An intrinsically stretchable room temperature phosphorescent polymer material and a preparation method thereof

Abstract

This invention discloses an intrinsically stretchable room-temperature phosphorescent polymer material and its preparation method, belonging to the field of polymer material preparation technology. This invention controls the chain length of the polymer material through atom transfer radical polymerization, controls the hydrophilicity / hydrophobicity of the blocks through hydrolysis, and then, through self-assembly, allows the basic units to spontaneously aggregate into a stable structure with a certain regular geometric appearance under non-covalent interactions. This effectively reduces the S1→T1 energy level difference, realizes more intersystem crossing (ISC) channels, and significantly enhances the spin-orbit coupling effect. This invention can effectively promote the occurrence of ISC, resulting in a long-afterglow polymer material with both long lifetime and high stretchability at room temperature, achieving a luminescence lifetime of 4 s and an elongation at break of 200%.

Description

Technical Field

[0001] This invention belongs to the field of polymer material preparation technology, specifically relating to an intrinsically stretchable room temperature phosphorescent polymer material and its preparation method. Background Technology

[0002] Long-afterglow luminescent materials refer to materials that continue to emit light for a period of time after excitation has ceased; they are also known as phosphorescent materials, or in everyday life, phosphorescent powder or long-afterglow powder. The luminescence principle of long-afterglow luminescent materials is photoluminescence, meaning that when the material is excited by a light source, it stores excitation energy in an excited state. When the excitation light source stops shining, the material slowly releases the stored energy in the form of photons.

[0003] Long-afterglow materials are currently limited to inorganic materials. Their further applications are restricted by drawbacks such as demanding processing conditions, scarce material sources, and the biotoxicity of rare-earth ions and heavy metals. Related research indicates that ultra-low temperature (77K) can suppress non-radiative transitions and achieve organic long-afterglow luminescence; however, the stringent ultra-low temperature conditions severely limit its practical application. Therefore, researchers have utilized strategies such as crystal-induced organic molecular construction, heavy atom effects, hydrogen bonding, self-assembly, host-guest doping, and polymer-based methods to achieve a series of organic materials with long-afterglow luminescence, aiming to replace inorganic long-afterglow luminescent materials.

[0004] Compared with inorganic long-afterglow materials, organic long-afterglow materials have advantages such as flexibility, ease of synthesis, low toxicity, and ease of modification. Therefore, the development of room-temperature stretchable long-afterglow luminescent materials is imperative. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide an intrinsically stretchable room temperature phosphorescent polymer material and its preparation method, so as to solve the technical problems of high toxicity of inorganic long afterglow materials, harsh processing conditions, and organic long afterglow materials that can only emit light at ultra-low temperatures.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] This invention discloses a method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material, comprising the following steps:

[0008] S1: After mixing the initiator with the luminescent group and the monomer, copper bromide and ligand are added, followed by the addition of the reducing agent and solvent to obtain mixed solution A; mixed solution A is heated in an anaerobic environment to carry out the reaction, and after the reaction is completed, reaction product A is obtained. Reaction product A is added dropwise to an aqueous methanol solution, centrifuged and dried to obtain polymer A;

[0009] S2: After mixing polymer A obtained in S1 with monomers, copper bromide, ligands, solvents and reducing agents are added to obtain mixed solution B; mixed solution B is heated in an anaerobic environment to carry out the reaction, and reaction product B is obtained after the reaction is completed. Reaction product B is added dropwise to an aqueous methanol solution, centrifuged and dried to obtain polymer B; polymer B is self-assembled to obtain an intrinsically stretchable room temperature phosphorescent polymer material.

[0010] Further, in S1, the luminescent group in the initiator with the luminescent group is one or more of carbazole, benzophenone, naphthalenedicarboximide, biphenyl, phenylboronic acid and phenothiazine;

[0011] The preparation process of the biphenyl-containing initiator is as follows: p-hydroxybiphenyl, dichloromethane and triethylamine are mixed under ice bath conditions, then 2-bromoisobutyryl bromide is added, and the mixture is stirred, filtered and rotary evaporated to obtain the biphenyl-containing initiator.

[0012] Further, the ratio of the amount of p-hydroxybiphenyl, dichloromethane, triethylamine and 2-bromoisobutyryl bromide is (4.9-5.1) g : (10-30) mL : (3.5-3.8) g : (7.0-7.5) mL; and the stirring time is 30 min to 60 min.

