A cyclic olefin ionomer long afterglow material and a method of making the same

Abstract

The application discloses a long afterglow material of cyclic olefin ion copolymer and a preparation method thereof, relates to the field of long afterglow materials, and the long afterglow material has a polymer with different counter ions, ester groups and chromophores as a matrix, the luminescent performance of the polymer is adjusted by controlling the content of different structural units in the polymer and the length of alkyl chains, the type of ions and the type of chromophores in norbornene derivatives containing ions in the norbornene derivatives. At the same time, the intrinsic polymer-based long afterglow material and different types of chromophores endow the material with stable long afterglow luminescent performance covering the full color gamut. The preparation method is simple, the prepared long afterglow material has the characteristics of long luminescent lifetime, dynamically adjustable long afterglow luminescent performance and the like, and has excitation dependence and irradiation dependence.

Description

Technical Field

[0001] This invention relates to the field of long afterglow materials, specifically to a cyclic olefin ionic copolymer long afterglow material and its preparation method. Background Technology

[0002] Polymer-based methods are one strategy for achieving long-afterglow luminescence. This involves immobilizing phosphors within a polymer matrix, utilizing the rigid environment provided by the polymer matrix to promote phosphorescence in the initial phosphor. This rigid environment is primarily constructed through intramolecular and intermolecular interactions, such as hydrogen bonding, electrostatic interactions, covalent bonds, and ionic interactions. While hydrogen bonding, electrostatic interactions, and covalent bonds have been widely applied, ionic polymer-based long-afterglow materials have received relatively little attention. Summary of the Invention

[0003] To address the aforementioned shortcomings of the prior art, this invention provides a long afterglow material of cyclic olefin ionic copolymers and its preparation method.

[0004] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0005] A long afterglow material of cyclic olefin ionic copolymer and its preparation method are provided, which includes the following general structural formula:

[0006]

[0007] Wherein, R1 and R2 are aliphatic or aromatic groups; R3 is nitrogen, phosphorus or boron; R4 is a group with color-producing ability; x, y and z are the degree of polymerization, and z is not 0, x and y cannot be 0 at the same time; m and n are the number of methylene groups, and X is an anion.

[0008] Furthermore, X can be a bromide ion, a bis(trifluoromethanesulfonyl)imide anion, a perfluorobutylsulfonic acid anion, a trifluoromethanesulfonate anion, or a methanesulfonate anion.

[0009] Furthermore, when R1 and R2 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.

[0010] Its structural formulas are as follows:

[0011] ·H

[0012] ·OH, ·CH2OH, ·CH3CH3OH

[0013] ·NH2、·-NH2、

[0014]

[0015] When R1 and R2 are aromatic groups, they include phenyl, naphthyl, anthracene, indene, 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, and 3-fluorophenyl. 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-T-Butylphenyl, 3-T-Butylphenyl, 4-T-Butylphenyl, 2,6-Di-T-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-di-trifluoromethylphenyl, 3,5-di-trifluoromethylphenyl, 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;

[0016] Its structural formulas are as follows:

[0017]

[0018]

[0019]

[0020] Furthermore, the group possessing chromogenic ability can be any of the following general structural formulas:

[0021]

[0022]

[0023] Among them, R5, R6, R7, R8, R9 and R 10 It is an aliphatic or aromatic group, and A, A1 and A2 are nitrogen, phosphorus, sulfur or oxygen elements.

[0024] R5, R6, R7, R8, R9 and R 10 When the radical is aliphatic, 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, formic acid, acetate, propionic acid, n-butyric acid, isobutyric acid, methyl formate, methyl acetate, methyl propionic acid, n-butyric acid Methyl ester 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, boric acid group, fluoro group, 1-fluoromethyl, 1-fluoroethyl, 1-fluoron-propyl, 1-fluoroisopropyl, chloro group, 1-chloromethyl, 1-chloroethyl, 1-chloron-propyl, 1-chloroisopropyl, bromo group, 1-bromomethyl, 1-bromoethyl, 1-bromon-propyl, 1-bromoisopropyl, iodo group, 1-iodomethyl, 1-iodoethyl, 1-iodon-propyl, 1-iodoisopropyl, trifluoro group, trifluoromethyl, trifluoroethyl, trifluoron-propyl, trifluoroisopropyl;

[0025] R5, R6, R7, R8, R9 and R 10When the aromatic group is phenyl, naphthyl, anthraceneyl, pyrene, 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-di(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-amine 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 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-Acrylonitrilephenyl, 3-Acrylonitrilephenyl, 4-Acrylonitrilephenyl, 2,6-Diacrylonitrilephenyl, 3,5-Diacrylonitrilephenyl, 2,4,6-Triacrylonitrilephenyl, 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.

