CN111848927B - Phosphorescent polymer material and preparation method and application thereof - Google Patents

Phosphorescent polymer material and preparation method and application thereof Download PDF

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CN111848927B
CN111848927B CN202010668985.0A CN202010668985A CN111848927B CN 111848927 B CN111848927 B CN 111848927B CN 202010668985 A CN202010668985 A CN 202010668985A CN 111848927 B CN111848927 B CN 111848927B
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phosphor
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CN111848927A (en
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王国杰
武波
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University of Science and Technology Beijing USTB
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Abstract

The invention provides a phosphorescent polymer material and a preparation method and application thereof, relates to the technical field of organic luminescent materials and anti-counterfeiting materials, can obtain a pure organic polymer material with high-efficiency long-life room-temperature phosphorescent property, greatly prolongs the phosphorescent service life, improves the phosphorescent quantum efficiency, and has the advantages of simple preparation, cheap raw materials and good stability; the method effectively inhibits the non-radiative decay of various organic phosphors through a compact three-dimensional epoxy polymer network, thereby simultaneously realizing ultra-long service life and high quantum yield in a polymer film; the absolute phosphorescence quantum yield of the prepared phosphorescence polymer material is more than 8.35%, and the phosphorescence lifetime is more than 2.28 s; the retention time of the phosphorescent property at room temperature is 7s or more. The technical scheme provided by the invention is suitable for the process of preparing the room-temperature phosphorescent material.

Description

Phosphorescent polymer material and preparation method and application thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of organic luminescent materials and anti-counterfeiting materials, in particular to a phosphorescent polymer material and a preparation method and application thereof.
[ background of the invention ]
The ultra-long room temperature phosphorescent material has unique advantages in the fields of information encryption, medical imaging, optical display and the like due to the lasting phosphorescence. With the rapid development of organic optical displays and flexible sensors, pure organic ultralong room temperature phosphorescent materials are an outstanding alternative to traditional inorganic or organometallic phosphors due to their high transparency and low cost. Related researchers have proposed methods to obtain pure organic ultralong room temperature phosphorescent materials, such as crystal engineering, H-aggregates, host-guest interactions, deuteration, etc. However, in these methods, the problems of poor film forming property, poor dispersibility, complex synthesis steps, high cost, and harsh conditions for manufacturing and using are common, which seriously hinders their practical application. The outstanding properties of polymers, such as elasticity, flexibility, film-forming ability and transparency, make film-forming polymeric materials with long-term phosphorescent emission very promising for the manufacture and processing of optical devices. Therefore, it is necessary to develop a pure organic ultra-long room temperature phosphorescent material based on polymer. However, in pure organic molecules without heavy atoms, the generation of long-lived triplet excitons is not common, and triplet excitons in organic materials are highly concentrated and are readily dissipated by vibration and oxygen consumption. Two important factors should be considered when designing new purely organic ultralong room temperature phosphorescent materials: (1) by effectively improving the spin-orbit coupling between the lowest excited singlet state and the triplet state in the organic molecule; (2) the nonradiative relaxation path from the lowest excited triplet state to the ground state is suppressed as much as possible.
Accordingly, there is a need to develop a phosphorescent polymer material, a method of preparing the same, and applications thereof to address the deficiencies of the prior art to solve or mitigate one or more of the problems set forth above.
[ summary of the invention ]
In view of the above, the invention provides a phosphorescent polymer material, and a preparation method and an application thereof, and the phosphorescent polymer material can be a pure organic polymer material with high efficiency, long service life and room-temperature phosphorescent property, so that the phosphorescent service life is greatly prolonged, the phosphorescent quantum efficiency is improved, and the phosphorescent polymer material is simple to prepare, cheap in raw materials and good in stability.
In one aspect, the present invention provides a method for preparing a phosphorescent polymer material, which is characterized by effectively suppressing non-radiative decay of a plurality of organic phosphors through a dense three-dimensional epoxy polymer network, thereby simultaneously achieving an ultra-long lifetime and a high quantum yield in a polymer thin film.
