An intrinsically dynamic color-adjustable cyclic olefin copolymer long-lasting glow material and its application

Abstract

The present invention discloses an intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material and its application, wherein the material comprises a cyclic olefin copolymer of any one of the following structural formulas: wherein: R 1、 R2, R3, and R4 are substituents, R5 is a chromophore, and a, b, c, d, and e represent the degree of polymerization. This material exhibits excellent processing properties, enabling the fabrication of complex-shaped light-emitting devices. Its long-lasting emission color is adjustable across the entire visible light range, exhibiting stable long-lasting emission in aqueous, acidic, alkaline, and high-temperature environments. It has applications in anti-counterfeiting, encryption, imaging, lighting, and detection.

Description

Technical Field

[0001] The invention relates to an intrinsic type dynamically color-adjustable cycloolefin copolymer long-afterglow material and application thereof, belonging to the technical field of long-afterglow materials. Background Art

[0002] Intrinsic dynamic color tunability refers to the ability of a material to change color under different conditions without the need for external physical or chemical treatment. This property is particularly important in long-lasting luminescence materials, allowing them to adjust their emission color based on environmental changes or other intrinsic factors after the excitation source is removed. In-depth research on intrinsically dynamic color tunable long-lasting luminescence materials holds broad application prospects in optoelectronics, biochemical sensing, anti-counterfeiting, and other fields. Related research has also reported a dynamically tunable, pure organic long-lasting luminescence material synthesized via a nucleophilic reaction. This material exhibits color tunability under different conditions and has potential applications in data encryption. For example, CN110093151A discloses a color-tunable organic long-lasting luminescence material, its preparation method, and its application. By varying the ratio of 1,8-dicarboxylic acid and NH₅COOH, this material can achieve fluorescence color changes from milky white to blue, and from yellow to green, at room temperature and in atmospheric conditions. However, in aqueous environments or at high temperatures, the luminescence stability is less than ideal and is susceptible to quenching.

[0003] Polymer-based long-lasting glow materials offer low biotoxicity, environmental friendliness, excellent processability, and variable and tunable luminescence properties. They are widely used in imaging, lighting, road signs, architectural decoration, information anti-counterfeiting, encryption, and safety and emergency warning systems. In recent years, these materials have attracted widespread attention from researchers both domestically and internationally. However, common polymer long-lasting glow materials exhibit unstable luminescence in aqueous environments or at high temperatures, and are prone to quenching. For example, CN110093151A discloses the use of cycloolefin polymers in long-lasting glow materials. The material preparation method comprises: adding an organic solvent to a reaction flask, followed by the addition of a phosphor and a cycloolefin polymer matrix; after complete dissolution at room temperature, the solution is spin-coated onto a quartz wafer; and the temperature is maintained at 30-80°C for 1-2 hours until the solvent evaporates completely, resulting in a long-lasting glow polymer film. This material is a blend of the cycloolefin polymer matrix and the phosphor. The cycloolefin polymer is a continuous phase, imparting processability and water resistance to the material; the phosphor is a dispersed phase, imparting long-lasting luminescence properties to the material. While the long-lasting glow material designed by this invention can ensure that phosphorescence emission is not quenched by water, it is still susceptible to quenching at high temperatures. Furthermore, the stability of polymer-based long-lasting glow materials prepared by physical doping is relatively poor, and the phosphor is prone to migration, resulting in a significant decrease in long-lasting glow luminescence performance. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide an intrinsically dynamic, color-adjustable cyclic olefin copolymer long-afterglow material and its application. By rationally designing the structure, the present invention solves the technical problems of the existing polymer-based long-afterglow materials being prone to water quenching and thermal quenching and having poor stability.

[0005] Furthermore, the present invention also provides applications of the material.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] An intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material, characterized by comprising any one of the following general structural formulas:

[0008]

[0009] Where: R 1、 R2, R3 and R4 are substituents, R5 is a chromophore, and a, b, c, d and e are the degrees of polymerization.

[0010] The R 1、 When R2, R3 and R4 are aliphatic groups, they include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or adamantyl.

