KR20030083030A - Polymer fluorophores for chemiluminescence comprising pherylene unit fluorophore, manufacturing method thereof, and chemiluminescent composition comprising the polymer fluorophores - Google Patents

Abstract

PURPOSE: Provided is a chemiluminescence polymer phosphor comprising a perylene unit, which is less harmful than conventional monomer phosphors and effectively transfers the energy converted from the chemical energy. CONSTITUTION: The chemiluminescence polymer phosphor comprising a perylene unit is obtained by the polycondensation of 1,6,7,12-tetrakis(4-tert-butylphenoxy)-3,4,9,10-perylene tetracarboxylic dianhydride represented by the formula 1 as a perylene phosphor unit, with a diamine having a pliable group through an imide bond. The chemiluminescence polymer phosphor is used in a chemiluminescence composition together with a chemical energy transferring system consisting of oxalate/peroxide/organic base that is capable of providing the chemical energy for the luminescence of the phosphor.

Description

Polymer fluorophores comprising a perylene unit phosphor, a method for manufacturing the same and a chemiluminescent composition comprising the polymer fluorophores {Polymer fluorophores for chemiluminescence comprising pherylene unit fluorophore, manufacturing method approx, and chemiluminescent composition comprising the polymer fluorophores}

The present invention relates to a polymer phosphor comprising a perylene unit phosphor, a method of manufacturing the same, and a chemiluminescent composition comprising the polymer phosphor. More specifically, the present invention relates to a polymeric fluorescent substance comprising a perylene unit phosphor as a monomer, a method for producing the same, and a method for producing the same, and a chemiluminescent composition comprising the polymeric fluorescent substance as a monomer. will be.

In chemiluminescence, some of the chemical reaction product is produced in an excited state and then emits light when it returns to the ground state. As represented by Equation 1, chemiluminescence includes a chemical reaction, and the intensity of emitted light is proportional to the chemiluminescence reaction rate and the quantum efficiency of the chemiluminescence reaction system.

[Equation 1]

Where I _CL is the intensity of emitted light, Φ _CL is the quantum efficiency (number of photons generated per reaction molecule) and dP (t) / dt is the reaction rate. The quantum efficiency of chemiluminescent systems is generally from 0.01 to 0.3. In general, the energy required to make the electronic excited state is obtained from a chemical reaction. In order to generate light having a wavelength of visible light, it must be a chemical reaction capable of generating at least 40 to 70 kcal / mol of energy. Most of these chemical reactions are oxidation / reduction reactions, which include dissociation of chemical bonds and electron transfer reactions. Chemiluminescence began in earnest with the development of a new light emission method using peroxyoxalate by the reaction of hydrogen peroxide and aryl oxalate esters (EA Chandross, Tetrahedron Lett. , 761 (1963). M; M. Rauhut, BG Roberts, and AM Semsel, J. Am. Chem. Soc. , 88, 3604 (1966); LJ Bollyky, M. Loy, BG Roberts, RH Whiteman, AV Lannotta, MM Rauhut, and AM Semsel, J. Am. Chem. Soc ., 89, 6515 (1967); LJ Bollyky, BG Roberts, and MM Rauhut, J. Am. Chem. Soc. , 89, 6523 (1967); LJ Bollyky, BG Robert.RH Whitman. And JE Lancaster, J. Org.Chem., 34, 836 (1969); DR Maulding, RA Clarke, BG Robert, and MM Rauhut, J. Org.Chem., 33, 250 (1968)) . Currently used chemiluminescent phosphors are 9,10-diphenylanthracene (9,10-diphenylanthracene), 9,10-bis (phenylethynyl) anthracene (9,10-bis (phenylethynyl) anthracene), perylene ( perylene) and rubrene (HF Mark et al, " Encyclopedia of Chemical Technology ", vol 5, John Wiley & Sons, New York, p. 416, 1979).

If the unit phosphor (molecular phosphor) can be introduced into the polymer main chain for chemiluminescence and can be made into a polymer phosphor, harmful properties can be removed when the phosphor is spilled, and the structure of the unit phosphor is regularly distributed in the polymer to give chemical energy. It will be possible to effectively transfer energy converted from

Compounds containing perylene units have been known and studied since 1913, and have been spotlighted as excellent photo-stable pigments and bat dyes. Pigments and dyes containing perylene units exhibit luminescent wavelengths at long wavelengths due to their extended resonances, and have recently been adapted to their derivative synthesis and various applications with various applications with very strong fluorescence.