[0013] Furthermore, in S1 and S2, the stabilizer in the monomer is removed by alkaline alumina before use; the monomer is methyl acrylate, tert-butyl acrylate, butyl methacrylate, methyl methacrylate, or tert-butyl methacrylate.

[0014] Further, in S1 and S2, the ligand is one or more of tripyridylmethyleneamine, tris(2-dimethylaminoethyl)amine, and N,N,N',N',N'',N''-pentamethyldiethylenetriamine; the reducing agent is one or more of azobisisobutyronitrile, benzoyl peroxide, and ammonium persulfate; the solvent is dioxane, tetrahydrofuran, N,N-dimethylformamide, anisole, or dimethyl sulfoxide; the heating is performed by oil bath heating; the oil bath heating temperature is 70-80°C, and the time is 1-3 hours.

[0015] Further, in S1, in the mixed solution A, the molar ratio of the initiator with the luminescent group, monomer, copper bromide, ligand and reducing agent is (1.00~1.01):(50~2000):(0.03~0.035):(0.03~0.035):(0.3~0.35); the volume ratio of the added solvent to the monomer is (1~1.5):(1~1.2); the volume ratio of the reaction product A to the aqueous methanol solution is (1~2)g:(10~100)mL; in the aqueous methanol solution, the volume ratio of methanol to water is 1:1; and the drying temperature is 60~80℃.

[0016] Further, in S2, in the mixed solution B, the molar ratio of polymer A, monomer, copper bromide, ligand and reducing agent is (1.00~1.01):(300~2000):(0.03~0.035):(0.18~0.21):(0.3~0.35); the volume ratio of the added solvent to the monomer is (1~1.5):(1~1.2); the volume ratio of reaction product B to the methanol aqueous solution is (1~2)g:(10~100)mL; in the methanol aqueous solution, the volume ratio of methanol to water is 1:1; the drying temperature is 60~80℃.

[0017] Further, in S2, the step of self-assembling polymer B is as follows: polymer B is dissolved in dichloromethane, then trifluoroacetic acid is added, stirred at room temperature, precipitated in petroleum ether, rotary evaporated and dried to obtain an intermediate polymer, the intermediate polymer is redissolved with dioxane, and then added to deionized water at 0-5°C to complete the self-assembly.

[0018] Further, the ratio of polymer B to dichloromethane is (1-5) g : (10-50) mL; the molar ratio of trifluoroacetic acid to tert-butyl in polymer B is (5-3) : (1.00-1.05); and the ratio of intermediate polymer to dioxane is (1-2) g : (1-3) mL.

[0019] The present invention also discloses an intrinsically stretchable room-temperature phosphorescent polymer material prepared by the above preparation method.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] This invention discloses a method for preparing an intrinsically stretchable room-temperature phosphorescent polymer. Because atom transfer radical polymerization can retain active chain ends, a large initiator can be formed after polymerization with the first hard-segment monomer. Then, utilizing its active chain ends, polymerization with the second soft-segment monomer forms an intrinsically flexible long-afterglow polymer with controllable molecular weight, possessing both hard and soft segments. After hydrolysis, the hard-segment monomers, due to their hydrophilic carboxyl groups, can self-assemble in deionized water. By controlling the chain length of the polymer through atom transfer radical polymerization method, controlling the hydrophilicity / hydrophobicity of the blocks through hydrolysis, and then through self-assembly, the basic units spontaneously aggregate into a stable structure with a certain regular geometric appearance under non-covalent interactions. This effectively reduces the S1→T1 energy level difference, achieves more intersystem crossing (ISC) channels, and significantly enhances the spin-orbit coupling effect. This invention can effectively promote the occurrence of ISC, resulting in a long-afterglow polymer material with both long lifetime and high stretchability at room temperature, exhibiting an ultra-long afterglow lifetime at room temperature.

