CN113461908A - Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof - Google Patents
Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof Download PDFInfo
- Publication number
- CN113461908A CN113461908A CN202110667550.9A CN202110667550A CN113461908A CN 113461908 A CN113461908 A CN 113461908A CN 202110667550 A CN202110667550 A CN 202110667550A CN 113461908 A CN113461908 A CN 113461908A
- Authority
- CN
- China
- Prior art keywords
- room temperature
- dynamic covalent
- covalent bond
- triphenylamine derivative
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention discloses a room temperature phosphorescent material based on the synergistic effect of a dynamic covalent bond polymer (vitrimer) and a triphenylamine derivative and a preparation method thereof, and relates to the field of organic room temperature luminescent materials. The vibration and rotation of triphenylamine molecules are limited by a three-dimensional crosslinking network structure of a dynamic covalent bond, the pure organic room-temperature phosphorescence is achieved by avoiding contact quenching with oxygen, moisture and other environments, the phosphorescence afterglow time is controlled by modifying the three-dimensional crosslinking network and regulating and controlling triphenylamine derivatives, and the crosslinked polymer can be recycled and recycled in an environment-friendly manner due to the thermodynamic property of the dynamic covalent bond polymer. The composite material is simple to prepare, does not need complicated and tedious synthesis, is suitable for large-scale production and commercialization, can be applied and popularized in the fields of anti-counterfeiting, biological imaging and the like, and has a very large application prospect in actual life.
Description
Technical Field
The invention belongs to the field of photoluminescent materials, and relates to an organic long afterglow photoluminescent material applied to an anti-counterfeiting mark and a preparation method thereof.
Background
The luminescent material makes contribution to the daily life of human beings due to unique luminescent performance and superior practical characteristics, and the development of the luminescent material is concerned by related researchers. The room temperature phosphorescent material is one of a plurality of luminescent materials, has the advantages of stability, long service life and the like, can be used at room temperature, and can be widely applied to the fields of biosensing, cell imaging, photoelectricity and the like. However, most of the existing room temperature phosphorescent materials are inorganic materials, wherein most of the existing room temperature phosphorescent materials contain heavy metal ions or copper series elements and steel series elements, the heavy metal elements not only have toxicity and can harm human bodies, but also have very rare resources, high price and very limited source channels, and cannot meet the requirements of production and life, so that the development of novel room temperature phosphorescent materials has to be considered to meet the existing requirements. Therefore, the pure organic room temperature phosphorescent material is favored by the majority of researchers due to the advantages of good biocompatibility, easy adjustment of performance, wide raw material sources and the like. As an effective means, the room-temperature phosphorescence promoting effect of the dynamic covalent bond polymer on the designed triphenylamine derivative is utilized to realize effective warm phosphorescence emission, and the room-temperature phosphorescence effect of the polymer is adjusted by the inclusion effect of the phosphorescence groups in the polymer on the basis, so that the room-temperature phosphorescence material with more excellent phosphorescence emission effect and larger practical application potential is obtained.
Disclosure of Invention
Aiming at the problems, the invention aims at excavating a pure organic room-temperature phosphorescent material and a room-temperature phosphorescent system which can emit effective room-temperature phosphorescence, and provides a room-temperature phosphorescent material based on the synergistic effect of a dynamic covalent bond polymer and a triphenylamine derivative.
In the invention, a target polymer can be obtained through simple synthesis and preparation processes, and the triphenylamine derivative is introduced into the polymer through the interaction between the polymer and a host and a guest of a phosphorescent group in the polymer on the basis of the polymer, so that the phosphorescent light-emitting property and the light-emitting effect of the polymer are changed, and a more effective room-temperature phosphorescent material is obtained.