They are not only light sticks, but also have various applications, such as fluorescent solar collectors, photovoltaic devices, dye lasers, molecular switches and organic light emitting devices. (Zolinger, H. color chemistry, New York, 1991).

Recently, perylenetetracarboxilic diimide and quaterylenetetracarboxilic acid diimide, which have expanded perylene units, have been synthesized. Due to the structure, the maximum light emission wavelength appears at about 665 to 780 nm. In addition, the quantum efficiency is close to about 1.0, and is also applied to potential ECL labels for analysis (Sang Kwon Lee, J. Chem. Soc ., 121, 3513-3520 (1999)). In addition, active research in the field of display has been applied and studied in organic electroluminescence, 1,6,7,12-tetraphenoxy-N, N'-bis (2,6-diisopropylphenyl)- Perylene-3,4,9,10-bis (dicarboxyimide) (1,6,7,12-tetraphenoxy-N, N'-bis (2,6-diisopropylphenyl) -perylene-3,4,9, 10-bis (dicarboximide) is being studied as an electron transport material (P. Ranke, Appl. Phy. Lett 71, (10) 1332-1334 (1997)). The thin film is formed by chemical vapor deposition (CVD), and its purity and deposition conditions are very difficult to polymerize to form a film by spin coating (P. Ranke, Appl. Phy. Lett 71. (10) 1332-1334 (1997); HW Schmidt et al. Synthetic Metals 102, 1110-1112). However, perylene and 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride) containing perylene units have poor solubility, stability, and processability in organic solvents. Its applicability is poor.

The present inventors improve the solubility in organic solvents by introducing a flexible group and an aromatic ring such as a phenoxy group, deimidize the synthesized phosphor, and imide bonds with the diamine containing a soft group to the organic solvent. Synthesis of a polymeric fluorescent substance comprising perylene units, which can be applied as a red chemiluminescent substance, as a unit phosphor, which enhances solubility and stability, and investigates its luminescence properties as a phosphor and an organic electroluminescent substance of chemiluminescence. A polymer fluorescent substance containing a unit was synthesized, and it was confirmed that it could be used as a fluorophore, thus completing the present invention.

An object of the present invention is to introduce a perylene unit phosphor into the polymer backbone, which is less harmful than the conventional monomer phosphors when the phosphor is leaked, and the perylene unit phosphor as a fluorescent substance is regularly distributed to transfer energy converted from chemical energy It is to provide a polymer phosphor comprising a perylene unit phosphor having an advantage that can be effectively.

Another object of the present invention is to provide a method for producing a polymer phosphor comprising a perylene unit phosphor as described above.

Still another object of the present invention is to provide a chemiluminescent composition comprising a polymer phosphor comprising a perylene unit phosphor as described above.

1 is an ultraviolet / visible light absorption spectrum of TTBPDA and a polymer phosphor used as a unit phosphor in the present invention.

2 is a light emission spectrum of TTBPDA and polymer phosphors used as unit phosphors in the present invention.

3 is a chemiluminescence spectrum of TTBPDA and polymer phosphors used as unit phosphors in the present invention.

Figure 4 is a spectrum showing the emission duration of the TTBPDA used as the unit phosphor in the present invention and the polymer phosphors of Examples 1 and 2 of the present invention.

The polymeric fluorescent substance including the perylene unit phosphor according to the present invention is 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10 as the perylene unit phosphor of Formula 1 Perylene tetracarboxylic dianhydride (1,6,7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter referred to as 'TTBPDA') It reacts and polycondenses by imide bond.