The above aspects and any possible implementations further provide an implementation in which the organic phosphor is an organic small molecule phosphor; the organic small molecule phosphor is a first phosphor or a second phosphor;
the first phosphor is: any one or two mixtures of N, N, N ', N' -tetramethyl benzidine and triphenylamine;
the second phosphor is: any one or a mixture of more than two of 4,4' -dihydroxybiphenyl, N, N, N ', N ' -tetramethyl-1, 4-phenylenediamine and 2, 6-diphenylphenol.
The above aspects and any possible implementations further provide an implementation in which the epoxy polymer is polymerized by curing an epoxy matrix; the epoxy matrix is any one of 2, 2-bis- (4-glycinyloxybenzene) propane and bisphenol A epoxy resin with the number average molecular weight lower than 2000.
The above-described aspect and any possible implementation manner further provide an implementation manner, and a specific process of the method includes: under the action of protective atmosphere, the first phosphor is doped into the epoxy matrix according to a certain proportion and stirred uniformly, then the curing agent is added according to a certain proportion and stirred until the mixture is transparent, and the final phosphorescent polymer material is obtained after curing.
The above-described aspect and any possible implementation manner further provide an implementation manner, and a specific process of the method includes: and dissolving the second phosphor in the liquid curing agent in proportion, uniformly stirring, mixing with the epoxy matrix, stirring until the mixture is transparent, and curing to obtain the final phosphorescent polymer material.
The above aspects and any possible implementations further provide an implementation in which the curing agent is any one of an aliphatic diamine, a polyamine, and a tertiary amine.
The aspect and any possible implementation described above, further provides an implementation in which the molar ratio of the phosphorescent small molecule of the first phosphor or the second phosphor to the epoxy group in the epoxy matrix is 1: 10-1000, wherein the molar ratio of the curing agent to the epoxy group in the epoxy matrix is 1: 1 to 8.
The above aspects and any possible implementation manner further provide an implementation manner, wherein the curing temperature is 25 ℃ to 140 ℃, and the curing time is 12 hours to 48 hours.
In another aspect, the present invention provides a phosphorescent polymer material, wherein the phosphorescent polymer material is prepared by any one of the above preparation methods;
the absolute phosphorescence quantum yield of the phosphorescence polymer material is more than 8.35%, and the phosphorescence service life of the phosphorescence polymer obtained by fitting according to a phosphorescence attenuation curve is 0.14-0.65 s; the visible phosphorescence visible to the naked eye can be maintained for more than three seconds at the temperature of 60 ℃.
In another aspect, the present invention provides a use of a phosphorescent polymer material, wherein the phosphorescent polymer material is prepared by any one of the above preparation methods; the phosphorescent polymer material is applied as a room-temperature phosphorescent material, an anti-counterfeiting material or a biomedical imaging material.