[0026] A long afterglow material of the above-mentioned cyclic olefin ionic copolymer includes the following specific steps:

[0027] S1: Dissolve two or more of the following in an organic solvent: ionic norbornene derivatives, norbornene derivatives containing ester groups, or norbornene derivatives containing chromophores.

[0028] S2: Add catalyst to the mixture and polymerize at room temperature for 0.5-24 hours;

[0029] S3: The polymer solution after the reaction is completed is added dropwise to the precipitant. The precipitated solid is filtered, washed, and dried to obtain the long afterglow material of the cyclic olefin ionic copolymer.

[0030] Furthermore, the organic solvent is one or more of methanol, ethanol, acetone, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, N,N-dimethylformamide, or dimethyl sulfoxide.

[0031] Furthermore, the catalyst is a metal-centered organic compound; the metal is ruthenium, molybdenum, tungsten, nickel, palladium, iron, cobalt, rhodium, copper, gold, platinum, titanium, zirconium, hafnium, aluminum, zinc, magnesium, or boron.

[0032] Furthermore, the molar ratio of ionic norbornene derivatives, ester-containing norbornene derivatives, chromophore-containing norbornene derivatives, and catalyst is 0–600:0–600:0.1–10:1.

[0033] Furthermore, the precipitant is one or more of the following: water, methanol, ethanol, n-pentane, n-hexane, n-heptane, or petroleum ether.

[0034] The beneficial effects of this invention are as follows:

[0035] The long-afterglow material proposed in this invention uses polymers with different counterions, ester groups, and chromophores as a matrix. The luminescent properties of the polymer are adjusted by controlling the content of different structural units in the polymer, the alkyl chain length and ion type in the norbornene derivative containing ions, and the type of chromophore in the norbornene derivative. Simultaneously, the intrinsic polymer-based long-afterglow material and the different types of chromophores endow the material with stable long-afterglow luminescence properties covering the entire color gamut.

[0036] The preparation method of the present invention is simple, and the long afterglow material prepared has the characteristics of long luminescence lifetime and dynamically adjustable long afterglow luminescence performance, and also has excitation dependence and irradiation dependence. Attached Figure Description

[0037] Figure 1 The following are the 1H NMR spectra of the long afterglow materials in Examples 1 and 2;

[0038] Figure 2 The following are the 1H NMR spectra of the long afterglow materials in Examples 3 and 4;

[0039] Figure 3 The following are the 1H NMR spectra of the long afterglow materials in Examples 5, 6, 7, 8, and 9;

[0040] Figure 4 This is a schematic diagram of the afterglow luminescence of the long afterglow materials in Examples 1 and 2;

[0041] Figure 5 This is a schematic diagram of the afterglow luminescence of the long afterglow materials in Examples 3 and 4;

[0042] Figure 6 The diagram shows the afterglow luminescence of the long afterglow materials in Examples 5, 6, 7, 8, and 9. Detailed Implementation

[0043] The specific embodiments of the present invention are described below to enable those skilled in the art to understand the present invention. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various changes are obvious as long as they are within the spirit and scope of the present invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0044] Example 1

[0045] S1: Weigh 6.0 mmol of ionic norbornene derivative and 0.06 mmol of chromophore-containing norbornene derivative and place them in a polymerization flask. In this embodiment, the ionic norbornene derivative is 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazol-3-ammonium bromide; the chromophore-containing norbornene derivative is N-naphthalene-5-norbornene-2,3-dicarboximide; use ultra-dry dichloromethane and ultra-dry N,N-dimethylformamide in a 5:1 ratio to obtain a mixed organic solvent. Take 30 mL of the prepared mixed organic solvent and add it to the polymerization flask. Stir with a magnetic stirrer at 500 r / min for 5 minutes to obtain a uniformly mixed solution.

[0046] S2: After stirring, add 0.01 mmol of Grubbs third-generation catalyst and continue stirring the polymerization reaction at room temperature for 5 hours; in specific implementation, the polymerization reaction time can also be 0.5, 1, 10, 15, 20 or 24 hours, and any one of the ranges from 0.5 to 24 hours is acceptable.

[0047] S3: After the reaction is complete, take 300 mL of n-hexane in a beaker, and add the polymer solution obtained from the static reaction dropwise into the n-hexane. During the dropwise addition process, stir vigorously with a stir bar. Filter the precipitated solid, wash it with n-hexane, and vacuum dry it overnight at 40°C using a DZF-6020 vacuum drying oven to obtain a dry long afterglow material.

[0048] Example 2

[0049] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 6.0 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazolium-3-trifluoromethanesulfonate and 0.06 mmol of N-naphth-5-norbornene-2,3-dicarboximide.