[0022] The present invention also discloses an intrinsically stretchable room-temperature phosphorescent polymer material prepared by the above preparation method. According to relevant experimental results, its luminescence lifetime reaches 4s and its elongation at break reaches 200%. It is a polymer long afterglow material that combines long lifetime and high stretchability under room temperature conditions and has broad application prospects. Attached Figure Description

[0023] Figure 1 Thermomechanical analysis curves of the intrinsically stretchable room-temperature phosphorescent polymer material of the present invention;

[0024] Where: a - the relationship between the loss tangent of the material and temperature; b - the relationship between the storage modulus of the material and temperature;

[0025] Figure 2 The tensile stress-strain curve of the intrinsically stretchable room-temperature phosphorescent polymer material of the present invention is shown. Detailed Implementation

[0026] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0027] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0028] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0029] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0030] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0031] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0032] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0033] Example 1

[0034] A method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material includes the following steps:

[0035] S1: Dissolve 5g of p-hydroxybiphenyl in 10mL of anhydrous dichloromethane, then add 3.567g of triethylamine under ice bath conditions, then add 7mL of 2-bromoisobutyryl bromide and stir for 30min. After filtration and rotary evaporation, the initiator containing biphenyl is obtained.

[0036] 0.128 g of biphenyl initiator was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0053 g of tripyridinium methyleneamine, and 20 mL of N,N-dimethylformamide were added. Subsequently, 0.01 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70 °C oil bath under an oxygen-free environment for 3 h. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 30 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0037] S2: Redissolve 2.80g of polymer A with a molecular weight of 20000 in 10mL of anisole and add it to a Schroeder flask. Then add 5mL of butyl methacrylate, 0.00052g of copper bromide, 0.0042g of tripyridylmethyleneamine, and 5mL of... N,N-dimethylformamide and 0.002 g of azobisisobutyronitrile were mixed, and finally 5 mL of anisole was added to obtain mixed solution B. After sealing, nitrogen gas was bubbled in to remove oxygen. Mixed solution B was heated and stirred in an oil bath at 70 °C for 3 h in an oxygen-free environment. After the reaction was completed, reaction product B was obtained. Reaction product B was added dropwise to 20 mL of methanol and water in a 1:1 volume ratio, and precipitation, centrifugation, and drying were performed to obtain polymer B. 3 g of polymer B was redissolved in 20 mL of DCM, and 5 g of trifluoroacetic acid was added. The mixture was stirred overnight at room temperature, precipitated in 20 mL of petroleum ether, rotary evaporated, and dried to obtain intermediate polymer. Intermediate polymer was redissolved in 6 mL of dioxane and self-assembled in 30 mL of deionized water at 3 °C to obtain an intrinsically stretchable room temperature phosphorescent polymer material (the target degree of polymerization of the second-stage BMA monomer is 400).

[0038] The tert-butyl acrylate and butyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0039] Example 2

[0040] A method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material includes the following steps:

[0041] S1: Dissolve 5g of p-hydroxybiphenyl in 20mL of anhydrous dichloromethane, then add 3.567g of triethylamine under ice bath conditions and mix, then add 7mL of 2-bromoisobutyryl bromide and stir for 30min. After filtration and rotary evaporation, the initiator containing biphenyl is obtained.

[0042] 0.128 g of biphenyl initiator was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0051 g of tripyridinium methyleneamine, and 20 mL of N,N-dimethylformamide were added. Subsequently, 0.01 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 30 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0043] S2: 1.40 g of polymer A with a molecular weight of 20000 was redissolved in 10 mL of anisole and added to a Schroeder flask. Then, 5 mL of butyl methacrylate, 0.00026 g of copper bromide, 0.0021 g of tripyridinium methyleneamine, 5 mL of N,N-dimethylformamide, and 0.001 g of azobisisobutyronitrile were added. Finally, 5 mL of anisole was added to obtain mixed solution B. The flask was then sealed and nitrogen gas was bubbled in to purge oxygen. Mixed solution B was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was complete, reaction product B was obtained. Polymer B was added dropwise to 20 mL of a methanol-water aqueous solution with a volume ratio of 1:1, precipitated, centrifuged, and dried to obtain polymer B. 4 g of polymer A was redissolved in 20 mL of DCM, and 6 g of trifluoroacetic acid was added. The mixture was stirred overnight at room temperature, precipitated in 25 mL of petroleum ether, rotary evaporated, and dried to obtain an intermediate polymer. The intermediate polymer was redissolved in 3 mL of dioxane, and self-assembled in 30 mL of deionized water at 5 °C to obtain an intrinsically stretchable room-temperature phosphorescent polymer material (the target degree of polymerization of the second-stage BMA monomer is 800).

[0044] The tert-butyl acrylate and butyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0045] Example 3

[0046] A method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material includes the following steps:

[0047] S1: Dissolve 5g of p-hydroxybiphenyl in 25mL of anhydrous dichloromethane, then add 3.567g of triethylamine under ice bath conditions, mix, then add 7mL of 2-bromoisobutyryl bromide and stir for 30min. After filtration and rotary evaporation, obtain the initiator containing biphenyl.