Compared with the prior art, the invention can obtain the following technical effects: the pure organic phosphorescent micromolecule doped polymer material provided by the invention can be used as a long-life room temperature phosphorescent material, has high phosphorescent quantum efficiency and long-life room temperature phosphorescent property, and can be used in the fields of anti-counterfeiting materials, information encryption, data storage, medical imaging and the like; the pure organic phosphorescent micromolecule doped room-temperature phosphorescent polymer material with high efficiency and long service life provided by the invention has the advantages of ultra-long service life room-temperature phosphorescent property, high phosphorescent quantum yield, simplicity in preparation, cheap raw materials, good stability, capability of being prepared in a large scale and the like; the visible phosphorescence which can be seen by naked eyes for more than three seconds can be maintained at the high temperature of 60 ℃; the phosphorescence life of the phosphorescence polymer obtained by phosphorescence attenuation curve fitting is 0.14-0.65 s.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a phosphorescence spectrum of a room temperature phosphorescent polymer material provided in example 1 of the present invention;
FIG. 2 is a phosphorescence attenuation curve of the room temperature phosphorescent polymer material provided in example 1 of the present invention;
FIG. 3 is a phosphorescent photograph of the room temperature phosphorescent polymer material provided in example 1 of the present invention at different times after being excited by ultraviolet light and the light source is removed;
FIG. 4 is a photograph of a double encrypted model prepared from the room temperature phosphorescent polymer material provided in example 1 of the present invention;
FIG. 5 is a phosphorescence spectrum of a room temperature phosphorescent polymer material provided in example 2 of the present invention;
FIG. 6 is a phosphorescence attenuation curve of a room temperature phosphorescent polymer material provided in example 2 of the present invention;
FIG. 7 is a phosphorescence spectrum of a room temperature phosphorescent polymer material provided in example 3 of the present invention;
FIG. 8 is a phosphorescence attenuation curve of a room temperature phosphorescent polymer material provided in example 3 of the present invention;
FIG. 9 shows the phosphorescence spectrum of the room temperature phosphorescent polymer material provided in example 4 of the present invention;
FIG. 10 is a phosphorescence decay curve of a room temperature phosphorescent polymer material provided in example 4 of the present invention;
FIG. 11 is a phosphorescence spectrum of a room temperature phosphorescent polymer material provided in example 5 of the present invention;
FIG. 12 is a phosphorescence attenuation curve of the room temperature phosphorescent polymer material provided in example 5 of the present invention.
[ detailed description ] embodiments
For better understanding of the technical solutions of the present invention, the following detailed descriptions of the embodiments of the present invention are provided with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The invention provides a method for preparing a pure organic room-temperature phosphorescent polymer material with high efficiency and long service life, which effectively inhibits the non-radiative decay of various organic phosphors mainly through a compact three-dimensional epoxy polymer network, thereby simultaneously realizing ultra-long service life and high quantum yield in a polymer film. The preparation method is simple and strong in universality. The pure organic high efficiency long life room temperature phosphorescent polymer material can be excited by ultra low power (i.e. as low as 5 microwatts per square centimeter) ultraviolet light or by sunlight only. In addition, the film may have significant phosphorescence that is visible to the naked eye for more than three seconds at elevated temperatures up to 60 ℃. The pure organic high-efficiency long-life room temperature phosphorescent polymer material provided by the invention can be used in the fields of anti-counterfeiting materials, information encryption, data storage, medical imaging and the like.
The high-efficiency long-life room-temperature phosphorescent polymer material provided by the invention comprises three parts of organic micromolecular phosphor, an epoxy matrix and a curing agent:
(1) pure organic small molecule phosphors used to prepare room temperature phosphorescent polymer materials include:
Figure BDA0002581598090000051
Figure BDA0002581598090000061
the phosphor may be any one of the above five organic small molecule phosphors, or may be a combination of any two or more.
(2) An epoxy matrix for use in the preparation of room temperature phosphorescent polymer materials comprising any one of 2, 2-bis- (4-glycidoxybenzene) propane (i.e. bisphenol a diglycidyl ether, formula F) and a low viscosity bisphenol a type epoxy resin having a number average molecular weight of less than 2000.
An epoxy matrix for use in the preparation of room temperature phosphorescent polymer materials comprising any one of 2, 2-bis- (4-glycidoxybenzene) propane (i.e. bisphenol a diglycidyl ether, formula F) and a low viscosity bisphenol a type epoxy resin having a number average molecular weight of less than 2000.
Figure BDA0002581598090000062
(3) The curing agent for curing the epoxy resin includes any one of aliphatic diamine, polyamine, and tertiary amine such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, triethylamine, tetramethylethylenediamine, etc.
The preparation method of the high-efficiency long-life room temperature phosphorescent polymer material comprises a scheme I and a scheme II:
the organic phosphorescent small molecules shown in the formulas A and B are suitable for scheme one:
dissolving the organic phosphorescent micromolecules shown in the formulas A and B in the epoxy matrix under the protection of nitrogen, uniformly stirring, and cooling to room temperature; mixing the mixture with the liquid curing agent in a certain proportion, stirring until the mixture is transparent, injecting the mixture into a mold, and curing to obtain the phosphorescent material.
