CN115058126A - Styrene hemicyanine fluorescent dye, preparation method thereof and application thereof in rare earth colorful long afterglow luminescent material - Google Patents

Styrene hemicyanine fluorescent dye, preparation method thereof and application thereof in rare earth colorful long afterglow luminescent material Download PDF

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CN115058126A
CN115058126A CN202210525907.4A CN202210525907A CN115058126A CN 115058126 A CN115058126 A CN 115058126A CN 202210525907 A CN202210525907 A CN 202210525907A CN 115058126 A CN115058126 A CN 115058126A
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rare earth
luminescent material
afterglow luminescent
styrene
fluorescent dye
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CN115058126B (en
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宋立军
吴银财
赵丹
林凤龙
王胜龙
王辛坤
李金蕾
张炎
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Fujian Institute of Research on the Structure of Matter of CAS
Mindu Innovation Laboratory
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Fujian Institute of Research on the Structure of Matter of CAS
Mindu Innovation Laboratory
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

The invention discloses a styrene hemicyanine fluorescent dye, a preparation method thereof and application thereof in rare earth colorful long afterglow luminescent materials. The styrene hemicyanine fluorescent dye is obtained by reacting N-methyldiphenylamine with N-methyldiphenylamine to obtain a compound A and then reacting the compound A with 1, 4-dimethylpyridine iodide. The invention synthesizes a novel high-efficiency light conversion inclusion compound and realizes the surface coating of the rare earth long afterglow luminescent material. By regulating and controlling the formula and concentration of the high-efficiency light conversion inclusion compound, the light color of the rare earth long afterglow material can be adjusted by utilizing the continuous emission photons of the rare earth long afterglow material to be absorbed by the light conversion layer. Finally, the color of the compound is changed from green, yellow to orange by different adding proportions of the light conversion agent.

Description

Styrene hemicyanine fluorescent dye, preparation method thereof and application thereof in rare earth colorful long-afterglow luminescent material
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a styrene hemicyanine fluorescent dye, a preparation method thereof and application thereof in rare earth colorful long-afterglow luminescent materials.
Background
The long-afterglow luminescent material is a substance which can absorb solar energy or artificial light source and can continuously emit visible light after the excitation is stopped. Because it has the function of self-lighting, it is an energy-storing and energy-saving luminescent material, and has wide application in the industries of safety indication, traffic sign, architectural decoration, night lighting, etc., and has wide application prospect. The existing commercialization is mainly blue-green and yellow-green rare earth long afterglow luminescent materials, and the research on the method for adjusting the light color of the rare earth long afterglow luminescent materials has important scientific research significance and practical value.
According to the literature report, the perovskite quantum dots with strong absorption and high fluorescence quantum yield are coated on the surface of the rare earth long afterglow material in a spin mode to serve as an effective light conversion layer, so that the light color conversion of the rare earth long afterglow material is achieved, but the spin coating preparation process is suitable for the research of small-batch laboratory levels, and therefore the practical application is limited. In addition, tetraethoxysilane is adopted as a silicon coating reagent, and fluorescent pigment is packaged on the surface of the rare earth long afterglow material through a sol-gel process, so that the output is converted from blue-green light to red light, but the persistence duration is short and the brightness is low due to the influence of the silicon coating.
The cyclodextrin is a cylindrical structure with a cavity, and hydroxyl is distributed on the outer side of the cavity and has hydrophilicity; the hydrogen atoms and oxygen atoms on glycosidic bonds form an inner cavity of the cyclodextrin, the cyclodextrin has hydrophobicity, and the guest molecules are selectively adsorbed according to the actions among subjects and guests, such as Van der Waals force, hydrophobic acting force, hydrogen bond interaction force and the like, so that the inclusion compound with a specific molecular ratio is formed. According to the invention, the cyclodextrin is modified by using the coupling agent, and the space isolation of the self-made styrene hemicyanine fluorescent dye fluorophore is realized by using the inclusion effect of the modified cyclodextrin cavity, so that the photoelectric energy coupling and the quenching of fluorescence emission generated in the solid-state crystallization process of the fluorescent material are avoided, and the high-efficiency fluorescent material is prepared to be used as a light conversion agent. Meanwhile, a large amount of hydroxyl on the outer side of the modified cyclodextrin is combined with aluminum, strontium, oxygen and other atoms on the surface of the surface-modified rare earth long afterglow material through hydrogen bonds, electrostatic interaction and the like, and finally the rare earth colorful long afterglow luminescent material with excellent luminescent performance is prepared.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a styrene hemicyanine fluorescent dye, a preparation method thereof, and an application thereof in a rare earth multicolor long afterglow luminescent material.