[0048] 0.128 g of biphenyl initiator was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0052 g of tripyridinium methyleneamine, and 20 mL of N,N-dimethylformamide were added. Subsequently, 0.01 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 35 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0049] S2: 2.23 g of polymer A with a molecular weight of 20000 was redissolved in 10 mL of anisole and added to a Schroeder flask. Then, 5 mL of butyl methacrylate, 0.00026 g of copper bromide, 0.0025 g of tripyridinium methyleneamine, 5 mL of N,N-dimethylformamide, and 0.005 g of azobisisobutyronitrile were added. Finally, 5 mL of anisole was added to obtain mixed solution B. The flask was then sealed and nitrogen gas was bubbled in to purge oxygen. Mixed solution B was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was complete, reaction product B was obtained. Polymer B was added dropwise to 15 mL of a methanol-water aqueous solution with a volume ratio of 1:1, precipitated, centrifuged, and dried to obtain polymer B. 3 g of polymer B was redissolved in 15 mL of DCM, and 4 g of trifluoroacetic acid was added. The mixture was stirred overnight at room temperature, precipitated in 20 mL of petroleum ether, rotary evaporated, and dried to obtain an intermediate polymer. The intermediate polymer was redissolved in 5 mL of dioxane and self-assembled in 20 mL of deionized water at 3 °C to obtain an intrinsically stretchable room temperature phosphorescent polymer material (the target degree of polymerization of the second-stage BMA monomer is 1200).

[0050] The tert-butyl acrylate and butyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0051] Example 4

[0052] A method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material includes the following steps:

[0053] S1: Dissolve 5g of p-hydroxybiphenyl in 25mL of anhydrous dichloromethane, then add 3.567g of triethylamine under ice bath conditions, mix, then add 7mL of 2-bromoisobutyryl bromide and stir for 30min. After filtration and rotary evaporation, obtain the initiator containing biphenyl.

[0054] 0.128 g of biphenyl initiator was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0052 g of tripyridinium methyleneamine, and 20 mL of N,N-dimethylformamide were added. Subsequently, 0.01 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 35 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0055] S2: Dissolve 0.8g of polymer A with a molecular weight of 20000 in 10mL of anisole and add it to a Schroeder flask. Then add 8mL of butyl methacrylate, 0.00026g of copper bromide, 0.0025g of tripyridinium methyleneamine, 10mL of N,N-dimethylformamide, and 0.005g of azobisisobutyronitrile. Finally, add 5mL of anisole to obtain mixed solution B. After sealing, purge with nitrogen to remove oxygen. Place mixed solution B in a 70℃ oil bath under an oxygen-free environment and heat with stirring for 3 hours. After the reaction is complete, obtain reaction product B. Add 5 mL of methanol and water in a 1:1 volume ratio to a methanol-water aqueous solution, precipitate, centrifuge, and dry to obtain polymer B; redissolve 0.5 g of polymer A in 10 mL of DCM, add 2 g of trifluoroacetic acid, stir overnight at room temperature, precipitate in 20 mL of petroleum ether, rotary evaporate, and dry to obtain an intermediate polymer; redissolve the intermediate polymer in 5 mL of dioxane, add 20 mL of deionized water at 3 °C to complete self-assembly, and obtain an intrinsically stretchable room temperature phosphorescent polymer material (the target degree of polymerization of the second-stage BMA monomer is 1200);

[0056] The tert-butyl acrylate and butyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0057] Example 5

[0058] A method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material includes the following steps:

[0059] S1: Dissolve 5.38 g of 2-hydroxycarbazole in 25 mL of anhydrous dichloromethane, then add 3.567 g of triethylamine under ice bath conditions and mix, then add 7 mL of 2-bromoisobutyryl bromide and stir for 60 min. After filtration and rotary evaporation, obtain the initiator containing carbazole.