[0011] The structural formula is as follows:

[0012]

[0013] The R 1、When R2, R3 and R4 are aromatic groups, they are: phenyl, naphthyl, anthracenyl, indenyl, fluorenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,6-dibromophenyl, 3,5-dibromophenyl, 2,4,6-tribromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,6-diiodophenyl, 3,5-diiodophenyl, 2,4,6-triiodophenyl, 2-fluorophenyl, 3-fluorophenyl phenyl, 4-fluorophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, 2,3,4,5,6,-pentafluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2,6-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2,6-di-tert-butylphenyl phenyl, 3,5-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, 2,6-diphenylphenyl, 3,5-diphenylphenyl, 2,4,6-triphenylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2,6-ditrifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 2,4,6-tris(trifluoromethyl)phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2,6-dinitrophenyl, 3,5-dinitrophenyl, 2,4,6-trinitrophenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,6-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-(3,5-dimethylphenyl)phenyl, 2,6-bis(3,5-dimethylphenyl)phenyl, 2-(3,5-ditrifluoromethylphenyl)phenyl, 2,6-bis(3,5-ditrifluoromethylphenyl)phenyl, 2-(3,5-dimethoxyphenyl)phenyl, 2,6-bis(3,5-dimethoxyphenyl)phenyl, 2-(3,5-diphenylphenyl)phenyl or 2,6-bis(3,5-diphenylphenyl)phenyl.

[0014] The structural formula is as follows:

[0015]

[0016] or

[0017]

[0018] or

[0019]

[0020] or

[0021]

[0022] Furthermore, the chromophore R5 is any one of the following structural formulas:

[0023]

[0024] or

[0025]

[0026] Among them: R6, R7, R8, R9, R 10 and R 11 A, A1 and A2 are one of atoms such as N, P, S and O.

[0027] R6, R7, R8, R9, R 10 and R 11 When it is an aliphatic group, it includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hydroxy, 1-hydroxymethyl, 1-hydroxyethyl, 1-hydroxyn-propyl, 1-hydroxyisopropyl, amino, 1-aminomethyl, 1-aminoethyl, 1-aminon-propyl, 1-aminoisopropyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, formate, acetate, propionate, n-butyrate, isobutyrate, methyl formate, methyl acetate, methyl propionate, n-butyrate Methyl group, methyl isobutyrate group, formaldehyde group, acetaldehyde group, propionaldehyde group, n-butyraldehyde group, isobutyraldehyde group, formonitrile group, acetonitrile group, propionitrile group, butyronitrile group, isobutyronitrile group, boronic acid group, fluoro group, 1-fluoromethyl group, 1-fluoroethyl group, 1-fluoro-n-propyl group, 1-fluoroisopropyl group, chloro group, 1-chloromethyl group, 1-chloroethyl group, 1-chloro-n-propyl group, 1-chloroisopropyl group, bromo group, 1-bromomethyl group, 1-bromoethyl group, 1-bromo-n-propyl group, 1-bromoisopropyl group, iodo group, 1-iodomethyl group, 1-iodoethyl group, 1-iodo-n-propyl group, 1-iodoisopropyl group, trifluoro group, trifluoromethyl group, trifluoroethyl group, trifluoro-n-propyl group, trifluoroisopropyl group.

[0028] The structural formula is as follows:

[0029] or

[0030] or

[0031]

[0032] R6, R7, R8, R9, R 10 and R 11When it is an aromatic group, it includes phenyl, naphthyl, anthracenyl, pyrenyl, benzyl, benzyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, 2,6-diphenylphenyl, 3,5-diphenylphenyl, 2,4,6-triphenylphenyl, 2-(3,5-dimethylphenyl)phenyl, 2,6-bis(3,5-dimethylphenyl)phenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2,6-diaminophenyl, 3,5-diaminophenyl, 2,4,6-triaminophenyl, 2-(aminophenyl)phenyl, 3-(aminophenyl)phenyl, 4-(aminophenyl)phenyl, 2-(diphenylamino)phenyl, 3-(diphenylamino)phenyl, 4-(diphenylamino)phenyl, 3-([1,1'-biphenyl]-4- phenyl, 3-([1,1'-biphenyl]-4-amino)phenyl, 3-(N-phenyl-[1,1'-biphenyl]-4-amino)phenyl, 3-(di[1,1'-biphenyl]-4-amino)phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2,6-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-tert-butylphenyl, 3- tert-Butylphenyl, 4-tert-butylphenyl, 2,6-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,6-dibromophenyl, 3,5-dibromophenyl, 2,4,6-tribromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,6-diiodophenyl, 3,5-diiodophenyl, 2,4,6-triiodophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, 2 ,4,6-trifluorophenyl, 2,3,4,5,6,-pentafluorophenyl, 2-nitrilephenyl, 3-nitrilephenyl, 4-nitrilephenyl, 2,6-dinitrilephenyl, 3,5-dinitrilephenyl, 2,4,6-trinitrilephenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2,6-ditrifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 2,4,6-tris(trifluoromethyl)phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2,6-dinitrophenyl, 3,5-dinitrophenyl, 2,4,6-trinitrophenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,6-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 2,6-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4,6-tricarboxyphenyl.