In order to realize the purpose, the invention adopts the following technical scheme:
a styrene hemicyanine fluorescent dye has the following structural formula:
Figure 100002_DEST_PATH_IMAGE001
the structure of the high-temperature resistant glass has the high temperature resistance of up to 150 ℃, and is in an indirect benzene ring and splayed-like structure linear structure, so that the glass is easier to structurallyThe coating is realized, and the emission spectrum can reach 650 nm.
Further, the preparation method of the styrene hemicyanine fluorescent dye comprises the following steps:
(1) reacting N-methyldiphenylamine with phosphorus oxychloride in N, N-dimethylformamide to obtain a compound A, namely 4, 4' - (methylamine) bis-benzaldehyde;
(2) and reacting the compound A with 1, 4-dimethylpyridine iodide to obtain the styrene hemicyanine fluorescent dye.
Further, the synthesis method of the compound a obtained in the step (1) specifically comprises the following steps:
1) putting the flask into ice water containing NaCl, and adding N, N-dimethylformamide after the flask body is completely cooled;
2) slowly dripping phosphorus oxychloride into the flask, keeping the temperature change in the dripping process within the range of 0-5 ℃, and forming a viscous state after the dripping is finished;
3) removing the NaCl-containing ice water bath, and continuously stirring at 600-1200 rpm for 10-60 min at 20-40 ℃ in a nitrogen atmosphere;
4) dissolving N-methyldiphenylamine in N, N-dimethylformamide, and dropwise adding into the flask containing the viscous mixture by using an injector;
5) heating the flask to 50-90 ℃, and continuously reacting for 0.5-3 h under the protection of nitrogen;
6) transferring the reaction liquid in the flask into an ice water mixture, and then adjusting the pH value of the reaction liquid to 6.5-7.5 by using a sodium carbonate solid;
7) extracting with dichloromethane, drying with anhydrous sodium sulfate, and concentrating under reduced pressure;
8) purified by silica gel chromatography and purified by ethyl acetate/petroleum ether (v/v = 1: 5-20) and eluting to obtain the compound A.
Further, the step (2) is specifically as follows:
1) adding the compound A and 1, 4-dimethyl pyridine iodized salt into ethanol;
2) carrying out reflux reaction at 60-90 ℃ for 2-8 h to obtain black purple precipitate;
3) subjecting the precipitate to CH treatment 2 C l2 /CH 3 And (5) recrystallizing OH (v/v = 1: 0.5-3) to obtain a compound B, namely the styrene hemicyanine fluorescent dye.
The invention also provides a rare earth colorful long afterglow luminescent material prepared by the styrene hemicyanine fluorescent dye, which comprises the following components:
the component A comprises: one of beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxybutyl beta-cyclodextrin and methyl beta-cyclodextrin;
the component B comprises: a styrene hemicyanine fluorescent dye;
and the component C is as follows: rare earth long afterglow luminescent material SrAl 2 O 4 ：Eu 2+ ,Dy 3+ ；
And (D) component: one of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the component E is one of silicone oil, acrylic acid and ethyl orthosilicate;
and F, component: at least one of water, ethanol, toluene, m-xylene and isoamyl alcohol;
and (2) component X: benzene.
The invention also provides a preparation method of the rare earth colorful long afterglow luminescent material, which comprises the following steps:
(1) modifying cyclodextrin: a, X, D and F are prepared into a dilute solution Y, ultrasonic dispersion is carried out for 15-60 min, and standing is carried out for 12-24 h, so as to obtain modified cyclodextrin Z;
(2) preparing a high-efficiency light conversion inclusion compound: preparing a G dilute solution from Z and F, carrying out ultrasonic dispersion for 15-90 min, and standing for 6-24 h; then adding B, stirring and reacting for 1-12H at the temperature of 25-60 ℃ and the rpm of 400-; finally, drying the H at 70-140 ℃ for 4-24H, taking out and grinding the H into powder to obtain a light conversion agent I;
(3) preparing a rare earth colorful long-afterglow luminescent material: preparing the solution J from the I, the C and the F obtained in the step (2), stirring at 400-1200rpm at 25-60 ℃ for 5-30min, heating to 70-100 ℃, adding the D and the E, continuing stirring for 20-90min, separating the filtrate, freeze-drying the solid for 12-48h, taking out, grinding and screening to obtain the rare earth colorful long afterglow luminescent material.