The invention provides a room temperature phosphorescent material of a dynamic covalent bond polymer, which is a room temperature phosphorescent material based on the synergistic effect of a dynamic covalent bond polymer and a triphenylamine derivative, and the room temperature phosphorescent material of the triphenylamine derivative-dynamic covalent bond polymer is a room temperature phosphorescent material formed by the coordination of triphenylamine derivative molecules doped into the dynamic covalent bond polymer and a polymerization catalyst TBD; wherein the triphenylamine derivative molecules comprise triphenylamine derivative TPA1-CZ, triphenylamine derivative TPA2-CZ, triphenylamine derivative 1 and triphenylamine derivative 2;
wherein the triphenylamine derivative TPA1-CZ/TAP2-CZ has the following structure:
the triphenylamine derivative 1 has the following structure:
the triphenylamine derivative 2 is a molecule formed by triphenylamine and aggregation-induced emission groups (AIEgenes), and has the following structure:
the triphenylamine derivative-dynamic covalent bond polymer room temperature phosphorescent material is a room temperature phosphorescent material formed by doping triphenylamine derivative molecules into a dynamic covalent bond polymer and collaboratively forming, wherein the dynamic covalent bond polymer (called as vitrimer) is a novel epoxy resin, and the minimum structural unit of the polymer is as follows:
the minimum structural unit of the dynamic covalent bond polymer molecule vitrimer.
In the structure of the triphenylamine derivative 1, R is selected from at least one of the following groups: cyano, carboxyl, amido, sulfonic, nitro, halogen (-Cl, -Br, -I), trihalomethyl (-CF)3，-CCl3) Dimethylamino group, tertiary amine positive ion (-N)+R3) TPA-CN molecules are formed when R is cyano (-CN).
Preferably, when R is cyano (-CN), TPA-CN molecules are formed.
Wherein, the AIE group (AIEgens) in the triphenylamine derivative 2 is selected from at least one of the following groups, wherein X ═ F/Cl/Br/I:
preferably, when R ═ AIEgen1(TPE), TPE-TPA molecules are formed.
Preferably, the structures of TPA2-CZ, TPA-CN and TPE-TPA are sequentially
TPA2-CZ, TPA-CN, TPE-TPA structure
The dynamic covalent bond polymer vitrimer is polymerized by monomer bisphenol A diglycidyl ether and adipic acid:
polymerization of monomer 1: bisphenol a type diglycidyl ether polymerization monomer 2: adipic acid
In the polymerization preparation process of the dynamic covalent bond polymer room temperature phosphorescent material, a polymerization catalyst used is 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, which is TBD for short.
Wherein the dynamic covalent bond polymer vitrimer has unique polymer network transition performance under the response of thermal stimulus. The performance is also embodied in the room temperature phosphorescent material of the dynamic covalent bond polymer formed by doping the triphenylamine derivative in the dynamic covalent bond polymer. The transesterification process for the polymer structure network is as follows:
the first purpose of the invention is to provide a room temperature phosphorescent thin film material of a dynamic covalent bond polymer, and further discloses a preparation method of the room temperature phosphorescent material with synergistic effect of the polymer and a triphenylamine derivative, and the technical purpose of the invention is realized by the following technology:
the preparation method of the triphenylamine derivative-dynamic covalent bond polymer vitrimer room temperature phosphorescent material comprises the following steps:
the method comprises the following steps: adding a certain amount of bisphenol A diglycidyl ether, adipic acid, TBD and triphenylamine molecules into a 4mL centrifuge tube;
step two: placing the centrifugal tube and the medicines therein in an oven at 60 ℃ for 4-6 minutes for later use;
step three: placing a glass culture dish in the heating sleeve as a reaction container, and placing a polytetrafluoroethylene film matched with the culture dish in the culture dish for placing reactants;
step four: transferring the reactant in the centrifugal tube to a polytetrafluoroethylene die pad, adjusting the temperature to 180 ℃, and carrying out polymerization reaction for 1.5-2.5 hours;
step five: uniformly stirring along with the rise of the reaction temperature until a little wire drawing condition occurs, and immediately taking part of the mixture and transferring the part of the mixture to a glass slide for sample preparation;
step six: placing a pre-polymerized sample in the middle of the two glass slides, and arranging 0.3mm gaskets on the periphery to prevent overflow;
step seven: placing the mixture in an oven at 160 ℃ for polymerization reaction for 1.5 to 2.5 hours;
step eight: and cooling to room temperature after polymerization is completed, and taking out the film after polymerization from the polytetrafluoroethylene template to obtain the TPE-TPA-vitrier room-temperature phosphorescent material.
Preferably, the stoichiometric ratio of bisphenol A diglycidyl ether, adipic acid and TBD in the preparation method is 1: 1: when the concentration is 0.1, the prepared phosphorescent film has the best optical and mechanical properties.
Preferably, the stoichiometric ratio of the polymerization catalyst TBD to the triphenylamine molecules is 100: 1, the resulting phosphorescent thin film material has the best phosphorescence efficiency after excitation.