The organic phosphorescent small molecules shown in the formulas C, D and E are suitable for the scheme II:
dissolving the organic phosphorescent micromolecules shown in the formulas C, D and E in the liquid curing agent according to a certain proportion, and uniformly stirring; mixing the mixture with the epoxy matrix in a certain proportion, stirring until the mixture is transparent, injecting the mixture into a mold, and curing to obtain the phosphorescent material.
In the two preparation methods, the molar ratio of the organic phosphorescent micromolecules shown as the formula A, the formula B, the formula C, the formula D and the formula E to the epoxy group in the epoxy matrix is 1: 10 to 1000, preferably 1: 100. the molar ratio of the curing agent to the epoxy group in the epoxy matrix is 1: 1 to 8, preferably 1: 2. the curing temperature is 25-140 ℃, the reaction time is 12-48 hours, preferably 25 ℃ is kept for 24 hours, and then 80 ℃ is kept for 4 hours.
Specific examples are provided below, and the experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents, instruments, etc. used are commercially available unless otherwise specified.
Example 1:
the preparation method of the pure organic high-efficiency long-life room temperature phosphorescent polymer material doped with the molecule (N, N, N ', N' -tetramethyl benzidine) shown in the formula A comprises the following steps:
dissolving organic phosphorescent micromolecules (TMB molecules) shown in a formula A in 2, 2-bis- (4-glycinyloxybenzene) propane serving as an epoxy matrix under the protection of nitrogen, stirring uniformly, and cooling to room temperature. Wherein the molar ratio of the organic phosphorescent micromolecules to the epoxy groups in the epoxy matrix is 1: 100. mixing the mixture with an aliphatic curing agent ethylenediamine, wherein the molar ratio of the curing agent ethylenediamine to epoxy groups in the epoxy matrix is 1: 2. stirring to be transparent, injecting into a mold, keeping at 25 ℃ for 24 hours, and keeping at 80 ℃ for 4 hours to obtain the phosphorescent material.
FIG. 1 shows the phosphorescence spectrum of the prepared pure organic high efficiency long life room temperature phosphorescent polymer material doped with the molecule of formula A (N, N, N ', N' -tetramethylbenzidine), and the absolute phosphorescence quantum yield is 8.35% by test. FIG. 2 is a phosphorescence decay curve of the room temperature phosphorescent material at 528nm, and the phosphorescence lifetime is 2.28 seconds by fitting. Fig. 3 is a phosphorescent photograph of the room temperature phosphorescent material at different time intervals after being excited by ultraviolet light and the light source is removed, and it can be seen that the room temperature phosphorescent material has an ultra-long room temperature phosphorescent property, and the maintenance time of the room temperature phosphorescent material is more than 7 s. Fig. 4 is a photograph of a double-encrypted model prepared by applying the room temperature phosphorescent material, wherein the sample is colorless under natural light, a geometric figure formed by blue fluorescence is displayed under ultraviolet light, and encrypted information formed by phosphorescence is displayed after the ultraviolet lamp is turned off.
Example 2:
the preparation method of the pure organic high-efficiency long-life room temperature phosphorescent polymer material doped with the molecule (triphenylamine) shown in the formula B comprises the following steps:
dissolving the organic phosphorescent micromolecule (triphenylamine) shown in the formula B in 2, 2-bis- (4-glycinyloxybenzene) propane serving as an epoxy matrix under the protection of nitrogen, stirring uniformly, and cooling to room temperature. Wherein the molar ratio of the organic phosphorescent micromolecules to the epoxy groups in the epoxy matrix is 1: 100. mixing the mixture with an aliphatic curing agent ethylenediamine, wherein the molar ratio of the curing agent ethylenediamine to epoxy groups in the epoxy matrix is 1: 2. stirring to be transparent, injecting into a mold, keeping at 25 ℃ for 24 hours, and keeping at 80 ℃ for 4 hours to obtain the phosphorescent material.