Further, the mass ratio of A, X, D to F in step (1) is 1: 0.05-0.5: 0.005-0.02: 100 to 300.
Further, the mass ratio of Z to F in the step (2) is 1: 100-500, and the mass ratio of B to A in G is 1: 0.5-2.
Further, the mass ratio of I, C to F in step (3) is 1: 2-10: 100-300.
Further, the mass ratio of D to I in the step (3) is 1: 20-100; the mass ratio of E to I is 1: 20-100.
Has the advantages that: the invention synthesizes a novel high-efficiency light conversion inclusion compound and realizes the surface coating of the rare earth long afterglow luminescent material. By regulating and controlling the formula and concentration of the high-efficiency light conversion inclusion compound, the light color of the rare earth long afterglow material can be adjusted by utilizing the continuous emission photons of the rare earth long afterglow material to be absorbed by the light conversion layer. Finally, the color of the compound is changed from green, yellow to orange by different adding proportions of the light conversion agent as shown in figure 1. The innovative design concept of coating the surface of the rare earth long-afterglow luminescent material by adopting the efficient light conversion inclusion compound provides a new visual angle for widening the colorful color luminescence of the long-afterglow luminescent material, and opens up a new direction for the new application of the colorful lasting luminescent material.
Drawings
FIG. 1 is a color coordinate diagram; the color coordinate graph is roughly divided into an upper left region, a lower right region and a middle region according to the direction, wherein the upper left region is a greenish region, the lower left region is a bluish region and a purple region, the lower right region is a reddish region, the middle region is a yellow region, the color of the upper left region towards the lower left region is gradually changed from green to pale green, pale blue and blue, the color of the lower left region towards the lower right region is gradually changed from purple to pale purple, pink and red, and the color of the upper left region towards the lower right region is gradually changed from green to pale green, yellow, orange and red. The invention mainly coats the light conversion material on the surface of the green long-afterglow luminescent material, thereby realizing the controllable adjustment of the color from the upper left area to the lower right area, and further preparing the colorful long-afterglow luminescent material; FIG. 1 shows the positions of color coordinates corresponding to examples and comparative examples; examples 7 to 13 each correspond to K 1 -K 7 Comparative examples 1 to 3, corresponding to K respectively 8 -K 10 ，K 0 Is a blank long afterglow luminescent material; k 0 -K 10 The coordinates corresponding to the color code system are respectively K 0 （0.28，0.61）,K 1 （0.52，0.42）,K 2 （0.47，0.46）, K 3 （0.45，0.48）, K 4 （0.57，0.41）,K 5 （0.52，0.44）, K 6 （0.51，0.45）, K 7 （0.54，0.44）, K 8 （0.39，0.52）, K 9 （0.34，0.54）,K 10 （0.29，0.60）。
Detailed Description
Example 1
Preparation of styryl hemicyanine fluorescent dye
(1) The synthesis method of the obtained compound A comprises the following steps: (1) putting the flask into ice water containing NaCl, and adding N, N-dimethylformamide after the flask body is completely cooled; (2) slowly dripping phosphorus oxychloride into the flask, keeping the temperature change in the dripping process within the range of 0-5 ℃, and forming a viscous state after the dripping is finished; (3) removing the NaCl-containing ice water bath, and continuously stirring at 600-1200 rpm for 10-60 min at 20-40 ℃ in a nitrogen atmosphere; (4) dissolving 4, 4' - (methylamine) bis-benzaldehyde in N, N-dimethylformamide, and dropwise adding the solution into the viscous mixture in the flask by using a syringe; (5) heating the flask to 50-90 ℃, and continuously reacting for 0.5-3 h under the protection of nitrogen; (6) carefully transferring the reaction solution in the flask into an ice water mixture, and then adjusting the pH value of the reaction solution to 6.5-7.5 by using sodium carbonate solid; (7) extracting with dichloromethane, drying with anhydrous sodium sulfate, and concentrating under reduced pressure; (8) separating and purifying by using a silica gel chromatographic column, and eluting by using ethyl acetate/petroleum ether (v/v = 1: 5-20) to obtain the compound A. (9) Adding the compound A and 1, 4-dimethyl pyridine iodized salt into ethanol; (10) carrying out reflux reaction at 60-90 ℃ for 2-8 h to obtain black purple precipitate; (11) subjecting the precipitate to CH treatment 2 C l2 /CH 3 And (5) recrystallizing OH (v/v = 1: 0.5-3) to obtain a compound B, namely the styrene hemicyanine fluorescent dye.