Most preferably, the triphenylamine molecules are TPA2-CZ, TPA-CN and TPE-TPA molecules, and the phosphorescent thin film material has the best phosphorescent efficiency and phosphorescent service life.
The invention discloses a room temperature phosphorescence luminescent property of a room temperature phosphorescence material based on the synergistic effect of a polymer and a triphenylamine derivative:
the pure triphenylamine derivative molecules do not generate phosphorescence emission phenomenon after being excited at room temperature, and after the molecules are doped and introduced into the dynamic covalent bond polymer, the obtained doped polymer is the room-temperature phosphorescence material of the triphenylamine derivative-dynamic covalent bond polymer, and the material can generate effective room-temperature phosphorescence emission after being excited by light.
According to the preferred scheme, the invention discloses the room temperature phosphorescence characteristics of TPA2-CZ-vitrimer, TPA-CN-vitrimer and TPE-TPA-vitrimer room temperature phosphorescence materials;
the dynamic covalent bond polymer vitrimer has no room temperature phosphorescence emission after being excited by an ultraviolet light source, and TPA2-CZ-vitrimer, TPA-CN-vitrimer and TPE-TPA-vitrimer polymers obtained by introducing TPA2-CZ, TPA-CN and TPE-TPA can generate effective room temperature phosphorescence emission after being excited by the ultraviolet light source; in addition, the room-temperature phosphorescence emission effect of the polymer is changed by adjusting the concentrations of TPA-CZ, TPA-CN and TPE-TPA and the length of a monomer chain segment of the polymer, so that the purpose of adjusting the luminescence effect of the polymer is achieved.
Considering the relation between the luminous intensity of the room-temperature phosphorescent film and the concentration of phosphorescent molecules and the aggregation quenching effect of the phosphorescent molecules comprehensively, the weight ratio of the phosphorescent molecule triphenylamine derivative in the film material is as follows: 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.5%, 0.75%, 1%, 2%, 5%, 10%.
Preferably, the weight ratio of the triphenylamine derivative of the phosphorescent molecule to the film material is between 0.2% and 1%.
Finally, the invention discloses a room temperature phosphorescent material based on a polymer and a triphenylamine derivative and application of a preparation method thereof in daily production and life.
The invention relates to a pure organic room temperature phosphorescence emission technology, which further promotes intersystem crossing of phosphorescence group excited state electrons from a singlet state to a triplet state and limits non-radiation relaxation of phosphorescence group by the limiting effect of the polymer on TPA2-CZ, TPA-CN and TPE-TPA on the basis of the polymer, thereby realizing effective room temperature phosphorescence emission.
The polymer obtained after introducing the triphenylamine derivatives TPA2-CZ, TPA-CN and TPE-TPA can emit room temperature phosphorescence with different service lives and quantum yields, so that the introduction of the triphenylamine derivatives TPA2-CZ, TPA-CN and TPE-TPA can be said to adjust the room temperature phosphorescence effect of the polymer. The method has the advantages of simple synthesis of the related polymer, wide raw material source and low cost, and the preparation process of the composite material of the polymer and the triphenylamine derivatives TPA2-CZ, TPA-CN and TPE-TPA is very easy, so the method is hopeful to be used for large-scale production quantification in factories, and lays a solid foundation for the application of the room temperature phosphorescent material in actual production life.
Advantageous effects
The phosphorescent thin film material generates room temperature phosphorescence under the excitation of an ultraviolet lamp and has long-life afterglow. Different triphenylamine derivative molecules are applied in the dynamic covalent polymer, so that the persistence time of the film phosphorescence can be differentiated, and the film phosphorescence can have the anti-counterfeiting marking capability. And the material has the characteristics of green recovery and cyclic utilization. The preparation method designed by the invention is simple, the raw material source is wide, the price is low, and the preparation process of the composite material of the polymer and the triphenylamine derivatives TPA2-CZ, TPA-CN and TPE-TPA is very easy, so that the preparation method is hopeful to be applied to large-scale production quantification of factories, and a solid foundation is laid for the application of the room temperature phosphorescent material in actual production life.
Drawings
FIG. 1 is a normalized ultraviolet absorption spectrum and photoluminescence spectrum of a methylene chloride solution of TPA 2-CZ.