[0033] The structural formula is as follows:

[0034]

[0035] or

[0036]

[0037] or

[0038]

[0039] or

[0040]

[0041] or

[0042]

[0043] The polymerization degrees a, b, c and d are all 0-10000, and a, b, c and d are not all 0 at the same time; e is 10-10000;

[0044] The molecular weight of the intrinsic dynamically color-adjustable cycloolefin copolymer long-afterglow material is 10,000-1,000,000.

[0045] The molar fraction of the ester-containing cyclic structure in the intrinsic dynamically color-adjustable cyclic olefin copolymer long-lasting glow material is 0 mol% (not included) to 100 mol% (not included).

[0046] The molar fraction of the chromophore-containing cyclic structural unit in the intrinsic type dynamically color-adjustable cyclic olefin copolymer long-lasting glow material is 1 mol% (inclusive) to 100 mol% (exclusive).

[0047] The present invention also provides a method for preparing an intrinsic type dynamically color-adjustable cycloolefin copolymer long-afterglow material, comprising the following steps:

[0048] Add the required amounts of an organic solvent, an ester-containing cycloolefin monomer, a chromophore-containing cycloolefin monomer, and a catalyst to a polymerization bottle. After polymerization for 2-10 hours, add a precipitant to obtain a long-lasting glow material. The molar ratio of the ester-containing cycloolefin monomer, the chromophore-containing cycloolefin monomer, and the catalyst is 1-100:1000:0.1-10. The ratio of the solvent to the monomers (including the ester-containing cycloolefin monomer and the chromophore-containing cycloolefin monomer) is 1-100 mL:1 g.

[0049] The organic solvent is one or a mixture of water, methanol, ethanol, acetone, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, N,N-dimethylformamide, and dimethyl sulfoxide;

[0050] The catalyst is one or a mixture of organic compounds or organic complexes with a metal center of ruthenium, molybdenum, tungsten, nickel, palladium, iron, cobalt, rhodium, copper, gold, platinum, titanium, zirconium, hafnium, aluminum, zinc, magnesium, boron, etc.;

[0051] The present invention also discloses the application of the intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material. The intrinsic type cyclic olefin copolymer long afterglow material obtained by the above preparation method is applied to lighting, imaging, road marking and warning, product anti-counterfeiting, information encryption, biological identification, and sensing.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] 1. The long-lasting glow material of the present invention is a polymer with a cyclic main chain structure, flexibly controllable side groups, and rich in ester groups. This effectively improves the luminescence lifetime, environmental tolerance, and thermal quenching resistance of the long-lasting glow material. Furthermore, by copolymerizing with various chromophore-containing cycloolefin monomers, the material is endowed with long-lasting luminescence properties covering the entire color range, enabling the material to maintain excellent long-lasting luminescence performance in high temperature, water, high humidity, acidic, or alkaline environments. Measurements have shown that the afterglow duration of the long-lasting glow material of the present invention is similar in air, water, acidic solutions, and alkaline solutions, demonstrating its excellent environmental tolerance. The material also maintains its long-lasting luminescence properties at temperatures above 100°C, demonstrating its excellent thermal quenching resistance.

[0054] 2. The long afterglow material of the present invention also has the characteristics of long luminescence lifetime and dynamically adjustable long afterglow luminescence performance. According to spectroscopy data, the phosphorescence lifetime is greater than 100ms and has excitation dependence and irradiation dependence.