[Formula 1]

Method for producing a polymeric fluorescent substance containing a perylene unit phosphor according to the present invention, (1) 1,6,7,12-tetrakis (4-t-butylphenoxy)-as the perylene unit phosphor of the formula (1) 3,4,9,10-perylenetetracarboxylic dianhydride (1,6,7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter referred to as 'TTBPDA' ) Manufacturing step; (2) a first dissolving step of dissolving the TTBPDA in an inert organic solvent such as meta-cresol under a nitrogen atmosphere to prepare a first reaction solution; (3) a second dissolution step of preparing a second reaction solution by dissolving a diamine having a soft group in an inert organic solvent such as meta-cresol; (4) a first reaction step of mixing the first reaction solution and the second reaction solution with each other and reacting at 170 to 210 ° C. for 6 to 10 hours under a nitrogen atmosphere; (5) A third reaction solution in which isoquinoline is dissolved in an inert organic solvent such as meta-cresol is added to the reaction mixture of the first reaction step, and stirred for 40 to 56 hours at the same temperature range to react. Two reaction stages; And (6) washing the reaction mixture in which the second reaction step is completed with an aqueous sodium hydrogen carbonate solution, recrystallization, and then vacuum drying at 70 to 90 ° C. to obtain a final product and a post-treatment step. Is done.

In addition, the chemiluminescent composition comprising a polymer phosphor comprising a perylene unit phosphor according to the present invention, 1,6,7,12-tetrakis (4-t- butylphenoxy as a perylene unit phosphor of Formula 1 ), 3,4,9,10-perylenetetracarboxylic dianhydride (1,6,7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter 'TTBPDA' 1 to 10 g of a polymer phosphor comprising a perylene unit phosphor formed by reacting with a diamine having a flexible group and polycondensing with an imide bond, and an oxalate / peroxide / to supply chemical energy for luminescence to the polymer phosphor. It comprises a chemical energy transfer system consisting of an organic base, the chemical energy transfer system is bis (2,4-dinitrophenyl) oxalate, bis (pentafluorophenyl) oxalate, bis (2, 4, 6- trichloro Lophenyl) oxalate, bis [2,4,5-trichloro- 10-30 mM oxalate selected from the group consisting of 6- (pentyloxycarbonyl) phenyl] oxalate or bis (2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate (CPPO); , 1 to 2 times the concentration of oxalate, such as hydrogen peroxide, and organic base groups of 1/50 to 1/30 times the concentration of oxalate, such as sodium benzoate and sodium salicylate.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The polymeric fluorescent substance including perylene unit phosphor according to the present invention is 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10 as the perylene unit phosphor of Chemical Formula 1 Perylene tetracarboxylic dianhydride (1,6,7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter referred to as 'TTBPDA') It is characterized in that the reaction is made by polycondensation with an imide bond.

The method for producing the perylene unit phosphor of Chemical Formula 1 is already known.

The perylene unit phosphor of Formula 1 is connected to each other by condensation polymerization by imide bonds with diamines in the form of dianhydrides to form a very close polymer phosphor, and the obtained polymer phosphor has a plurality of perylene unit phosphors in the main chain. It will be included.

Method for producing a polymeric fluorescent substance containing a perylene unit phosphor according to the present invention, (1) 1,6,7,12-tetrakis (4-t-butylphenoxy)-as the perylene unit phosphor of the formula (1) 3,4,9,10-perylenetetracarboxylic dianhydride (1,6,7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter referred to as 'TTBPDA' ) Manufacturing step; (2) a first dissolving step of dissolving the TTBPDA in an inert organic solvent such as meta-cresol under a nitrogen atmosphere to prepare a first reaction solution; (3) a second dissolution step of preparing a second reaction solution by dissolving a diamine having a soft group in an inert organic solvent such as meta-cresol; (4) a first reaction step of mixing the first reaction solution and the second reaction solution with each other and reacting at 170 to 210 ° C. for 6 to 10 hours under a nitrogen atmosphere; (5) A third reaction solution in which isoquinoline is dissolved in an inert organic solvent such as meta-cresol is added to the reaction mixture of the first reaction step, and stirred for 40 to 56 hours at the same temperature range to react. Two reaction stages; And (6) washing the reaction mixture in which the second reaction step is completed with an aqueous sodium hydrogen carbonate solution, recrystallization, and then vacuum drying at 70 to 90 ° C. to obtain a final product and a post-treatment step. Characterized in that made.

1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride of the above (1) (1,6,7,12-tetrakis ( The production step of 4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride (hereinafter referred to as 'TTBPDA') is a step of preparing according to a known method of preparing perylene unit phosphors. It can be connected to each other by condensation polymerization by imide bonds with diamines in the form of dianhydrides to form very tight polymer phosphors.