FIG. 2 is a normalized combination of the photoluminescence and phosphorescence spectra of TPA2-CZ-vitrimer in the solid state.
FIG. 3 is a graph of the lifetime of TPA2-CZ-vitrimer at 365 nm.
FIG. 4 is a graph of UV absorption spectra and photoluminescence spectra of a TPA-CN methylene chloride solution normalized to a combined spectrum.
FIG. 5 is a graph of a TPA-CN-vitrimer normalized to its photoluminescence and phosphorescence spectra in the solid state.
FIG. 6 is a graph of the lifetime of TPA-CN-vitrimer at 365 nm.
FIG. 7 is a graph of UV absorption spectra and photoluminescence spectra of TPE-TPA in methylene chloride normalized to a standard value.
FIG. 8 is a combined spectrum of TPE-TPA-vitrimer normalized to the photoluminescence and phosphorescence spectra in the solid state.
FIG. 9 is a graph of the lifetime of TPE-TPA-vitrimer at 365 nm.
FIG. 10 is an anti-counterfeiting application of a phosphorescent dynamic covalent polymer vitrimer material.
FIG. 11 is a graphical representation of the shape memory properties and reworkability of a dynamically covalently bonded polymeric film.
Detailed Description
The properties and applications of the room temperature phosphorescent material according to the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited to the following examples. The specific details are set forth in the preferred embodiments of the invention. The starting materials used in the present invention are commercially available or commercially ordered and are described herein.
Example 1
Preparation method of TPA2-CZ-vitrimer (dynamic covalent polymer) room temperature phosphorescent material
Bisphenol A diglycidyl ether (1mmol, 0.34g), adipic acid (1mmol, 0.146g), TBD (0.01mmol, 0.014g) and TPA-CZ (the stoichiometric ratio of TBD to TPA-CZ is 100: 1) were placed in a 4mL centrifuge tube in an oven at 60 ℃ for 5 minutes for use, a glass petri dish was placed in a heating mantle as a reaction vessel, and a polytetrafluoroethylene film fitted to the petri dish was placed in the petri dish for holding the reactants to prevent the polymer from sticking to the glassware. And transferring the reactant in the centrifugal tube to a polytetrafluoroethylene film, adjusting the temperature to 180 ℃, uniformly stirring along with the temperature rise until a little wire drawing condition occurs, immediately taking part of the reactant, transferring the part of the reactant to a glass slide for sample preparation, and researching the optical performance of the sample. The pre-polymerized sample is placed in the middle of the two glass slides, and 0.3mm gaskets are additionally arranged on the periphery of the two glass slides to prevent overflow. The sample was held at both ends by a jig and placed in an oven at 160 ℃ for polymerization for two hours. After the polymerization was completed, the reaction mixture was taken out and cooled to room temperature. The TPA 2-CZ-vitrier room temperature phosphorescent material can be obtained.
Example 2
Preparation method of TPA-CN-vitrimer room temperature phosphorescent material
Bisphenol A diglycidyl ether (1mmol, 0.34g), adipic acid (1mmol, 0.146g), TBD (0.01mmol, 0.014g) and TPA-CN (the stoichiometric ratio of TBD to TPA-CN is 100: 1) were placed in a 4mL centrifuge tube in an oven at 60 ℃ for 5 minutes, a glass petri dish was placed in a heating mantle as a reaction vessel, and a polytetrafluoroethylene film fitted to the petri dish was placed in the petri dish for holding the reactants to prevent the polymer from adhering to the glassware. And transferring the reactant in the centrifugal tube to a polytetrafluoroethylene film, adjusting the temperature to 180 ℃, uniformly stirring along with the temperature rise until a little wire drawing condition occurs, immediately taking part of the reactant, transferring the part of the reactant to a glass slide for sample preparation, and researching the optical performance of the sample. The pre-polymerized sample is placed in the middle of the two glass slides, and 0.3mm gaskets are additionally arranged on the periphery of the two glass slides to prevent overflow. The sample was held at both ends by a jig and placed in an oven at 160 ℃ for polymerization for two hours. After the polymerization was completed, the reaction mixture was taken out and cooled to room temperature. The TPA-CN-vitrimer room temperature phosphorescent material can be obtained.