[0055] 3. The polymer-based, color-tunable, long-lasting glow material designed in this invention not only offers a wider and more flexible color control range, but also boasts excellent processing properties, enabling fabrication into large-area, flexible devices with complex structures. Applications include lighting, imaging, road marking and warning systems, product anti-counterfeiting, information encryption, and biometric identification or sensing. The material maintains relatively stable photophysical properties in high-temperature, water- or high-humidity environments, as well as in acidic or alkaline environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1are the hydrogen nuclear magnetic resonance spectra of the long afterglow materials of Examples 1-4 of the present invention; a is the hydrogen nuclear magnetic resonance spectrum of the long afterglow polymer obtained in Example 1, b is the hydrogen nuclear magnetic resonance spectrum of the long afterglow polymer obtained in Example 2, c is the hydrogen nuclear magnetic resonance spectrum of the long afterglow polymer obtained in Example 3, and d is the hydrogen nuclear magnetic resonance spectrum of the long afterglow polymer obtained in Example 4.

[0057] Figure 2 These are the long afterglow luminescence conditions of the long afterglow materials of Examples 1-4 of the present invention in the air; a is the long afterglow luminescence condition of the long afterglow polymer obtained in Example 1 in the air, b is the long afterglow luminescence condition of the long afterglow polymer obtained in Example 2 in the air, c is the long afterglow luminescence condition of the long afterglow polymer obtained in Example 3 in the air, and d is the long afterglow luminescence condition of the long afterglow polymer obtained in Example 4 in the air.

[0058] Figure 3 This is the long afterglow luminescence of the long afterglow material in acid, alkali and water in Example 1 of the present invention;

[0059] Figure 4 This is the long afterglow luminescence of the long afterglow material in acid, alkali and water in Example 2 of the present invention;

[0060] Figure 5 This is the long afterglow luminescence of the long afterglow material in acid, alkali and water in Example 3 of the present invention;

[0061] Figure 6 This is the long afterglow luminescence of the long afterglow material in acid, alkali and water in Example 4 of the present invention;

[0062] Figure 7 This is the long afterglow luminescence of the long afterglow material of Example 5 of the present invention at high temperature;

[0063] Figure 8 This is the dynamically color-adjustable long-afterglow luminescence of the long-afterglow material of Example 6 of the present invention. DETAILED DESCRIPTION

[0064] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto.

[0065] For polymer-based long-lasting glow materials, polymer rigidity can be enhanced by increasing intermolecular chain interactions, enhancing main chain rigidity, and increasing side group steric hindrance. This invention, by preparing a cycloolefin copolymer with a cyclic main chain structure, large steric hindrance side groups, and ester groups, effectively improves the luminescence lifetime, environmental tolerance, and thermal quenching resistance of polymer-based long-lasting glow materials, enabling them to maintain excellent long-lasting luminescence performance in high-temperature, aqueous or high-humidity environments, and in acidic or alkaline environments.

[0066] 1. Preparation method of intrinsic dynamically color-adjustable cyclic olefin copolymer long-lasting glow material

[0067] Example 1

[0068] Dichloromethane (20 mL), 0.036 g (0.1 mmol) of N-pyrenyl-5-norbornene-2,3-dicarboximide, and 1.52 g (10 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After reacting for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 1.

[0069] Example 2

[0070] Dichloromethane (20 mL), 0.0415 g (0.1 mmol) of N-(N-propyl-1,8-naphthalimide)-5-norbornene-2,3-dicarboximide, and 1.52 g (10 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After reacting for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 2.

[0071] Example 3

[0072] Dichloromethane (20 mL), 0.029 g (0.1 mmol) of N-naphthyl-5-norbornene-2,3-dicarboximide, and 1.52 g (10 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After reacting for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 3.

[0073] Example 4

[0074] Dichloromethane (20 mL), 0.039 g (0.1 mmol) of N-phenanthrene-5-norbornene-2,3-dicarboximide amine, and 1.52 g (10 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After reacting for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 4.

[0075] Example 5

[0076] Dichloromethane (20 mL), 0.039 g (0.1 mmol) of N-phenanthrene-5-norbornene-2,3-dicarboxylic acid imide amine, 1.8 g (4 mmol) of 5-norbornene-2,3-dicarboxylic acid adamantane-1-yl ester, and 0.91 g (6 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After the reaction for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 5.