[0060] 0.136 g of initiator containing carbazole was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0041 g of tris(2-dimethylaminoethyl)amine, and 20 mL of dioxane were added. Subsequently, 0.012 g of benzoyl peroxide and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was bubbled in to purge oxygen. The mixed solution A was heated and stirred in a 70 °C oil bath under an oxygen-free environment for 3 h. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 40 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0061] S2: 0.76 g of polymer A with a molecular weight of 20000 was redissolved in 10 mL of anisole and added to a Schroeder flask. Then, 10 mL of methyl acrylate, 0.0003 g of copper bromide, 0.0028 g of tripyridylmethyleneamine, 10 mL of dioxane, and 0.0058 g of benzoyl peroxide were added. Finally, 5 mL of anisole was added to obtain mixed solution B. The flask was then sealed and nitrogen gas was bubbled in to purge oxygen. Mixed solution B was heated and stirred in an 80°C oil bath for 1 hour under an oxygen-free environment. After the reaction was complete, reaction product B was obtained. Reaction product B was added dropwise to 10 mL of... In a methanol-water solution with a volume ratio of 1:1, precipitate, centrifuge, and dry to obtain polymer B; redissolve 0.45g of polymer A in 10mL of DCM, add 2.5g of trifluoroacetic acid, stir overnight at room temperature, precipitate in 25mL of petroleum ether, rotary evaporate, and dry to obtain intermediate polymer; redissolve intermediate polymer in 5mL of dioxane, and complete self-assembly in 20mL of deionized water at 3℃ to obtain an intrinsically stretchable room temperature phosphorescent polymer material (the target degree of polymerization of the second-stage MA monomer is 1200).

[0062] The tert-butyl acrylate and methyl acrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0063] Example 6

[0064] S1: Dissolve 5.82 g of 2-hydroxybenzophenone in 25 mL of anhydrous dichloromethane, then add 3.567 g of triethylamine under ice bath conditions and mix, then add 7 mL of 2-bromoisobutyryl bromide and stir for 45 min. After filtration and rotary evaporation, an initiator containing benzophenone is obtained.

[0065] 0.156 g of initiator containing benzophenone was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0036 g of N,N,N',N”,N”-pentamethyldiethylenetriamine, and 20 mL of dioxane were added. Subsequently, 0.012 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 40 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0066] S2: Dissolve 0.80g of polymer A with a molecular weight of 20000 in 10mL of anisole and add it to a Schroeder flask. Then add 10mL of methyl methacrylate, 0.0003g of copper bromide, 0.0028g of tripyridylmethyleneamine, 10mL of tetrahydrofuran, and 0.0047g of ammonium persulfate. Finally, add 5mL of anisole to obtain mixed solution B. Seal the flask and purge with nitrogen to remove oxygen. Place mixed solution B in a 75°C oil bath under an oxygen-free environment and heat with stirring for 1.5h. After the reaction is complete, obtain reaction product B. Add reaction product B dropwise to 10 mL of anisole. In a methanol-water solution with a volume ratio of 1:1, precipitate, centrifuge, and dry to obtain polymer B; redissolve 0.48g of polymer A in 10mL of DCM, add 2.6g of trifluoroacetic acid, stir overnight at room temperature, precipitate in 25mL of petroleum ether, rotary evaporate, and dry to obtain intermediate polymer; redissolve intermediate polymer in 5mL of tetrahydrofuran, and complete self-assembly in 20mL of deionized water at 3℃ to obtain an intrinsically stretchable room temperature phosphorescent polymer material (the target degree of polymerization of the second-stage MMA monomer is 1200);

[0067] The tert-butyl acrylate and methyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0068] Example 7

[0069] S1: Dissolve 5.46 g of N-hydroxyphthalimide in 25 mL of anhydrous dichloromethane, then add 3.567 g of triethylamine under ice bath conditions and mix, then add 7 mL of 2-bromoisobutyryl bromide and stir for 45 min. After filtration and rotary evaporation, an initiator containing naphthalimide is obtained.

[0070] 0.148 g of initiator containing naphthalenedicarboximide was added to a Schroeder flask, followed by 20 mL of tert-butyl acrylate. Then, 0.000669 g of copper bromide, 0.0036 g of N,N,N',N”,N”-pentamethyldiethylenetriamine, and 20 mL of dioxane were added. Subsequently, 0.012 g of azobisisobutyronitrile and 20 mL of anisole were added to the mixed solution A. The flask was then sealed and nitrogen gas was introduced to purge oxygen. The mixed solution A was heated and stirred in a 70°C oil bath under an oxygen-free environment for 3 hours. After the reaction was completed, reaction product A was obtained. Reaction product A was added dropwise to 40 mL of a methanol-water aqueous solution with a volume ratio of 1:1. After precipitation, centrifugation, and drying, polymer A was obtained.