[0050] Example 3

[0051] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 6.0 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazolium-3-trifluoromethanesulfonate and 0.06 mmol of N-pyrene-5-norbornene-2,3-dicarboximide.

[0052] Example 4

[0053] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 6.0 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazolium-3-trifluoromethanesulfonate and 0.06 mmol of N-pyrene-5-norbornene-2,3-dicarboximide.

[0054] Example 5

[0055] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 4.8 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazol-3-trifluoromethanesulfonate, 1.2 mmol of 1-(bicyclo[2.2.1]hept-5-5-norbornene-2-acetate and 0.06 mmol of N-naphth-5-norbornene-2,3-dicarboximide.

[0056] Example 6

[0057] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 3.6 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazol-3-trifluoromethanesulfonate, 2.4 mmol of 1-(bicyclo[2.2.1]hept-5-5-norbornene-2-acetate and 0.06 mmol of N-naphth-5-norbornene-2,3-dicarboximide.

[0058] Example 7

[0059] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 2.4 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazol-3-trifluoromethanesulfonate, 3.6 mmol of 1-(bicyclo[2.2.1]hept-5-5-norbornene-2-acetate and 0.06 mmol of N-naphth-5-norbornene-2,3-dicarboximide.

[0060] Example 8

[0061] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 1.2 mmol of 1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3-butyl-1-hydro-imidazol-3-trifluoromethanesulfonate, 4.8 mmol of 1-(bicyclo[2.2.1]hept-5-5-norbornene-2-acetate and 0.06 mmol of N-naphth-5-norbornene-2,3-dicarboximide.

[0062] Example 9

[0063] The difference between this embodiment and Example 1 is that the raw materials added to the polymerization bottle in step S1 are 6 mmol of 1-(bicyclo[2.2.1]hept-5-5-norbornene-2-acetate and 0.06 mmol of N-naphthalene-5-norbornene-2,3-dicarboximide.

[0064] The long afterglow materials prepared in Examples 1-9 were subjected to 1H NMR spectroscopy for analysis. The results are as follows: Figure 1-3 As shown, based on the 1H NMR spectroscopy data, the structural formula of the long afterglow material prepared in Example 1 is as follows: R3 represents nitrogen, R4 represents naphthyl group, and X represents bromide ion; the structural formula of the long afterglow material obtained in Example 2 is as follows: R3 is nitrogen, R4 is naphthyl, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 3 is as follows: R3 is nitrogen, R4 is pyrene, and X is bromide ion; the structural formula of the long afterglow material obtained in Example 4 is as follows: R3 is nitrogen, R4 is pyrene, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 5 is as follows: R1 is methyl, R3 is nitrogen, R4 is naphthyl, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 6 is as follows: R1 is methyl, R3 is nitrogen, R4 is naphthyl, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 7 is as follows: R1 is methyl, R3 is nitrogen, R4 is naphthyl, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 8 is as follows: R1 is methyl, R3 is nitrogen, R4 is naphthyl, and X is trifluoromethanesulfonate anion; the structural formula of the long afterglow material prepared in Example 9 is as follows: Its R1 is methyl, R3 is nitrogen, and R4 is naphthyl.

[0065] The long afterglow materials obtained in Examples 1-9 were used to prepare polymer films. The specific method was as follows: 30 mg of long afterglow material was completely dissolved in 1 mL of methanol at room temperature, and the solution was spin-coated onto a quartz plate. The temperature was kept constant at 60°C for 1 hour until the methanol was completely evaporated, and the long afterglow polymer film was obtained.

[0066] Each polymer film was irradiated with ultraviolet light at a wavelength of 310 nm or 365 nm for 30 seconds, and the afterglow time was measured. The results are as follows: Figure 4-6 As shown in Table 1;

[0067] Table 1

[0068] Example 1 310nm green 2s Example 2 310nm green 6s Example 3 365nm red 1s Example 4 365nm red 2s Example 5 310nm green 6s Example 6 310nm green 6s Example 7 310nm green 6s Example 8 310nm green 7s Example 9 310nm green 7s

[0069] As shown in Table 1, the method of the present invention can produce luminescent long-afterglow materials, and the methods of Examples 8 and 9 have the longest afterglow duration.

[0070] A binary copolymer synthesized from ionic norbornene derivatives and chromophore-containing norbornene derivatives utilizes strong ionic interactions to suppress nonradiative transitions of the chromophore, thereby achieving room-temperature phosphorescence. By changing the type of ions, it was found that the emission duration is significantly affected by the counterions. Furthermore, changing the type of chromophore correspondingly alters the emission color, enabling flexible control of the emission color from green to red.

[0071] The synthesized terpolymer contains ionic groups, ester groups, and chromophores. Under the electrostatic interaction provided by the ester groups, the glass transition temperature gradually increases with the increase of ester group content, the intermolecular forces are enhanced, the nonradiative transition of the chromophores is greatly suppressed, and the luminescence duration gradually increases.

