric acid and deionized water to the stirred mixed solution, and then adding ether to extract an organic phase, adding anhydrous magnesium sulfate to the extracted organic phase for drying, filtering the dried organic phase and rotary evaporating to remove the solvent, obtaining a product after the solvent is removed, and purifying the product after the solvent is removed by column chromatography in a mass ratio of petroleum ether: ethyl acetate = 5:1, and then recrystallizing from ethyl acetate to obtain a di(4-fluorophenyl)phenylphosphine oxide monomer; Step 2, synthesizing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material: dissolving a di(4-fluorophenyl)phenylphosphine oxide monomer and a bisphenol monomer in an organic solvent, adding a catalyst and a water-carrying agent, mixing and stirring to obtain a stirred mixed solution, heating the stirred mixed solution to 140-160° C., stirring and reacting and dehydrating for 3 hours, then heating the mixed solution to 190-200° C., performing a polymerization reaction for 5 hours, until the viscosity of the mixed solution no longer increases, to obtain a solution after the polymerization reaction, adding the solution after the polymerization reaction into a dilute hydrochloric acid solution, mixing and stirring until a white precipitate is precipitated, filtering and collecting the white precipitate, purifying the white precipitate, and obtaining a polyarylether phosphine oxide intrinsic room temperature phosphorescent material.

2. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 1, characterized in that: In step 2, the bisphenol monomer includes one or more of bisphenol A, bisphenol AF, bisphenol F, bisphenol S, hydroquinone, resorcinol, biphenol, phenolphthalein, phenolphthalein and bisphenolfluorene.

3. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 2, characterized in that: In step 2, the organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and cyclopentane sulfone, the catalyst is one or more of potassium carbonate, sodium carbonate and sodium hydroxide, and the water-carrying agent is one or more of molecular sieves and toluene.

4. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 3, characterized in that: In step 2, the purification process includes acid boiling, Soxhlet extraction and drying.

5. The method for preparing the polyarylether phosphine oxide intrinsic room temperature phosphorescent material according to claim 4, characterized in that: In step 1, the reaction equation of the synthesis route of bis(4-fluorophenyl)phenylphosphine oxide is:

6. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 5, characterized in that: In step 2, the reaction equation for the synthesis route of polyaryletherphosphine oxide is:

7. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 6, characterized in that: The polyarylether phosphine oxide prepared by the method for preparing the polyarylether phosphine oxide intrinsic room temperature phosphorescent material described in claims 1-6 has the following general structural formula: Wherein, HO-Ar1-OH and HO-Ar2-OH are bisphenol monomers, and the bisphenol monomers include one or more of bisphenol A, bisphenol AF, bisphenol F, bisphenol S, hydroquinone, resorcinol, biphenol, phenolphthalein, phenolphthalein and bisphenolfluorene; n is a percentage ranging from 0 to 100%.

8. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 7, characterized in that: The method for preparing a polyarylether phosphine oxide thick film based on the method for preparing a polyarylether phosphine oxide intrinsic room temperature phosphorescent material comprises the following steps: S1: dissolving 1 g of poly(arylene ether phosphine oxide) in 2 mL of N,N-dimethylacetamide solvent to obtain a mixed solution, placing the mixed solution on a constant temperature heated magnetic stirrer, heating and stirring at 80° C. for 2 hours to obtain a completely dissolved poly(arylene ether phosphine oxide) concentrated solution; S2: Put the cleaned and dried glass plate into a vacuum oven and preheat it at 60°C for 30 minutes. Take out the glass plate and place it on the coating machine. Adjust the scraper height to 1000 μm, the coating speed to 50 cm / min, the coating stroke to 30 cm, and perform the coating operation. S3: Pour the concentrated solution of polyarylether phosphine oxide evenly on the glass plate and start scraping. After scraping, put the glass plate together with the coating into a vacuum oven, and slowly heat it at a rate of 80°C for 2 hours, 100°C for 2 hours, 120°C for 2 hours, and 150°C for 6 hours. After the solvent is completely evaporated, evacuate the vacuum oven and continue drying for 12 hours. After the solvent is completely evaporated, stop heating, take out the glass plate from the vacuum oven after natural cooling, cut the area with a film thickness of 175±5μm, and seal it for later use.

9. The method for preparing the polyaryletherphosphine oxide intrinsic room temperature phosphorescent material according to claim 8, characterized in that: The preparation method of the polyarylether phosphine oxide thin film is consistent with the preparation method of the above-mentioned thick film, wherein the solution is prepared by dissolving 1g of polyarylether phosphine oxide in 10mL of N,N-dimethylacetamide solvent and stirring to obtain a mixed dilute solution, and the dilute solution is naturally cast on a glass plate, and then taken out after drying in a vacuum oven. The thickness of the polyarylether phosphine oxide film is between 80 and 100 μm.

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