[0071] S2: Dissolve 0.78g of polymer A with a molecular weight of 20000 in 10mL of anisole and add it to a Schroeder flask. Then add 10mL of tert-butyl methacrylate, 0.0003g of copper bromide, 0.0028g of tripyridinium methyleneamine, 10mL of tetrahydrofuran, and 0.0045g of ammonium persulfate. Finally, add 5mL of anisole to obtain mixed solution B. After sealing, purge with nitrogen to remove oxygen. Place mixed solution B in a 75℃ oil bath under an oxygen-free environment and heat with stirring for 1.5h. After the reaction is complete, obtain reaction product B. Add reaction product B dropwise to 10mL of... Polymer B was obtained by precipitation, centrifugation, and drying in a methanol-water aqueous solution with a volume ratio of 1:1. 0.70 g of polymer A was redissolved in 13 mL of DCM, and 3.8 g of trifluoroacetic acid was added. The mixture was stirred overnight at room temperature, precipitated in 30 mL of petroleum ether, rotary evaporated, and dried to obtain an intermediate polymer. The intermediate polymer was redissolved in 5 mL of tetrahydrofuran and self-assembled in 30 mL of deionized water at 3°C ​​to obtain an intrinsically stretchable room-temperature phosphorescent polymer (the target degree of polymerization of the second-stage tert-BMA monomer is 1200).

[0072] The tert-butyl acrylate and tert-butyl methacrylate used in the above preparation process need to have their stabilizers removed by alkaline alumina before use.

[0073] In the implementation of this invention, the monomers used to synthesize the intrinsically stretchable room-temperature phosphorescent polymer material can be common monomers such as methyl acrylate, butyl acrylate, butyl methacrylate, methyl methacrylate, and tert-butyl methacrylate. The target degree of polymerization can be any degree of polymerization above 50. The reaction time can be any time above 2 hours. The solvents that can be used in this invention are one of the following: dioxane, N,N-dimethylformamide, tetrahydrofuran, anisole, and dimethyl sulfoxide. The drying temperature described in this invention can be any temperature above 50°C.

[0074] Furthermore, in specific implementations of this invention, the separation method can be any of the following methods: centrifugation using a centrifuge, or filtration using a vacuum pump.

[0075] Figure 1 The figures shown are the thermomechanical analysis curves of the intrinsically stretchable room-temperature phosphorescent polymer materials prepared in Examples 1 to 3. Figure 1 As can be seen from a, the glass transition temperature of these three embodiments is approximately 55°C, and the glass transition temperature increases with the degree of polymerization of the second-stage BMA monomer. Figure 1 As can be seen from b, the higher the degree of polymerization of BMA monomers, the lower their energy storage modulus, indicating that their resilience is worse.

[0076] Figure 2The figure shows the tensile stress-strain curves of the intrinsically stretchable room-temperature phosphorescent polymer materials prepared in Examples 1 to 3. It can be seen from the figure that as the length of the second BMA soft segment increases, the Young's modulus of the material remains almost unchanged, and its elongation at break increases.