Example 3
Preparation method of TPE-TPA-vitrimer room temperature phosphorescent material
Bisphenol A diglycidyl ether (1mmol, 0.34g), adipic acid (1mmol, 0.146g), TBD (0.01mmol, 0.014g) and TPE-TPA (the stoichiometric ratio of TBD to TPE-TPA is 100: 1) are placed in a 4mL centrifuge tube in an oven at 60 ℃ for 5 minutes for standby, a glass culture dish is placed in a heating jacket as a reaction container, and a polytetrafluoroethylene film matched with the culture dish is placed in the culture dish for placing reactants to prevent the polymer from being adhered to the glass culture dish. And transferring the reactant in the centrifugal tube to a polytetrafluoroethylene film, adjusting the temperature to 180 ℃, uniformly stirring along with the temperature rise until a little wire drawing condition occurs, immediately taking part of the reactant, transferring the part of the reactant to a glass slide for sample preparation, and researching the optical performance of the sample. The pre-polymerized sample is placed in the middle of the two glass slides, and 0.3mm gaskets are additionally arranged on the periphery of the two glass slides to prevent overflow. The sample was held at both ends by a jig and placed in an oven at 160 ℃ for polymerization for two hours. After the polymerization was completed, the reaction mixture was taken out and cooled to room temperature. So as to obtain the TPE-TPA-vitrier room temperature phosphorescent material.
FIG. 1 is a combined spectrum of TPA2-CZ solution after normalization of ultraviolet absorption spectrum and photoluminescence spectrum.
The spectrum specifically illustrates that the ultraviolet absorption characteristic peaks of the molecular TPA-CZ in the solution environment are two and are respectively positioned at 300nm and 358nm, the photoluminescence spectrum is obtained by taking 365nm as the excitation wavelength, and the photoluminescence spectrum has an obvious emission peak near 429 nm.
FIG. 2 is a normalized combination of the photoluminescence and phosphorescence spectra of TPA2-CZ-vitrimer in the solid state.
The spectrum is specifically illustrated as follows: the TPA-CZ-vitrimer was excited at 365nm as the excitation wavelength to obtain the photoluminescence spectrum and the phosphorescence spectrum in the figure. There is a distinct emission peak in the photoluminescence spectrum, around 417nm, in addition, a very distinct emission peak is seen in the TPA-CZ-vitrimer phosphor spectrum, around 518 nm. The Stokes shift is 104 nm. Namely, the TPA-CZ-vitrimer has phosphorescence in the light emitted after being excited by a light source at room temperature.
FIG. 3 is a graph of the lifetime of TPA2-CZ-vitrimer at 365 nm.
The spectrum is specifically illustrated as follows: as can be seen from the lifetime spectrum of the TPA-CZ-vitrimer, the phosphorescence lifetime of the TPA-CZ-vitrimer can reach 1052 ms.
FIG. 4 is a normalized integrated spectrum of the UV absorption spectrum and photoluminescence spectrum of the TPA-CN solution.
The spectrum is specifically illustrated as follows: the ultraviolet absorption characteristic peaks of the molecular TPA-CN in the solution environment are two and are respectively positioned at 298nm and 360nm, the photoluminescence spectrum is obtained by taking 365nm as the excitation wavelength, and the photoluminescence spectrum has an obvious emission peak near 474 nm.
FIG. 5 is a graph of a TPA-CN-vitrimer normalized to its photoluminescence and phosphorescence spectra in the solid state.
The spectrum is specifically illustrated as follows: the excitation of the TPA-CN-vitrimer with 365nm as the excitation wavelength gave the photoluminescence and phosphorescence spectra in the figure. There is a distinct emission peak in the photoluminescence spectrum, near 431 nm. furthermore, a very distinct emission peak is seen in the TPA-CN-vitrimer phosphorescence spectrum, near 521 nm. The Stokes shift is 90 nm. Namely, the TPA-CN-vitrimer has phosphorescence in the light emitted after being excited by the light source under the room temperature condition.
FIG. 6 is a graph of the lifetime of TPA-CN-vitrimer at 365 nm.
The spectrum is specifically illustrated as follows: as can be seen from the life spectra of the TPA-CZ-vitrimer, the phosphorescence life of the TPA-CZ-vitrimer can reach 940.51 ms.
FIG. 7 is a combined spectrum of TPE-TPA solution normalized by the UV absorption spectrum and photoluminescence spectrum.