FIG. 5 shows the phosphorescence spectrum of a prepared pure organic high efficiency long lifetime room temperature phosphorescent polymer material doped with a molecule of formula B (triphenylamine). FIG. 6 is a phosphorescence decay curve of the room temperature phosphorescent material at 500nm, and the phosphorescence lifetime is 0.22 seconds by fitting.
Example 3:
the preparation method of the pure organic high-efficiency long-life room temperature phosphorescent polymer material doped with C (4,4' -dihydroxybiphenyl) comprises the following steps:
dissolving the organic phosphorescent micromolecule (4,4' -dihydroxybiphenyl) shown in the formula C in the epoxy matrix 2, 2-bis- (4-glycinyloxybenzene) propane under the protection of nitrogen, stirring uniformly, and cooling to room temperature. Wherein the molar ratio of the organic phosphorescent micromolecules to the epoxy groups in the epoxy matrix is 1: 100. mixing the mixture with an aliphatic curing agent ethylenediamine, wherein the molar ratio of the curing agent ethylenediamine to epoxy groups in the epoxy matrix is 1: 2. stirring to be transparent, injecting into a mold, keeping at 25 ℃ for 24 hours, and keeping at 80 ℃ for 4 hours to obtain the phosphorescent material.
FIG. 7 is a phosphorescence spectrum of a prepared pure organic high efficiency long lifetime room temperature phosphorescent polymer material doped with C (4,4' -dihydroxybiphenyl) of formula. FIG. 8 is a phosphorescence decay curve of the room temperature phosphorescent material at 500nm, and the phosphorescence lifetime is 0.62 seconds by fitting.
Example 4:
the preparation method of the pure organic high-efficiency long-life room temperature phosphorescent polymer material doped with the formula D (N, N, N ', N' -tetramethyl-1, 4-phenylenediamine) comprises the following steps:
dissolving the organic phosphorescent micromolecule (N, N, N ', N' -tetramethyl-1, 4-phenylenediamine) shown in the formula D in epoxy matrix 2, 2-bis- (4-glycinyloxybenzene) propane under the protection of nitrogen, stirring uniformly, and cooling to room temperature. Wherein the molar ratio of the organic phosphorescent micromolecules to the epoxy groups in the epoxy matrix is 1: 100. mixing the mixture with an aliphatic curing agent ethylenediamine, wherein the molar ratio of the curing agent ethylenediamine to epoxy groups in the epoxy matrix is 1: 2. stirring to be transparent, injecting into a mold, keeping at 25 ℃ for 24 hours, and keeping at 80 ℃ for 4 hours to obtain the phosphorescent material.
FIG. 9 shows the phosphorescence spectra of the prepared pure organic high efficiency long lifetime room temperature phosphorescent polymer material doped with formula D (N, N, N ', N' -tetramethyl-1, 4-phenylenediamine). FIG. 10 is a phosphorescence decay curve at 490nm of the room temperature phosphorescent material, which is fitted to have a phosphorescence lifetime of 0.36 s.
Example 5:
the preparation method of the pure organic high-efficiency long-life room temperature phosphorescent polymer material doped with the formula E (2, 6-diphenylphenol) comprises the following steps:
dissolving the organic phosphorescent micromolecule (2, 6-diphenyl phenol) shown in the formula E in epoxy matrix 2, 2-bis- (4-glycinyloxybenzene) propane under the protection of nitrogen, stirring uniformly, and cooling to room temperature. Wherein the molar ratio of the organic phosphorescent micromolecules to the epoxy groups in the epoxy matrix is 1: 100. mixing the mixture with an aliphatic curing agent ethylenediamine, wherein the molar ratio of the curing agent ethylenediamine to epoxy groups in the epoxy matrix is 1: 2. stirring to be transparent, injecting into a mold, keeping at 25 ℃ for 24 hours, and keeping at 80 ℃ for 4 hours to obtain the phosphorescent material.