[0077] Example 6

[0078] Dichloromethane (20 mL), 0.036 g (0.1 mmol) of N-pyrenyl-5-norbornene-2,3-dicarboximide, 0.0415 g (0.1 mmol) of N-(N-propyl-1,8-naphthalene dicarboximide)-5-norbornene-2,3-dicarboximide, 0.039 g (0.1 mmol) of N-terphenyl-5-norbornene-2,3-dicarboximide amine, 0.039 g (0.1 mmol) of N-phenanthrene-5-norbornene-2,3-dicarboximide amine and 0.91 g (6 mmol) of 5-norbornene-2-yl acetate were injected into the polymerization bottle in sequence. After the system temperature stabilized, 0.0088 g (0.01 mmol) of Grubbs third-generation catalyst was added. After the reaction for 4 h, the mixture was poured into 200 mL of methanol to obtain cycloolefin copolymer 6.

[0079] 2. Result detection and performance testing

[0080] 1. Structure and performance testing

[0081] like Figure 1 As shown, a is the H NMR spectrum of the long afterglow polymer obtained in Example 1, b is the H NMR spectrum of the long afterglow polymer obtained in Example 2, c is the H NMR spectrum of the long afterglow polymer obtained in Example 3, and d is the H NMR spectrum of the long afterglow polymer obtained in Example 4. It was confirmed that the long afterglow polymers obtained in Examples 1-4 are intrinsic cycloolefin copolymer long afterglow materials containing ester groups and chromophores.

[0082] 2. Photophysical property detection

[0083] Example 7:

[0084] S1. Take the long afterglow polymer film prepared in Example 1 and vacuum dry it at 60° C. to a constant weight;

[0085] S2, irradiating the polymer film with ultraviolet light having a wavelength of 365 nm for 30 seconds;

[0086] S3. Turn off the light source and test the duration of the red afterglow emitted by the polymer film in air and water;

[0087] like Figure 2 and Figure 3 As shown, the polymer film emits red afterglow for 3 seconds in both air and water.

[0088] Example 8:

[0089] S1. Take the long afterglow polymer film prepared in Example 2 and vacuum dry it at 60° C. to a constant weight;

[0090] S2, irradiating the polymer film with ultraviolet light having a wavelength of 365 nm for 30 seconds;

[0091] S3. Turn off the light source and test the duration of the yellow afterglow emitted by the polymer film in air and water;

[0092] like Figure 2 and Figure 4 As shown, the polymer film emits a yellow afterglow for 2 seconds in both air and water.

[0093] It can be seen from this that the long afterglow material of the present invention has the same afterglow duration in air and in water, and the material of the present invention has excellent water resistance and good long luminous life.

[0094] Example 9:

[0095] S1. Take the long afterglow polymer film prepared in Example 5 and vacuum dry it at 60° C. to constant weight;

[0096] S2, irradiating the polymer film with ultraviolet light of a wavelength of 285 nm for 30 seconds;

[0097] S3, turning off the light source, and testing whether the polymer film has afterglow emission at 100°C;

[0098] like Figure 7 As shown, the polymer film emits a green afterglow at 100°C.

[0099] It can be seen that the long afterglow material of the present invention still has afterglow emission at high temperature, and the material of the present invention has excellent resistance to thermal quenching.

[0100] III. Testing of Other Embodiments

[0101] S1. Take the long afterglow polymer film prepared in Example 6 and vacuum dry it at 60° C. to constant weight;

[0102] S2, irradiating the polymer film with ultraviolet light having a wavelength of 365 or 285 nm for 30 seconds;

[0103] S3, turning off the light source, and testing the changes in afterglow of the polymer film at 80K, 240K, and room temperature;

[0104] like Figure 8 As shown, the polymer film can be tuned from cyan to red under different conditions.

[0105] In summary, the present invention sequentially injects the required amount of organic reagent, phosphor and ester-rich cycloolefin monomer into a polymerization flask, adds a metal complex as a catalyst, and obtains a long afterglow material after 2-10 hours of polymerization. The material has excellent processing properties and can be used to prepare light-emitting devices with complex shapes. The long afterglow material is prepared by multi-component copolymerization to form a polymer having a cyclic main chain structure, large steric hindrance side groups and ester-rich polymers, which can effectively improve the luminescence life, environmental factor tolerance, and thermal quenching resistance of the polymer-based long afterglow material. At the same time, copolymerization with different phosphors gives the material a long afterglow luminescence performance covering the entire color range. The long afterglow luminescence color is adjustable within the entire visible light range, so that the material of the present invention maintains excellent long afterglow luminescence performance under high temperature, water environment or high humidity environment, acidic or alkaline environment.