Example 2
Cyclodextrin modification-1
1g of beta-cyclodextrin, 0.05g of benzene, 0.01g of silane coupling agent and 100g of ethanol are prepared into a dilute solution Y1, ultrasonic dispersion is carried out for 30min, and standing is carried out for 24h, so as to obtain the modified beta-cyclodextrin Z1.
Example 3
Cyclodextrin modification-2
1g of hydroxypropyl beta-cyclodextrin, 0.05g of benzene, 0.005g of titanate coupling agent and 200g of water are prepared into a dilute solution Y2, ultrasonic dispersion is carried out for 45min, and standing is carried out for 24h, thus obtaining the modified hydroxypropyl beta-cyclodextrin Z2.
Example 4
Cyclodextrin modification 3
1g of hydroxybutyl beta-cyclodextrin, 0.5g of benzene, 0.02g of aluminate coupling agent and 300g of water are prepared into a dilute solution Y3, ultrasonically dispersed for 60min and kept stand for 18h to obtain the modified hydroxybutyl beta-cyclodextrin Z3.
Example 5
Cyclodextrin modification-4
Preparing a dilute solution Y3 from 1g of methyl beta-cyclodextrin, 0.3g of benzene, 0.015g of silane coupling agent and 200g of isoamyl alcohol, carrying out ultrasonic dispersion for 15min, and standing for 12h to obtain the modified methyl beta-cyclodextrin Z4.
Example 6
Cyclodextrin modification 5
Preparing a dilute solution Y4 from 1g of methyl beta-cyclodextrin, 0.5g of benzene, 0.015g of titanate coupling agent and 200g of toluene, ultrasonically dispersing for 30min, and standing for 24h to obtain the modified methyl beta-cyclodextrin Z5.
Example 7
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) preparing 1G Z1 and 100G toluene into G1 dilute solution, ultrasonically dispersing for 30min, and standing for 24 h.
(2) 2G of a styrene hemicyanine fluorescent dye was added to G1, and the reaction was stirred at 800 rpm for 6H at 25 ℃ to obtain H1.
(3) Drying H1 at 110 deg.C for 4H, taking out, and grinding into powder to obtain light conversion agent I1.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I1 and 2g SrAl 2 O 4 : Eu 2+ ，Dy 3+ And 100g of toluene is prepared into J1 solution, the solution is stirred for 10min at 800 rpm at 35 ℃, then heated to 70 ℃, 0.05g of silane coupling agent and 0.01g of acrylic acid are added, the stirring is continued for 60min, the filtrate is separated, the solid is frozen and dried for 24h, and then taken out to be ground and sieved, thus obtaining the rare earth colorful long afterglow luminescent material K 1 。
Example 8
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) preparing 1G Z2 and 200G isoamylol into G2 dilute solution, carrying out ultrasonic dispersion for 15min, and standing for 6 h.
(2) 1G of a styrene hemicyanine fluorescent dye was added to G2, and the reaction was stirred at 900 rpm at 45 ℃ for 2H to obtain H2.
(3) Drying H2 at 140 deg.C for 4H, taking out, and grinding into powder to obtain light conversion agent I2.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I2 and 5g SrAl 2 O 4 : Eu 2+ ，Dy 3+ Preparing J2 solution with 200g ethanol, stirring at 400 rpm for 30min at 25 deg.C, heating to 90 deg.C, adding 0.02g titanate coupling agent and 0.02g acrylic acid, stirring for 60min, separating filtrate, freeze drying for 12 hr, grinding, and sieving to obtain rare earth colorful long afterglow luminescent material K 2 。
Example 9
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) 1G Z3, 300G of water and 200G of toluene are prepared into G3 dilute solution, ultrasonic dispersion is carried out for 20min, and standing is carried out for 24 h.
(2) 0.67G of a styrene hemicyanine fluorescent dye was added to G3, and the reaction was stirred at 1000 rpm for 4H at 60 ℃ to obtain H3.
(3) Drying H3 at 70 deg.C for 24H, taking out, and grinding into powder to obtain light conversion agent I3.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I3 and 10g SrAl 2 O 4 : Eu 2+ ，Dy 3+ Mixing with 300g m-xylene to obtain J3 solution, stirring at 60 deg.C and 700 rpm for 20min, addingHeating to 80 deg.C, adding 0.01g aluminate coupling agent and 0.01g silicone oil, stirring for 30min, separating filtrate, freeze drying for 24 hr, grinding, and sieving to obtain rare earth colorful long afterglow luminescent material K 3 。
Example 10
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) preparing 1G Z4 and 300G ethanol into G4 dilute solution, ultrasonically dispersing for 30min, and standing for 12 h.
(2) 1.5G of a styrene hemicyanine fluorescent dye was added to G4, and the reaction was stirred at 600 rpm for 5H at 40 ℃ to obtain H4.
(3) Drying H4 at 105 deg.C for 10H, taking out, and grinding into powder to obtain light conversion agent I4.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I4 and 7g SrAl 2 O 4 : Eu 2+ ，Dy 3+ Mixing with 250g of isoamyl alcohol to prepare a J4 solution, stirring at the temperature of 40 ℃ and the rpm of 600 for 10min, heating to 75 ℃, adding 0.03g of silane coupling agent and 0.03g of silicone oil, continuously stirring for 40min, separating filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful long-afterglow luminescent material K 4 。
Example 11
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) preparing 1G Z2 and 200G ethanol into G5 dilute solution, ultrasonically dispersing for 15min, and standing for 24 h.
(2) 1G of a styrene hemicyanine fluorescent dye was added to G5, and the reaction was stirred at 1200rpm at 50 ℃ for 12H to obtain H5.
(3) Drying H5 at 80 deg.C for 12H, taking out, and grinding into powder to obtain light conversion agent I5.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I5 and 5g SrAl 2 O 4 : Eu 2+ ，Dy 3+ Mixing with 200g ethanol to obtain J5 solution, stirring at 35 deg.C and 700 rpm for 20min, heating to 85 deg.C, adding 0.02g aluminate coupling agent and 0.05g acrylic acid, stirring for 60min,separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful long-afterglow luminescent material K 5 。
Example 12
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) preparing 1G Z3 and 200G water into G6 dilute solution, ultrasonically dispersing for 30min, and standing for 6 h.
(2) 0.5G of a styrene hemicyanine fluorescent dye was added to G6, and the reaction was stirred at 600 rpm for 2H at 40 ℃ to obtain H6.
(3) Drying H6 at 100 deg.C for 12H, taking out, and grinding into powder to obtain light conversion agent I6.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
1g I6 and 3g SrAl 2 O 4 : Eu 2+ ，Dy 3+ Preparing a J6 solution with 200g of m-xylene, stirring at 400 rpm for 30min at 35 ℃, heating to 90 ℃, adding 0.01g of silane coupling agent and 0.01g of acrylic acid, continuing stirring for 60min, separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and sieving to obtain the rare earth colorful long-afterglow luminescent material K 6 。
Example 13
The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
(1) 1G Z3 and 200G of water are prepared into G7 dilute solution, ultrasonic dispersion is carried out for 30min, and standing is carried out for 12 h.
(2) 1G of a styrene hemicyanine fluorescent dye was added to G7, and the reaction was stirred at 600 rpm for 5H at 40 ℃ to give H7.
(3) Drying H7 at 105 deg.C for 10H, taking out, and grinding into powder to obtain light conversion agent I7.
(II) the preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
mixing 1g I7 and 5gSrAl 2 O 4 : Eu 2+ ，Dy 3+ Mixing with 200g of isoamyl alcohol to prepare a J7 solution, stirring at 600 rpm for 10min at 40 ℃, heating to 75 ℃, adding 0.02g of silane coupling agent and 0.02g of acrylic acid, continuously stirring for 40min, separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful rare earthLong afterglow luminescent material K 7 。
Comparative example 1
(1) The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
1) 1G of styrene hemicyanine fluorescent dye and 200G of water are prepared into G 8 Diluting the solution, ultrasonically dispersing for 30min, and standing for 12 h.
2）G 8 Stirring the reaction at 600 rpm for 5H at 40 ℃ to obtain H 8 。
3) H is to be 8 Drying at 105 deg.C for 10h, taking out, and grinding into powder to obtain light conversion agent I 8 。
(2) The preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
will be 1g I 8 And 5g SrAl 2 O 4 ：Eu 2+ ,Dy 3+ Prepared with 200g of isoamyl alcohol to obtain J 8 Stirring the solution at the temperature of 40 ℃ and the rpm of 600 for 10min, heating to 75 ℃, adding 0.02g of silane coupling agent and 0.02g of acrylic acid, continuing stirring for 40min, separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful long-afterglow luminescent material K 8 。
Comparative example 2
(1) The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
1) 1G Z3 was mixed with 200G of water to give G 9 Diluting the solution, ultrasonically dispersing for 30min, and standing for 12 h.
2）G 9 Stirring the reaction at 600 rpm for 5H at 40 ℃ to obtain H 9 。
3) Will H 9 Drying at 105 deg.C for 10h, taking out, and grinding into powder to obtain light conversion agent I 9 。
(2) The preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
will be 1g I 9 And 5g SrAl 2 O 4 ：Eu 2+ ,Dy 3+ Prepared with 200g of isoamyl alcohol to obtain J 9 Stirring the solution at the temperature of 40 ℃ and the rpm of 600 for 10min, heating to 75 ℃, adding 0.02g of silane coupling agent and 0.02g of acrylic acid, continuing stirring for 40min, separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful long-afterglow luminescent material K 9 。
Comparative example 3
(1) The preparation method of the high-efficiency light conversion inclusion compound comprises the following steps:
is free of
(2) The preparation method of the rare earth colorful long afterglow luminescent material comprises the following steps:
5g of SrAl 2 O 4 ：Eu 2+ ,Dy 3+ Prepared with 200g of isoamyl alcohol to obtain J 10 Stirring the solution at the temperature of 40 ℃ and the rpm of 600 for 10min, heating to 75 ℃, adding 0.02g of silane coupling agent and 0.02g of acrylic acid, continuing stirring for 40min, separating the filtrate, freeze-drying the solid for 48h, taking out, grinding and screening to obtain the rare earth colorful long-afterglow luminescent material K 10 。
SrAl 2 O 4 ：Eu 2+ ,Dy 3+ Untreated as a blank K 0 Photochromic adjustable rare earth long afterglow luminescent material K obtained in examples 1-7 and comparative examples 1-3 1 -K 10 See fig. 1.
The foregoing is only a preferred embodiment of the present invention and it should be noted that modifications and variations can be made by those skilled in the art without departing from the principle of the present invention and these modifications and variations should also be considered as the protection scope of the present invention.

Claims (10)

1. The styrene hemicyanine fluorescent dye is characterized by having a structural formula as follows:
Figure DEST_PATH_IMAGE001
。
2. a method for preparing the styrene hemicyanine fluorescent dye of claim 1, which comprises the steps of:
(1) reacting N-methyldiphenylamine with phosphorus oxychloride in N, N-dimethylformamide to obtain a compound A, namely 4, 4' - (methylamine) bis-benzaldehyde;
(2) and reacting the compound A with 1, 4-dimethylpyridine iodide to obtain the styrene hemicyanine fluorescent dye.
3. The method for preparing a styrene hemicyanine fluorescent dye according to claim 2, wherein the step (1) specifically comprises:
1) putting the flask into ice water containing NaCl, and adding N, N-dimethylformamide after the flask body is completely cooled;
2) slowly dripping phosphorus oxychloride into the flask, keeping the temperature change in the dripping process within the range of 0-5 ℃, and forming a viscous state after the dripping is finished;
3) removing the NaCl-containing ice water bath, and continuously stirring at 600-1200 rpm for 10-60 min at 20-40 ℃ in a nitrogen atmosphere;
4) dissolving N-methyldiphenylamine in N, N-dimethylformamide, and dropwise adding into the flask containing the viscous mixture by using an injector;
5) heating the flask to 50-90 ℃, and continuously reacting for 0.5-3 h under the protection of nitrogen;
6) transferring the reaction liquid in the flask into an ice water mixture, and then adjusting the pH value of the reaction liquid to 6.5-7.5 by using a sodium carbonate solid;
7) extracting with dichloromethane, drying with anhydrous sodium sulfate, and concentrating under reduced pressure;
8) separating and purifying with silica gel chromatographic column, and eluting with ethyl acetate/petroleum ether to obtain compound A.
4. The method for preparing a styrene hemicyanine fluorescent dye according to claim 2, wherein the step (2) is specifically as follows:
1) adding the compound A and 1, 4-dimethylpyridine iodonium salt into ethanol;
2) carrying out reflux reaction at 60-90 ℃ for 2-8 h to obtain black purple precipitate;
3) subjecting the precipitate to CH treatment 2 C l2 /CH 3 And (4) recrystallizing OH (v/v = 1: 0.5-3) to obtain a compound B, namely the styrene hemicyanine fluorescent dye.
5. A rare earth colorful long afterglow luminescent material prepared by the styrene hemicyanine fluorescent dye of claim 1, which is characterized in that: the rare earth colorful long-afterglow luminescent material comprises the following components:
the component A comprises: one of beta-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxybutyl beta-cyclodextrin and methyl beta-cyclodextrin;
the component B comprises: a styrene hemicyanine fluorescent dye;
and the component C is as follows: rare earth long afterglow luminescent material SrAl 2 O 4 ：Eu 2+ ,Dy 3+ ；
And (D) component: one of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the component E is one of silicone oil, acrylic acid and ethyl orthosilicate;
and F component: at least one of water, ethanol, toluene, m-xylene and isoamyl alcohol;
and (2) component X: benzene.
6. The method for preparing the rare earth colorful long afterglow luminescent material as claimed in claim 5, which is characterized in that: the method comprises the following steps:
(1) modifying cyclodextrin: a, X, D and F are prepared into a dilute solution Y, ultrasonic dispersion is carried out for 15-60 min, and standing is carried out for 12-24 h, so as to obtain modified cyclodextrin Z;
(2) preparing a high-efficiency light conversion inclusion compound: preparing a G dilute solution from Z and F, carrying out ultrasonic dispersion for 15-90 min, and standing for 6-24 h; then adding B, stirring and reacting for 1-12H at the temperature of 25-60 ℃ and the rpm of 400-; finally, drying the H at 70-140 ℃ for 4-24H, taking out and grinding the H into powder to obtain a light conversion agent I;
(3) preparing a rare earth colorful long-afterglow luminescent material: preparing solution J from the I, the C and the F obtained in the step (2), stirring at 400-1200rpm at 25-60 ℃ for 5-30min, heating to 70-100 ℃, adding the D and the E, continuously stirring for 20-90min, separating the filtrate, freeze-drying the solid for 12-48h, taking out, grinding and screening to obtain the rare earth colorful long afterglow luminescent material.
7. The method for preparing rare earth colorful long afterglow luminescent material according to claim 6, characterized in that: the mass ratio of A, X, D to F in the step (1) is 1: 0.05-0.5: 0.005-0.02: 100 to 300.
8. The method for preparing rare earth colorful long afterglow luminescent material according to claim 6, characterized in that: in the step (2), the mass ratio of Z to F is 1: 100-500, and the mass ratio of B to A in G is 1: 0.5-2.
9. The method for preparing rare earth colorful long afterglow luminescent material according to claim 6, characterized in that: the mass ratio of I, C to F in the step (3) is 1: 2-10: 100-300.
10. The method for preparing rare earth colorful long afterglow luminescent material according to claim 6, characterized in that: in the step (3), the mass ratio of D to I is 1: 20-100; the mass ratio of E to I is 1: 20-100.
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