The spectrum is specifically illustrated as follows: according to the excitation spectrum of TPE-TPA in the figure, only one ultraviolet absorption characteristic peak of molecule TPE-TPA in the solution environment is shown and is positioned at 300nm, the photoluminescence spectrum is obtained by taking 365nm as the excitation wavelength, and the photoluminescence spectrum has an obvious emission peak near 405 nm.
FIG. 8 is a combined spectrum of TPE-TPA-vitrimer normalized to the photoluminescence and phosphorescence spectra in the solid state.
The spectrum is specifically illustrated as follows: the TPE-TPA-vitrimer was excited with 365nm as the excitation wavelength to obtain the photoluminescence spectrum and the phosphorescence spectrum in the figure. There is a distinct emission peak in the photoluminescence spectrum, around 397nm, in addition, a very distinct emission peak is seen in the TPE-TPA-vitrimer phosphor spectrum, around 518 nm. The Stokes shift is 121 nm. Namely, the TPE-TPA-vitrimer has phosphorescence in the light emitted after being excited by the light source at room temperature.
FIG. 9 is a graph of the lifetime of TPE-TPA-vitrimer at 365 nm.
The spectrum is specifically illustrated as follows: as can be seen from the life spectra of the TPE-TPA-vitrimer, the phosphorescence life of the TPE-TPA-vitrimer can reach 778.61 ms.
FIG. 10 illustrates an anti-counterfeiting application of a phosphorescent dynamic covalent bond polymer material.
The figure is specifically illustrated as follows: different triphenylamine derivative molecules are applied in the dynamic covalent polymer, so that the persistence time of the thin film phosphor can be differentiated. As shown in the figure: the triphenylamine derivative-doped dynamic covalent bond polymer film is designed into a character of USTB, and under the excitation of an ultraviolet lamp, all the films in the shape of letters generate bright fluorescence; the phosphorescence intensity of the letter "US" is visually distinguished from that of the letter "TB" 5 seconds after the ultraviolet lamp is turned off, and only the letter "US" has phosphorescence and luminescence 8 seconds after the ultraviolet lamp is turned off, so that the letter "US" in the letter "USTB" can be considered to be specially marked, and the anti-counterfeiting effect is achieved.
Test example 1: recoverable and shape memory performance test of dynamic covalent bond polymer film
The TPA2-CZ-vitrimer dynamic covalent bond polymer film of example 1 was fabricated into a rectangular dynamic covalent bond polymer film by changing the mold cured in the fabrication process according to the fabrication method of example 1, as shown in FIG. 11.
After obtaining the rectangular film, testing the shape memory performance: as shown in fig. 11, after the rectangular film is folded at 90 ° in the middle by an external force at 80 ℃, the film is cooled and solidified, the folded shape of the film is maintained, and the film returns to a rectangular shape after being reheated to 80 ℃. And can be remolded by hot pressing after being broken due to its thermoplasticity at high temperature. Has excellent repeated processing capability.
The excellent mechanical property can expand the application range of the recyclable room temperature phosphorescent material based on the dynamic covalent bond polymer.
Claims (9)
1. A room temperature phosphorescent material of a dynamic covalent bond polymer is a room temperature phosphorescent material based on the synergistic effect of the dynamic covalent bond polymer and a triphenylamine derivative, and is characterized in that: the triphenylamine derivative-dynamic covalent bond polymer room temperature phosphorescent material is a room temperature phosphorescent material formed by doping triphenylamine derivative molecules into a dynamic covalent bond polymer and collaboratively forming; wherein the triphenylamine derivative molecules comprise triphenylamine derivative TPA1-CZ, triphenylamine derivative TPA2-CZ, triphenylamine derivative 1 and triphenylamine derivative 2; the structure of the phosphorescent molecule triphenylamine derivative TPA1-CZ/TAP2-CZ in the phosphorescent material is as follows:
the triphenylamine derivative 1 has the following structure:
the triphenylamine derivative 2 has the following structure:
the dynamic covalent bond polymer is called vitrimer, and is a novel epoxy resin, and the minimum structural unit of the dynamic covalent bond polymer is as follows:
2. the room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 1, wherein said triphenylamine derivative 1 has a structure wherein R is selected from at least one of the following groups: cyano, carboxyl, amido, sulfonic, nitro, halogen (-Cl, -Br, -I), trihalomethyl (-CF)3，-CCl3) Dimethylamino group, tertiary amine positive ion (-N)+R3) TPA-CN molecules are formed when R is cyano (-CN).