[0106] In addition, the long afterglow material of the present invention can be used in lighting, imaging, road marking and warning, product anti-counterfeiting, information encryption, biological identification, and sensing, and can still maintain relatively stable photophysical properties in high temperature, water environment or high humidity environment, acidic or alkaline environment.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the technical solutions. Those skilled in the art should understand that modifications or equivalent replacements of the technical solutions of the present invention that do not depart from the purpose and scope of the technical solutions of the present invention should be included in the scope of the claims of the present invention.

Claims

1. An intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material, characterized in that: Cyclic olefin copolymers comprising the following general structural formula: in: R1, R2, R3 and R4 include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or adamantyl; R5 is a chromophore selected from any of the following structural formulas: or wherein A, A1 and A2 are one of N, P, S and O atoms; R6, R7, R8, R9, R 10 and R 11 , including hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hydroxy, 1-hydroxymethyl, 1-hydroxyethyl, 1-hydroxy-n-propyl, 1-hydroxyisopropyl, amino, 1-aminomethyl, 1-aminoethyl, 1-amino-n-propyl, 1-aminoisopropyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, formate, acetate, propionate, n-butyrate, isobutyrate, methyl formate, methyl acetate, methyl propionate, methyl n-butyrate , methyl isobutyrate, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, formonitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, boronic acid, fluoro, 1-fluoromethyl, 1-fluoroethyl, 1-fluoro-n-propyl, 1-fluoroisopropyl, chloro, 1-chloromethyl, 1-chloroethyl, 1-chloro-n-propyl, 1-chloroisopropyl, bromo, 1-bromomethyl, 1-bromoethyl, 1-bromo-n-propyl, 1-bromoisopropyl, iodo, 1-iodomethyl, 1-iodoethyl, 1-iodo-n-propyl, 1-iodoisopropyl, trifluoro, trifluoromethyl, trifluoroethyl, trifluoro-n-propyl, trifluoroisopropyl; The polymerization degrees a, b, c and d are all 0-10000, and a, b, c and d are not 0 at the same time; e is 10-10000; and n is a natural number between 1 and 20.

2. The intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material according to claim 1, characterized in that: The cycloolefin copolymer is prepared by polymerizing an ester-containing cycloolefin monomer and a chromophore-containing cycloolefin monomer; wherein the ester-containing cycloolefin monomer comprises a cycloolefin monomer having any one of the following general structural formulas:

3. The intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material according to claim 2, characterized in that: The chromophore-containing cycloolefin monomer is selected from the following cycloolefin monomers of the general structural formula:

4. The intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material according to claim 1, characterized in that: The molecular weight of the intrinsic dynamically color-adjustable cycloolefin copolymer long-afterglow material is 10,000-1,000,000.

5. The intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material according to claim 2, characterized in that: The molar fraction of the ester group-containing cycloolefin structural unit is greater than 0 mol % and less than 100 mol %.

6. The intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material according to claim 2, characterized in that: The molar fraction of the chromophore-containing cycloolefin structural unit is greater than or equal to 1 mol % and less than 100 mol %.

7. The method for preparing the intrinsic type dynamically color-adjustable cycloolefin copolymer long afterglow material according to claim 1, characterized in that: The steps include: Add an organic solvent, an ester-containing cycloolefin monomer, a chromophore-containing cycloolefin monomer, and a catalyst into a polymerization bottle, polymerize for 2-10 hours, and then add a precipitant to obtain a long afterglow material; The molar ratio of the ester-containing cycloolefin monomer, the chromophore-containing cycloolefin monomer and the catalyst is 1-100:1000:0.1-10; and the usage ratio of the solvent to the monomer is 1-100 mL:1 g.

8. The method for preparing the intrinsic type dynamically color-adjustable cycloolefin copolymer long afterglow material according to claim 7, characterized in that: The organic solvent is one or a mixture of methanol, ethanol, acetone, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, N,N-dimethylformamide, and dimethyl sulfoxide.

9. An application of an intrinsic type dynamically color-adjustable cyclic olefin copolymer long afterglow material, characterized in that: The cyclic olefin copolymer long afterglow material obtained by the method of any one of claims 7 to 8 is used in lighting, imaging, road marking and warning, commodity anti-counterfeiting, information encryption, biological identification, and sensing.

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