FIG. 11 is a phosphorescence spectrum of a prepared pure organic high efficiency long lifetime room temperature phosphorescent polymer material doped with formula E (2, 6-diphenylphenol). FIG. 12 is a phosphorescence decay curve of the room temperature phosphorescent material at 425nm, and the phosphorescence lifetime is 0.14 seconds by fitting.
As can be seen from the above examples and experimental results, they all have high efficiency, long life, room temperature phosphorescent properties and encryption anti-counterfeiting effect.
The pure organic polymer material with high efficiency and long service life and room-temperature phosphorescence property is obtained by doping the pure organic micromolecular phosphor into the epoxy polymer matrix with the compact network structure, so that the phosphorescence service life is greatly prolonged, and the phosphorescence quantum efficiency is improved.
The phosphorescent polymer material provided by the embodiment of the application, the preparation method and the application thereof are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (9)

1. A method for preparing a phosphorescent polymer material, characterized in that non-radiative decay of an organic phosphor is effectively suppressed by a dense epoxy polymer network, thereby achieving both a prolonged lifetime and an improved quantum yield in a polymer thin film; the epoxy polymer is formed by curing and polymerizing an epoxy matrix;
the organic phosphor is an organic small molecule phosphor; the organic small molecule phosphor is a first phosphor or a second phosphor or a combination of both;
the first phosphor is: any one or two mixtures of N, N, N ', N' -tetramethyl benzidine and triphenylamine;
the second phosphor is: any one or a mixture of more than two of 4,4' -dihydroxybiphenyl, N, N, N ', N ' -tetramethyl-1, 4-phenylenediamine and 2, 6-diphenylphenol.
2. The method of claim 1, wherein the epoxy matrix is any one of 2, 2-bis- (4-glycidoxybenzene) propane and bisphenol a epoxy resin having a number average molecular weight of less than 2000.
3. The method for preparing the phosphorescent polymer material according to claim 1, wherein the specific process of the method comprises the following steps: under the action of protective atmosphere, the first phosphor is doped into the epoxy matrix according to a certain proportion and stirred uniformly, then the curing agent is added according to a certain proportion and stirred until the mixture is transparent, and the final phosphorescent polymer material is obtained after curing.
4. The method for preparing the phosphorescent polymer material according to claim 1, wherein the specific process of the method comprises the following steps: and dissolving the second phosphor in the liquid curing agent in proportion, uniformly stirring, mixing with the epoxy matrix, stirring until the mixture is transparent, and curing to obtain the final phosphorescent polymer material.
5. The method of claim 3 or 4, wherein the curing agent is any one of polyamine and tertiary amine.
6. The method of claim 3 or 4, wherein the molar ratio of phosphorescent small molecules of the first phosphor or the second phosphor to epoxy groups in the epoxy matrix is 1: 10-1000, wherein the molar ratio of the curing agent to the epoxy group in the epoxy matrix is 1: 1 to 8.
7. The method of claim 3 or 4, wherein the curing temperature is 25 ℃ to 140 ℃ and the curing time is 12 to 48 hours.
8. A phosphorescent polymer material, wherein the phosphorescent polymer material is prepared by the preparation method according to any one of claims 1 to 7;
the absolute phosphorescence quantum yield of the phosphorescence polymer material is more than 8.35%, and the phosphorescence service life of the phosphorescence polymer obtained by fitting according to a phosphorescence attenuation curve is 0.14-0.65 s; the visible phosphorescence visible to the naked eye can be maintained for more than three seconds at the temperature of 60 ℃.
9. Use of a phosphorescent polymer material, wherein the phosphorescent polymer material is prepared by the preparation method of any one of claims 1 to 7; the phosphorescent polymer material is applied as a room-temperature phosphorescent material, an anti-counterfeiting material or a biomedical imaging material.
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