3. The room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 1, wherein the triphenylamine derivative 2 has a structure in which the AIE group (AIEgens) is selected from at least one of the following groups, wherein X ═ F/Cl/Br/I, and when R is AIEgen1(TPE), TPE-TPA molecules are formed:
4. the room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 1, wherein: wherein the dynamic covalent bond polymer is formed by polymerizing the following monomers, and the monomer structure is as follows:
5. the room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 1, wherein: in the preparation process of the dynamic covalent bond polymer room temperature phosphorescent material, a polymerization catalyst used is 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, which is TBD for short.
6. The method for preparing the room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 1, wherein the triphenylamine derivative-room temperature phosphorescent polymer material with dynamic covalent bonds is prepared by the following steps:
the method comprises the following steps: adding a certain amount of bisphenol A diglycidyl ether, adipic acid, TBD and triphenylamine molecules into a centrifugal tube;
step two: placing the centrifugal tube and the medicines therein in an oven at 60 ℃ for 4-6 minutes for later use;
step three: placing a glass culture dish in the heating sleeve as a reaction container, and placing a polytetrafluoroethylene film matched with the culture dish in the culture dish for placing reactants;
step four: transferring the reactant in the centrifugal tube to a polytetrafluoroethylene die pad, adjusting the temperature to 180 ℃, and carrying out polymerization reaction for 1.5-2.5 hours;
step five: uniformly stirring along with the rise of the reaction temperature until a little wire drawing condition occurs, and immediately taking part of the mixture and transferring the part of the mixture to a glass slide for sample preparation;
step six: placing a pre-polymerized sample in the middle of two glass slides, and installing gaskets on the periphery of the glass slides to prevent overflow;
step seven: placing the mixture in an oven at 160 ℃ for polymerization reaction for 1.5 to 2.5 hours;
step eight: and cooling to room temperature after polymerization is finished, and taking out the film after polymerization from the polytetrafluoroethylene template to obtain the triphenylamine derivative-dynamic covalent bond polymer room temperature phosphorescent material.
7. The method for preparing triphenylamine derivative-dynamic covalent bond polymer according to claim 6, wherein: step one, the stoichiometric ratio of the bisphenol A diglycidyl ether, adipic acid and TBD is 1: 1: 0.1.
8. the method for preparing the room temperature phosphorescent polymer material with dynamic covalent bonds as claimed in claim 6, wherein the method comprises the following steps: step one, the stoichiometric ratio of the TBD to the triphenylamine molecules is 100: 1.
9. the use of the room temperature phosphorescent material with a dynamic covalent bond polymer as claimed in claim 1, wherein the room temperature phosphorescent material is used in the fields of photoluminescence materials and anti-counterfeiting, marking and lighting daily life.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667550.9A CN113461908B (en) | 2021-06-16 | 2021-06-16 | Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667550.9A CN113461908B (en) | 2021-06-16 | 2021-06-16 | Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113461908A true CN113461908A (en) | 2021-10-01 |
| CN113461908B CN113461908B (en) | 2022-04-15 |
Family
ID=77870060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110667550.9A Active CN113461908B (en) | 2021-06-16 | 2021-06-16 | Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461908B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115433343A (en) * | 2022-08-12 | 2022-12-06 | 深圳先进电子材料国际创新研究院 | Epoxy resin based ultra-long organic room temperature phosphorescent material and preparation method and application thereof |
| WO2023242041A1 (en) * | 2022-06-13 | 2023-12-21 | Universiteit Gent | Method for preparing an epoxy-derived covalent adaptable network |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306034A (en) * | 2018-03-16 | 2019-02-05 | 华东理工大学 | A kind of preparation method of pure organic long-life room temperature phosphorimetry polymer material of no heavy atom amorphous state |
| CN110407710A (en) * | 2018-04-28 | 2019-11-05 | 香港科技大学深圳研究院 | A kind of pure organic room temperature phosphorimetry material of triphenylamine derivative class and preparation method thereof |
| CN111393692A (en) * | 2020-03-22 | 2020-07-10 | 北京化工大学 | Rapid and mild preparation method of covalent bonding room temperature phosphorescent film |