[0077] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for preparing an intrinsically stretchable room temperature phosphorescent high molecular material, characterized in that, Comprise the following steps: S1: after mixing initiator with luminous group and monomer, copper bromide and ligand are added, then auxiliary agent and solvent are added in turn, mixed solution A is obtained; mixed solution A is heated to react under oxygen-free environment, reaction product A is obtained after reaction, reaction product A is dropped into methanol aqueous solution, centrifugation, drying treatment are carried out, polymer A is obtained; S2: after mixing polymer A obtained in S1 and monomer, copper bromide, ligand, solvent and auxiliary agent are added, mixed solution B is obtained; mixed solution B is heated to react under oxygen-free environment, reaction product B is obtained after reaction, reaction product B is dropped into methanol aqueous solution, centrifugation, drying treatment are carried out, polymer B is obtained; polymer B is self-assembled, and an intrinsic stretchable room-temperature phosphorescent polymer material is obtained; In S1, the initiator with luminous group is one or more of initiator with biphenyl, initiator with carbazole, initiator with benzophenone and initiator with naphthalene dicarboximide; the preparation process of the initiator with biphenyl is that p-hydroxy biphenyl, dichloromethane and triethylamine are mixed under ice bath condition, then 2-bromoisobutyryl bromide is added, stirring, filtration, rotary evaporation are carried out, and the initiator with biphenyl is obtained; In S1 and S2, the monomer is removed stabilizer therein by basic alumina before use; the monomer in S1 is tert-butyl acrylate; The monomer in S2 is methyl acrylate, butyl methacrylate, methyl methacrylate or tert-butyl methacrylate; The dosage ratio of p-hydroxy biphenyl, dichloromethane, triethylamine and 2-bromoisobutyryl bromide is (4.9~5.1) g:(10~30) mL:(3.5~3.8) g:(7.0~7.5) mL; the stirring time is 30 min~60 min; In S1, in mixed solution A, the molar ratio of the initiator with luminous group, monomer, copper bromide, ligand and auxiliary agent is (1.00~1.01):(50~2000):(0.03~0.035):(0.03~0.035):(0.3~0.35); the volume ratio of the added solvent to the monomer is (1~1.5):(1~1.2); the dosage ratio of reaction product A to methanol aqueous solution is (1~2) g:(10~100) mL; in the methanol aqueous solution, the volume ratio of methanol to water is 1:1; the drying temperature is 60~80℃; In S2, in mixed solution B, the molar ratio of polymer A, monomer, copper bromide, ligand and auxiliary agent is (1.00~1.01):(300~2000):(0.03~0.035):(0.18~0.21):(0.3~0.35); the volume ratio of the added solvent to the monomer is (1~1.5):(1~1.2); the dosage ratio of reaction product B to methanol aqueous solution is (1~2) g:(10~100) mL; in the methanol aqueous solution, the volume ratio of methanol to water is 1:1; the drying temperature is 60~80℃; In S2, the step of self-assembling polymer B is: dissolving polymer B in dichloromethane, adding trifluoroacetic acid, precipitating in petroleum ether after stirring at room temperature, and obtaining intermediate polymer after rotary evaporation and drying; redissolving the intermediate polymer in dioxane, adding deionized water at 0-5 DEG C to complete self-assembly; the ratio of polymer B to dichloromethane is (1-5) g:(10-50) mL; the molar ratio of trifluoroacetic acid to t-butyl in polymer B is (5-3):(1.00-1.05); the ratio of intermediate polymer to dioxane is (1-2) g:(1-3) mL. The auxiliary agent is one or more of azobisdimethyl isobutyronitrile, dibenzoyl peroxide and ammonium persulfate.

2. The method for preparing an intrinsically stretchable room-temperature phosphorescent polymer material according to claim 1, characterized in that, In S1 and S2, the ligand is one or more of trispyridyl methylene amine, tris (2-dimethylaminoethyl) amine and N,N,N',N'',N''-pentamethyl diethylene triamine; the solvent is dioxane, tetrahydrofuran, N,N-dimethylformamide, anisole or dimethyl sulfoxide; the heating is oil bath heating; the temperature of the oil bath heating is 70-80 DEG C, and the time is 1-3 h.

3. An intrinsically stretchable room temperature phosphorescent high molecular material, characterized in that, The intrinsic stretchable room-temperature phosphorescent polymer material is prepared by the preparation method of the intrinsic stretchable room-temperature phosphorescent polymer material in claim 1 or 2. In S2, the step of self-assembling polymer B is: dissolving polymer B in dichloromethane, adding trifluoroacetic acid, precipitating in petroleum ether after stirring at room temperature, and obtaining intermediate polymer after rotary evaporation and drying; redissolving the intermediate polymer in dioxane, adding deionized water at 0-5 DEG C to complete self-assembly; the ratio of polymer B to dichloromethane is (1-5) g:(10-50) mL; the molar ratio of trifluoroacetic acid to t-butyl in polymer B is (5-3):(1.00-1.05); the ratio of intermediate polymer to dioxane is (1-2) g:(1-3) mL. The auxiliary agent is one or more of azobisdimethyl isobutyronitrile, dibenzoyl peroxide and ammonium persulfate. In S1 and S2, the ligand is one or more of trispyridyl methylene amine, tris (2-dimethylaminoethyl) amine and N,N,N',N'',N''-pentamethyl diethylene triamine; the solvent is dioxane, tetrahydrofuran, N,N-dimethylformamide, anisole or dimethyl sulfoxide; the heating is oil bath heating; the temperature of the oil bath heating is 70-80 DEG C, and the time is 1-3 h. The intrinsic stretchable room-temperature phosphorescent polymer material is prepared by the preparation method of the intrinsic stretchable room-temperature phosphorescent polymer material in claim 1 or 2.

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