Claims

1. A long afterglow material of a cyclic olefin ion copolymer, characterized in that, Includes the following general structural formulas: Wherein, R1 and R2 are aliphatic or aromatic groups; R3 is nitrogen, phosphorus or boron; R4 is a group with color-producing ability; x, y and z are the degree of polymerization, and z is not 0, x and y cannot be 0 at the same time; m and n are the number of methylene groups, and X is an anion.

2. The long afterglow material of cyclic olefin ion copolymer according to claim 1, characterized in that, X is a bromide ion, a bis(trifluoromethanesulfonyl)imide anion, a perfluorobutylsulfonic acid anion, a trifluoromethanesulfonate anion, or a methanesulfonate anion.

3. The long afterglow material of cyclic olefin ion copolymer according to claim 1, characterized in that, When R1 and R2 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. When R1 and R2 are aromatic groups, they include phenyl, naphthyl, anthracene, indene, 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, and 3-fluorophenyl. 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-T-Butylphenyl, 3-T-Butylphenyl, 4-T-Butylphenyl, 2,6-Di-T-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-di-trifluoromethylphenyl, 3,5-di-trifluoromethylphenyl, 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.

4. The long afterglow material of cyclic olefin ion copolymer according to claim 1, characterized in that, The chromophore group is any one of the following general structural formulas: Among them, R5, R6, R7, R8, R9 and R 10 It is an aliphatic or aromatic group, and A, A1 and A2 are nitrogen, phosphorus, sulfur or oxygen elements.

5. The long afterglow material of cyclic olefin ion copolymer according to claim 4, characterized in that, R5, R6, R7, R8, R9 and R 10 When the radical is aliphatic, 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, formic acid, acetate, propionic acid, n-butyric acid, isobutyric acid, methyl formate, methyl acetate, methyl propionic acid, n-butyric acid Methyl ester 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, boric acid group, fluoro group, 1-fluoromethyl, 1-fluoroethyl, 1-fluoron-propyl, 1-fluoroisopropyl, chloro group, 1-chloromethyl, 1-chloroethyl, 1-chloron-propyl, 1-chloroisopropyl, bromo group, 1-bromomethyl, 1-bromoethyl, 1-bromon-propyl, 1-bromoisopropyl, iodo group, 1-iodomethyl, 1-iodoethyl, 1-iodon-propyl, 1-iodoisopropyl, trifluoro group, trifluoromethyl, trifluoroethyl, trifluoron-propyl, trifluoroisopropyl; R5, R6, R7, R8, R9 and R 10 When the aromatic group is phenyl, naphthyl, anthraceneyl, pyrene, 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-di(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-amine 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 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-Acrylonitrilephenyl, 3-Acrylonitrilephenyl, 4-Acrylonitrilephenyl, 2,6-Diacrylonitrilephenyl, 3,5-Diacrylonitrilephenyl, 2,4,6-Triacrylonitrilephenyl, 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.

6. A long afterglow material of a cyclic olefin ion copolymer according to any one of claims 1-5, characterized in that, The specific steps include the following: S1: Dissolve two or more of the following in an organic solvent: ionic norbornene derivatives, norbornene derivatives containing ester groups, or norbornene derivatives containing chromophores. S2: Add catalyst to the mixture and polymerize at room temperature for 0.5-24 hours; S3: The polymer solution after the reaction is completed is added dropwise to the precipitant. The precipitated solid is filtered, washed, and dried to obtain the long afterglow material of the cyclic olefin ionic copolymer.

7. The method for preparing the long afterglow material of the cyclic olefin ionic copolymer according to claim 6, characterized in that, The organic solvent is one or more of methanol, ethanol, acetone, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, N,N-dimethylformamide, or dimethyl sulfoxide.

8. The method for preparing the long afterglow material of the cyclic olefin ionic copolymer according to claim 6, characterized in that, The catalyst is a metal-centered organic compound; the metal is ruthenium, molybdenum, tungsten, nickel, palladium, iron, cobalt, rhodium, copper, gold, platinum, titanium, zirconium, hafnium, aluminum, zinc, magnesium, or boron.

9. The method for preparing the long afterglow material of the cyclic olefin ionic copolymer according to claim 6, characterized in that, The molar ratio of the ionic norbornene derivative, the ester-containing norbornene derivative, the chromophore-containing norbornene derivative, and the catalyst is 0–600:0–600:0.1–10:

1.

10. The method for preparing the long afterglow material of the cyclic olefin ionic copolymer according to claim 6, characterized in that, The precipitant is one or more of the following: water, methanol, ethanol, n-pentane, n-hexane, n-heptane, or petroleum ether.

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