| CN112646571A (en) * | 2020-11-24 | 2021-04-13 | 华南理工大学 | Organic room temperature phosphorescent doped material and preparation method and application thereof |
-
2021
- 2021-06-16 CN CN202110667550.9A patent/CN113461908B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306034A (en) * | 2018-03-16 | 2019-02-05 | 华东理工大学 | A kind of preparation method of pure organic long-life room temperature phosphorimetry polymer material of no heavy atom amorphous state |
| CN110407710A (en) * | 2018-04-28 | 2019-11-05 | 香港科技大学深圳研究院 | A kind of pure organic room temperature phosphorimetry material of triphenylamine derivative class and preparation method thereof |
| CN111393692A (en) * | 2020-03-22 | 2020-07-10 | 北京化工大学 | Rapid and mild preparation method of covalent bonding room temperature phosphorescent film |
| CN112646571A (en) * | 2020-11-24 | 2021-04-13 | 华南理工大学 | Organic room temperature phosphorescent doped material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEIDONG QIU ET AL.: ""Achieving Purely Organic Room-Temperature Phosphorescence Mediated by a Host− Guest Charge Transfer State"", 《J. PHYS. CHEM. LETT.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115161014B (en) * | 2022-06-09 | 2023-04-07 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| WO2023242041A1 (en) * | 2022-06-13 | 2023-12-21 | Universiteit Gent | Method for preparing an epoxy-derived covalent adaptable network |
| CN115433343A (en) * | 2022-08-12 | 2022-12-06 | 深圳先进电子材料国际创新研究院 | Epoxy resin based ultra-long organic room temperature phosphorescent material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113461908B (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113461908B (en) | Dynamic covalent bond polymer room temperature phosphorescent material and preparation method thereof | |
| Li et al. | Bright tricolor ultrabroad-band emission carbon dots for white light-emitting diodes with a 96.5 high color rendering index | |
| CN110079301A (en) | A kind of organic long-afterglow material and its preparation method and application | |
| CN109439322B (en) | Preparation method of carbon-containing photo-induced yellow light-emitting crystal and application of carbon-containing photo-induced yellow light-emitting crystal in white light LED | |
| CN113652227B (en) | Room-temperature phosphorescent polymer based on polyvinyl alcohol doping and preparation method and application thereof | |
| Wang et al. | Highly stretchable and stretch-induced fluorescence chromism self-healing materials based on boroxine and dynamic imine bond | |
| Zhang et al. | Aggregation-induced white emission of lanthanide metallopolymer and its coating on cellulose nanopaper for white-light softening | |
| CN111961461A (en) | Phosphorescent material, phosphorescent film, and preparation method and application thereof | |
| Liu et al. | Ultralong lifetime room temperature phosphorescence and dual-band waveguide behavior of phosphoramidic acid oligomers | |
| CN104497851A (en) | Ultraviolet cured rare earth polymer material and preparation method thereof | |
| CN105567226B (en) | Polysiloxanes functionalized carbon point and its preparation method and application | |
| CN113045978B (en) | Preparation method of carbon quantum dot-water-soluble polyurethane solution | |
| CN111848927B (en) | Phosphorescent polymer material and preparation method and application thereof | |
| CN113462383A (en) | Room-temperature phosphorescent material based on cellulose and preparation method and application thereof | |
| CN107629184B (en) | R-binaphthol polyurethane, preparation method and application | |
| CN107629182B (en) | A kind of polysiloxanes-benzoxazinyl- light-emitting film and its application on UV-LED lamp | |
| CN115678243A (en) | Polymer phosphorescent material with high quantum yield and long phosphorescent service life and preparation method thereof | |
| CN113072800B (en) | Preparation method of stretchable fluorescent photochromic material | |
| CN113861910B (en) | Preparation method of fluorescent powder-free recyclable epoxy adhesive for white light LED packaging | |
| CN117143278A (en) | Multi-component tunable polymer long afterglow luminescent material and application thereof | |
| CN115197162B (en) | Light activated organic long afterglow material and preparation method and application thereof | |
| CN116621878A (en) | Phosphor, long-life room-temperature phosphorescent material for light-driven phosphorescent growth and application | |
| CN114316945B (en) | Luminescent material and preparation method and application thereof | |
| CN113024752B (en) | Preparation method and application of pure organic undoped polymer room temperature phosphorescent material | |
| CN116284539A (en) | Intrinsic long-life organic room temperature phosphorescent material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |