CN1317334C - Intermolecular charge transfer type fluorescent dyes and use thereof - Google Patents
Intermolecular charge transfer type fluorescent dyes and use thereof Download PDFInfo
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- CN1317334C CN1317334C CNB2004100382892A CN200410038289A CN1317334C CN 1317334 C CN1317334 C CN 1317334C CN B2004100382892 A CNB2004100382892 A CN B2004100382892A CN 200410038289 A CN200410038289 A CN 200410038289A CN 1317334 C CN1317334 C CN 1317334C
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Abstract
The present invention relates to an intramolecular charge transfer type fluorescent dye and a preparation method thereof. Three excellent cavity transmission groups of triphenylamine, carbazole and phenothiazine are used as electron donors; nitrile groups with strong philic-electronic capability are used as electron acceptors; a series of P-shaped luminescent materials are prepared by the connection of C=N conjugated pi bonds formed through simple condensation reaction. The fluorescent dye prepared by the present invention is used as a red luminescent dye to be adulterated into a conjugated polymer. Experimental results indicate that the material is a red electroluminescent material with pure emission.
Description
Technical field
The present invention relates to a kind of electric charge in molecule transfer type fluorescence dye.
The invention still further relates to the preparation method of above-mentioned fluorescence dye.
The invention still further relates to the application of above-mentioned fluorescence dye.
Background technology
Organic electroluminescence device is a kind of novel technique of display that progressively tends to ripe in the present photoelectric device field and huge practical prospect is arranged.From Kodak (Tang, C.W. in 1987; Vanslyke, S.A.Appl.Phys.Lett.1987,51,913.) released efficiently since the organic electroluminescence device, rely on that its glow color is adjustable, high brightness, high-level efficiency, wide viewing angle, low power consumption, preparation technology are simple, can prepare excellent specific property and the potential application in the panchromatic demonstration of large-area flat-plate field such as crooked gentle screen, attracted the extensive concern of scientific circles and playing an active part in of international renowned company and mechanism, generally believed it is the most competitive technology in the technique of display of new generation.At present, though the existing commodity selling of display of organic electroluminescence, commercial process is significantly less than people's expectation, and one of them key reason is exactly the material that lacks excellent performance.Based on the panchromatic displaying scheme of red, green, blue three primary colours, but high performance green is of a great variety and practicability, the making much progress of blue emitting material, and red illuminating material then relatively obviously lacks.Therefore, the red illuminating material of exploitation excellent performance seems particularly important.
The electric charge in molecule transfer type fluorescence dye is the conjugated structure that is formed by connecting by a conjugated bridge by electron donor(ED) and electron acceptor(EA), between electron donor(ED) and the acceptor charge transfer takes place, and causes dyestuff to launch the light of long-wave band.Electron donor(ED) and acceptor of a great variety, and by suitable chemically modified, just can change the intrinsic performance (as glow color) of material, thereby this class material is synthesized and is applied in the photoelectric device field by design widely, such as biological fluorescent labeling, nonlinear optics, solar cell etc., especially in red electroluminescent field, occupy even more important status.The Tang of Kodak, C.W. etc. are doped to electric charge in molecule transfer type red luminescent dye DCM in the 8-hydroxyquinoline aluminum, have obtained first organic red electroluminescent device (Tang, C.W.; VanSlyke, S.A.; Chen, C.H.J.Appl.Phys.1989,65,3610.).Thereby, constantly developed based on the charge transfer type red light material of DCM configuration.At present, this type dyestuff mostly is and only contains the asymmetrical molecular structure of D-π-A (1:Chen, the C.H. that an electric charge is given a body and a charge receptor; Shi, J.; Tang, C.W.; Et al.Thin Sold Films, 2000,363,327.2:Wang, P.F.; Xie, Z.Y.; Lee, S.T.Chem.Mater.2003,15,1913.), because its strong charge transfer effect, the fluorescent quenching phenomenon is very serious; In order to overcome this problem, preparation of devices all adopts doping way, how with 8-hydroxyquinoline aluminum as the doped body material, incomplete energy shifts and causes device to present impure red emission (590-615nm), and the peak width at half height broad (greater than 100nm) of emission band, this is difficult to satisfy the strict demand of organic electroluminescence device to colourity.Add and help dopant, carry out transmission ofenergy (Hamada, Y. twice; Kanno, H.; Tsujioka, T.; Takahashi, H.; Usuki, T.Appl.Phys.Lett.1999,75,1682.), though improved the luminous of device to a certain extent; But make device preparing process complicated, lack operability.
Molecule with D-π-A-π-D symmetrical configurations contains two electric charges gives body, has two charge transferring channels, unique.Yet they but are that the by product in synthetic occurs as DCM class dyestuff the earliest, and viewpoint in the past thinks that symmetric molecule autofluorescence efficient is very low, even do not have fluorescence, can not be as luminescent material (Chen, C.H.; Tang, C.W.; Shi, J.MacromoleculesSymp, 1998,125,49.), therefore, the design of material and synthetic in all make great efforts to avoid the generation of this type compound.Yet people's such as Shim research but obtains unexpected result (Jung, B.J.; Yoon, C.B.; Shim, H.K.Adv.Func.Mater.2001,11,430.), be luminescent layer with the Compound D ADB of D-π-A-π-D symmetrical configurations, bright emitting red light produces, and the molecule of visible symmetrical configurations still can become the alternative of red light material.
At present, the material of saturated red emission still lacks, and rarely has document and patent report about having D-π-charge transfer type fluorescence dye of A-π-D configuration and the application in organic electroluminescent LED thereof.
Summary of the invention
The object of the present invention is to provide a kind of electric charge in molecule transfer type fluorescence dye.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned fluorescence dye,
Charge transfer type fluorescence dye with symmetrical molecule configuration provided by the invention, its structural formula be as shown in Equation 1:
(formula 1)
R is the aromatic heterocyclic electron donor(ED) in the formula: carbazole, thiodiphenylamine or triphenylamine and substitutive derivative thereof.
When electron donor(ED) be carbazoles structure as shown in Equation 2;
(formula 2)
R ' is alkyl, aryl or substituted aryl in the formula.
When electron donor(ED) be phenothiazines structure as shown in Equation 3;
(formula 3)
R ' is alkyl, aryl or substituted aryl in the formula.
When electron donor(ED) be the triphen amine structure as shown in Equation 4;
(formula 4)
R in the formula " be that hydrogen or carbon number are 1～3 alkyl
The method of the above-mentioned fluorescence dye of preparation provided by the invention, be as electron donor(ED) with triphenylamine, carbazole and three kinds of outstanding cavity transmission groups of thiodiphenylamine, itrile group with stronger electrophilic ability is as electron acceptor(EA), the C=N conjugated that forms by simple condensation reaction connects, and has prepared a series of P type luminescent material.
The fluorescence dye of the present invention's preparation is dye adulterated in conjugated polymers as emitting red light, and experimental result shows that this type of material is the red electroluminescent materials that a class has pure emission.
The present invention prepares the method for fluorescence dye, and key step is:
(1) prepared phosphorus oxychloride and N, the mixing solutions a of N-dimethyl-methane amide in 1: 1 by volume;
(2) N of preparation electron donor(ED), the mixing solutions b of N-dimethyl-methane amide, the concentration of electron donor(ED) is 1-3mol/L; Described electron donor(ED) is 9-alkyl carbazole, 9-aryl carbazole, 9-substituted aryl carbazole, 10-alkyl thiodiphenylamine, 10-aryl thiodiphenylamine, 10-substituted aryl thiodiphenylamine or triphenylamine and substituent thereof;
(3) add 4-7 ml soln a, reflux 10-20 hour among every ml soln b;
(4) step 3 product is added in 33% the aqueous sodium carbonate and stirred 0.5-2 hour, the volume ratio of step 3 product and aqueous sodium carbonate is 1: 2-5;
(5) step 4 product dichloromethane extraction separates and drying, and organic solvent is removed in evaporation, gets the electron donor(ED) of aldehyde radicalization;
(6) electron donor(ED) and the diamino succinonitrile of the aldehyde radicalization that obtains of step 5 are dissolved in the glacial acetic acid in the 0.5-2mmol/ml ratio, and the mol ratio of diamino succinonitrile and aldehyde radical electron donor(ED) is 1: 1.5-3;
(7) adding diacetyl oxide in the glacial acetic acid solution of step 6 is catalyzer, catalyzer and glacial acetic acid solution volume ratio 0.15-0.4: 5; Under the nitrogen atmosphere, 100-140 ℃ reflux 3-7 hour; Cool off, reactant places cold water, and dichloromethane extraction separates and drying, and organic solvent is removed in evaporation, gets target product.
Major advantage of the present invention is:
1. selected raw material reagent is all common agents, and intermediate is synthetic simple; Double condensation reaction carries out easily, does not need expensive catalysts; By product is easily separated; The target product productive rate is higher, and purity is good.
2. three materials all have good solubility, dissolve in fully in the organic solvents commonly used such as toluene, chloroform, tetrahydrofuran (THF).
3. the highest occupied molecular orbital of material (HOMO) energy level is higher, helps the injection and the transmission in hole.
4. the glow color of material is controlled, regulates the electric charge of material and gives body, and the emission of controlled material obtains pure narrow band red emission.
The fluorescence dye of the present invention's preparation has certain cavity transmission ability, can be used as red illuminating material and is applied in the organic electroluminescence device.
Description of drawings
Fig. 1 a is the uv-absorbing of series dyes Dye1-3;
Fig. 1 b is the fluorescence spectrum of series dyes Dye1-3;
Fig. 2 is the cyclic voltammetry curve of dyestuff Dye2;
Fig. 3 is the film uv-absorbing and the fluorescence spectrum of dyestuff Dye2 and material of main part;
Fig. 4 a is the film fluorescence spectrum under the different doping ratios with material of main part of dyestuff Dye2;
Fig. 4 b is the electroluminescent spectrum for the photodiode under the different doping ratios with material of main part of dyestuff Dye2;
Fig. 5 is the current-voltage curve of the photodiode under the different doping ratios with material of main part of dyestuff Dye2.
Embodiment
Synthetic route as shown in Figure 1.
1. the embodiment of reaction process a (with synthetic 9-(2 '-ethyl)-hexyl carbazole, compound 1 is an example):
In the there-necked flask of 100ml, under nitrogen protection, sodium hydroxide (0.18ml) is joined in dimethyl sulfoxide (DMSO) (DMSO) solution (60ml), vigorous stirring is after half an hour, and carbazole (0.03mol) joins in the above-mentioned system; Stir after 1 hour, 2-ethyl-hexyl bromide (0.03mol) slowly splashes into; Stirring at room 12 hours, reaction finishes.Concentrated reaction solution is removed part DMSO, pours in the water, with dichloromethane extraction repeatedly.Merge organic phase, anhydrous magnesium sulfate drying.Rotary evaporation in vacuo is removed organic solvent, and crude product is purified (leacheate-sherwood oil) through silica gel column chromatography, and product is lurid oily matter 9-(2 '-ethyl)-hexyl carbazole (productive rate 73%).
Adopt identical synthesis technique,, can obtain corresponding 9-alkyl carbazole, 9-aryl carbazole, 9-substituted aryl carbazole with the 2-ethyl-hexyl bromide in other alkyl bromide, aryl bromide, the substituted aryl bromine alternative reaction; Replace carbazole with thiodiphenylamine again, can obtain corresponding 9-alkyl thiodiphenylamine, 9-aryl thiodiphenylamine, 9-substituted aryl thiodiphenylamine.
2. the embodiment of reaction process b (with synthetic aldehyde radical triphenylamine, compound 3 is an example):
In the there-necked flask of 100ml, with the N of phosphorus oxychloride (0.12ml), (DMF solution slowly is added drop-wise in the DMF solution of triphenylamine (0.04mol) N-dimethyl-methane amide, dropwises reflux 15 hours; Reaction finishes, and mixing solutions becomes black thick, pours in the aqueous sodium carbonate of 33% (w/w), stirs 1 hour; Use dichloromethane extraction, merge organic phase, anhydrous magnesium sulfate drying; Rotary evaporation in vacuo is removed organic solvent, and crude product is purified through silica gel column chromatography, and (leacheate-methylene dichloride/sherwood oil 1: 2v/v), product is light yellow solid aldehyde radical triphenylamine (productive rate 69%).
Adopt identical synthesis technique, with the triphenylamine in substituted carbazole, substituted phenothiazine or the replacement triphenylamine alternative reaction, can obtain corresponding 3-aldehyde radical-9-alkyl carbazole, 3-aldehyde radical-9-aryl carbazole, 3-aldehyde radical-9-substituted aryl carbazole, 3-aldehyde radical-9-alkyl thiodiphenylamine, 3-aldehyde radical-9-aryl thiodiphenylamine, 3-aldehyde radical-9-substituted aryl thiodiphenylamine or replace the triphen amino-aldehyde.
3. the embodiment of reaction process c:
Embodiment (1): N, N '-two-[9-(2 '-ethyl-hexyl)-carbazole-vinyl]-succinonitrile (Dye 1)
In the there-necked flask of 100ml, 3-aldehyde radical-9-(2 '-ethyl-hexyl)-carbazole (42mmol) and diamino succinonitrile (20mmol) are placed the glacial acetic acid of about 40ml, add several diacetyl oxides as catalyzer, under nitrogen atmosphere, in 120 reflux 5 hours; After reaction stops, being cooled to room temperature, mixture is poured in the 150ml water, place after 4 hours, water dichloromethane extraction (60ml * 2); Merge organic phase, wash with water, anhydrous magnesium sulfate is in dry.Rotary evaporation in vacuo is removed organic solvent, and crude product is through silica gel column chromatography purification (leacheate-methylene dichloride/sherwood oil 1: 1v/v), obtain having the dark red solid (productive rate 72%) of metalluster.
Mass spectrum (MALDI-TOF-MS): m/z calculated value 686.4, observed value 687.6 (M
+);
Nucleus magnetic hydrogen spectrum (
1H-NMR) (300MHz, CDCl
3, ppm): δ=0.87-0.99 (m, 12H), 1.31-1.44 (broad, 16H), 2.11-2.14 (broad, 2H), 4.17-4.25 (d, 4H), 7.37-7.40 (t, 2H), 7.42-7.58 (m, 6H), 8.19-8.24 (d, 4H), 8.68 (s, 2H), 8.95 (s, 2H);
Ultimate analysis (Elemental analysis) calculated value C
46H
50N
6(%): C 80.43, and H 7.34, and N 12.23; Observed value C 80.04, H 7.37, N 12.04.
Embodiment (2): N, N '-two-(triphenylamine)-vinyl-succinonitrile (Dye 2)
In the there-necked flask of 100ml, aldehyde radical triphenylamine (42mmol) and diamino succinonitrile (20mmol) are placed the glacial acetic acid of about 40ml, add several diacetyl oxides as catalyzer, under nitrogen atmosphere, in 120 reflux 5 hours; After reaction stops, being cooled to room temperature, mixture is poured in the 150ml water, place after 4 hours, water dichloromethane extraction (60ml * 2); Merge organic phase, wash anhydrous magnesium sulfate drying with water.Rotary evaporation in vacuo is removed organic solvent, and crude product is through silica gel column chromatography purification (leacheate-methylene dichloride/sherwood oil 1: 1v/v), obtain having the dark red solid (productive rate 72%) of metalluster.
Mass spectrum (MALDI-TOF-MS): m/z calculated value 618.3; Observed value 618.4.
Nucleus magnetic hydrogen spectrum (
1H-NMR) (300MHz, CDCl
3, ppm): δ=7.03 (d, 4H), 7.19-7.22 (t, 12H), 7.32-7.36 (t, 8H), 7.78-7.80 (d, 4H), 8.61 (s, 2H);
Ultimate analysis (Elemental analysis) calculated value: C
42H
30N
6(%): C 81.53, and H 4.89, and N 13.58; Observed value: C 81.54, H 4.93, N 13.60.
Embodiment (3): N, N '-two-[9-(2 '-ethyl-hexyl)-thiodiphenylamine-vinyl]-succinonitrile (Dye3)
In the there-necked flask of 100ml, 3-aldehyde radical-9-(2 '-ethyl-hexyl)-thiodiphenylamine (42mmol) and diamino succinonitrile (20mmol) are placed the glacial acetic acid of about 40ml, add several diacetyl oxides as catalyzer, under nitrogen atmosphere, in 120 reflux 5 hours; After reaction stops, being cooled to room temperature, mixture is poured in the 150ml water, place after 4 hours, water dichloromethane extraction (60ml * 2); Merge organic phase, wash anhydrous magnesium sulfate drying with water.Rotary evaporation in vacuo is removed organic solvent, and crude product is through silica gel column chromatography purification (leacheate-methylene dichloride/sherwood oil 1: 1v/v), obtain having the dark red solid (productive rate 72%) of metalluster.
Mass spectrum (MALDI-TOF-MS) m/z: calculated value 750.4; Observed value 750.3;
Nucleus magnetic hydrogen spectrum (
1H-NMR) (300MHz, CDCl
3, ppm): δ=0.86-0.93 (t, 12H), 1.25-1.29 (t, 8H), 1.40-1.47 (m, 8H), 1.96-1.98 (t, 2H), 3.84 (s, 4H), 6.92-7.01 (m, 6H) 7.18-7.22 (d, 4H), 7.82 (d, 4H), 8.64 (s, 2H);
Ultimate analysis (Elemental analysis) calculated value C
46H
50N
6S
2(%): C 73.56, and H 6.71, and N 11.19; Calculated value C 72.94, H 6.66, N 11.10.
4. photophysical property
Dyestuff Dye1-3 in chloroformic solution uv-absorbing and fluorescence spectrum as shown in Figure 2.Along with the power supply capacity increase that electric charge in the molecular structure is given body, the equal red shift of the absorption of dyestuff and emmission spectrum: the absorption peak of dyestuff lays respectively at 506nm, 550nm and 556nm; Emission peak lays respectively at 552nm, 628nm and 685nm.With Luo Dan name B is reference (Parker, C.A.; Rees, W.T.Analyst, 1960,85,578.), measured the fluorescence quantum efficiency of dyestuff, the fluorescence quantum efficiency of dyestuff Dye2 is 39%.
5. electrochemical properties
The electrochemical properties of cyclic voltammetry test dye, test is at computer-controlled EG﹠amp; Carry out on GPotentiostat/Galvanostat model 283 electrochemical analysers.Adopt three traditional electrode test systems, platinum electrode is a working electrode, and Ag/AgCl is as reference electrode, and platinum filament is as counter electrode; Sample is dissolved in the methylene dichloride (1 * 10 of new steaming
-3M), Bu
4NPF
6(0.1M) as supporting electrolyte.Fig. 3 is the current voltage characteristic of dyestuff Dye2, and wherein forward has a pair of reversible redox peak, and negative sense has an irreversible oxidation peak, illustrates that this material is the P type.Method (Pommerehne, J. according to document; Vestweber, H.; Guss, W.; Et al., Adv.Mater.1995,7,551.), be the energy level that benchmark calculates dyestuff with the ferrocene.The HOMO energy level of three dyestuffs is respectively-5.546eV ,-5.351eV and-5.169eV, all can compare, so they will help the injection and the transmission in hole with the HOMO energy level of the hole mobile material TPD of classics.
6. luminosity
Shown dyestuff Dye2 and polymer body material uv-absorbing and the fluorescence spectrum under filminess among Fig. 4.Between the emission spectrum of polymer body and the absorption band of dyestuff sufficient overlapping is arranged, indicating that energy shifts efficiently.Fig. 5 a be dyestuff Dye2 with material of main part with the film photoluminescence spectrum under the different doping ratios, as can be seen, along with the increase of doping ratio, the energy trans effect increases gradually, the emission of polymer body weakens rapidly, up to completely dissolve, illustrates that energy shifts generation efficiently.We are anode with conductive glass ITO, and stable aluminium is negative electrode in the air, and 8-hydroxyquinoline aluminum is an electron transfer layer, and dyestuff Dye2 and polymer-doped system are luminescent layer, have prepared the luminescent device of serial simple structure.Along with the increase of doping content, the luminous pure red of convergence gradually luminous (shown in Fig. 5 b) of device.Doping ratio is 5% o'clock, device present the pure luminous 619nm of being positioned at, peak width at half height is 75nm only.Fig. 6 has provided electric current one voltage curve of the device under the different doping ratios, and the maximum external quantum efficiency of device is 0.38%.It is to be noted that this efficient is the result without the device of optimizing.The symmetrical charge transfer configuration fluorescence dye that has among the present invention will be the luminous pure red luminescent material of a class.
Claims (8)
1. electric charge in molecule transfer type fluorescence dye, its structure be as shown in Equation 1:
Formula 1
R is the aromatic heterocyclic electron donor(ED) in the formula: carbazole, thiodiphenylamine or triphenylamine and substitutive derivative thereof.
2. fluorescence dye as claimed in claim 1 is characterized in that, the structure that described aromatic heterocyclic electron donor(ED) is a carbazoles as shown in Equation 2:
Formula 2
R ' is alkyl, aryl or substituted aryl in the formula.
3. fluorescence dye as claimed in claim 1 is characterized in that, the structure that described aromatic heterocyclic electron donor(ED) is a phenothiazines as shown in Equation 3:
Formula 3
R ' is alkyl, aryl or substituted aryl in the formula.
4. fluorescence dye as claimed in claim 1 is characterized in that, the structure that described aromatic heterocyclic electron donor(ED) is the triphen amine as shown in Equation 4:
Formula 4
R in the formula " be that hydrogen or carbon number are the alkyl of 1-3.
5. method for preparing each described fluorescence dye of claim 1-4, key step is:
(1) prepared phosphorus oxychloride and N, the mixing solutions a of N-dimethyl-methane amide in 1: 1 by volume;
(2) N of preparation electron donor(ED), the mixing solutions b of N-dimethyl-methane amide, the concentration of electron donor(ED) is 1-3mol/L; Described electron donor(ED) is 9-alkyl carbazole, 9-aryl carbazole, 9-substituted aryl carbazole, 10-alkyl thiodiphenylamine, 10-aryl thiodiphenylamine, 10-substituted aryl thiodiphenylamine, triphenylamine or its substituent;
(3) add 4-7 ml soln a, reflux 10-20 hour among every ml soln b;
(4) step 3 product is added in 33% the aqueous sodium carbonate and stirred 0.5-2 hour, the volume ratio of step 3 product and aqueous sodium carbonate is 1: 2-5;
(5) step 4 product dichloromethane extraction separates and drying, and organic solvent is removed in evaporation, gets the electron donor(ED) of aldehyde radicalization;
(6) the aldehyde radical electron donor(ED) and the diamino succinonitrile that obtain of step 5 is dissolved in the glacial acetic acid in the 0.5-2mmol/ml ratio, and the mol ratio of diamino succinonitrile and aldehyde radical electron donor(ED) is 1: 1.5-3;
(7) adding diacetyl oxide in the glacial acetic acid solution of step 6 is catalyzer, catalyzer and glacial acetic acid solution volume ratio 0.15-0.4: 5; Under the nitrogen atmosphere, 100-140 ℃ reflux 3-7 hour; Cool off, reactant places cold water, and dichloromethane extraction separates and drying, and organic solvent is removed in evaporation, gets target product.
6. method as claimed in claim 4 is characterized in that the product that step 5 obtains is purified through silica gel column chromatography.
7. method as claimed in claim 4 is characterized in that the product that step 7 obtains is purified through silica gel column chromatography.
8. as the application of the described fluorescence dye of above-mentioned each claim in organic electroluminescence device.
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| CN101818055B (en) * | 2010-04-22 | 2013-03-13 | 苏州科技学院 | Triphenylamine group-containing quick fluorescence intensifier |
| CN113527285B (en) * | 2021-07-15 | 2023-09-05 | 中国林业科学研究院林产化学工业研究所 | D-A-pi-A-D fluorescent compound and preparation method thereof |
| CN115974846A (en) * | 2022-12-13 | 2023-04-18 | 深圳职业技术学院 | Synthetic method and application of organic dye fluorescent small molecule material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711802A2 (en) * | 1990-12-28 | 1996-05-15 | Dow Corning Corporation | Method of indicating a cure point for ultraviolet radiation curing compositions by color change |
| CN1049232C (en) * | 1994-09-29 | 2000-02-09 | 华东理工大学 | Fluorescent dye with double chromogens and preparing process thereof |
| CN1493645A (en) * | 2002-10-28 | 2004-05-05 | 中国科学院理化技术研究所 | Red fluorescent dye with star-shooting structure and synthetic method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711802A2 (en) * | 1990-12-28 | 1996-05-15 | Dow Corning Corporation | Method of indicating a cure point for ultraviolet radiation curing compositions by color change |
| CN1049232C (en) * | 1994-09-29 | 2000-02-09 | 华东理工大学 | Fluorescent dye with double chromogens and preparing process thereof |
| CN1493645A (en) * | 2002-10-28 | 2004-05-05 | 中国科学院理化技术研究所 | Red fluorescent dye with star-shooting structure and synthetic method and application thereof |
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