In the first dissolution step of (2) and the second dissolution step of (3), the TTBPDA is dissolved in a nitrogen atmosphere and a diamine having a soft group is dissolved in an inert organic solvent such as meta-cresol. To prepare.

In the first reaction step (4), the first reaction solution and the second reaction solution are mixed with each other, and reacted under a nitrogen atmosphere at 170 to 210 ° C. for 6 to 10 hours. The reaction is initiated to form polyimide by imide bonds so that the above-mentioned perylene unit phosphors are included in the main chain of the obtained polymer phosphor. If the reaction temperature of the first reaction step is less than 170 ℃, there may be a problem that the yield of the resulting polymeric fluorescent substance is not sufficiently reduced, the reverse reaction, such as decomposition of the reaction product when exceeding 210 ℃ Too high a heating temperature is not economical.

In the second reaction step of (5), a third reaction solution in which isoquinoline is dissolved in an inert organic solvent such as meta-cresol is added to the reaction mixture of the first reaction step, and 40 to 56 in the same temperature range. The reaction is carried out by stirring for a time, wherein isoquinoline acts as an imidization catalyst. If the reaction temperature of the second reaction step is less than 170 ℃, there may be a problem that the reaction does not occur sufficiently, the yield of the obtained polymer phosphor is lowered, on the contrary, if it exceeds 210 ℃, reverse reaction such as decomposition of the reaction product Too high a heating temperature is not economical. In addition, even if the stirring time is less than 40 hours, there may be a problem that the reaction time is not enough, yield is lowered, if it exceeds 56 hours, there is a disadvantage that it is not economical without the effect of improving the yield.

In the post-treatment step (6), the reaction mixture in which the second reaction step is completed is washed with an aqueous sodium hydrogen carbonate solution, recrystallized, and then vacuum-dried at 70 to 90 ° C. to obtain a final product. As a result, it can be understood as a step of removing the unreacted substances and impurities contained in the obtained product, that is, the polymeric fluorescent substance, increasing the purity of the polymeric fluorescent substance, and facilitating storage and handling by drying or the like. The drying temperature may be considered as a temperature range in which sufficient drying of the product can be carried out economically in a relatively short time.

In addition, the chemiluminescent composition comprising a polymer phosphor comprising a perylene unit phosphor according to the present invention, 1,6,7,12-tetrakis (4- t -butylphenoxy as a perylene unit phosphor of the formula (1) ), 3,4,9,10-Perylene tetracarboxylic dianhydride (1,6,7,12-tetrakis (4- t -butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter 'TTBPDA' 1 to 10 g of a polymer phosphor comprising a perylene unit phosphor formed by reacting with a diamine having a flexible group and polycondensing with an imide bond, and an oxalate / peroxide / to supply chemical energy for luminescence to the polymer phosphor. It comprises a chemical energy transfer system consisting of an organic base, the chemical energy transfer system is bis (2,4-dinitrophenyl) oxalate, bis (pentafluorophenyl) oxalate, bis (2, 4, 6- trichloro Rophenyl) oxalate, bis [2,4,5-trichloro 10-30 mM oxalate selected from the group consisting of -6- (pentyloxycarbonyl) phenyl] oxalate or bis (2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate (CPPO) And a peroxide of 1 to 2 times the concentration of oxalate such as hydrogen peroxide and an organic base of 1/50 to 1/30 times the concentration of oxalate such as sodium benzoate and sodium salicylate.

Examples of the oxalate of the chemical energy transfer system include bis (2,4-dinitrophenyl) oxalate, bis (pentafluorophenyl) oxalate, bis (2,4,6-trichlorophenyl) oxalate, bis [2 Selected from the group consisting of 4,5-trichloro-6- (pentyloxycarbonyl) phenyl] oxalate or bis (2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate (CPPO) Can be used, all of which are known for their preparation. The oxalate is preferably used 10 to 30mM, when less than 10mM may have a problem that the chemiluminescence time is shortened, on the contrary, more than 30mM is irrelevant to the chemical reaction but some insoluble parts are generated Or wasteful use by overuse.

Hydrogen peroxide may be used as the peroxide of the chemical energy transfer system, and it is also known to those skilled in the art that it can be purchased and used commercially. Preferably, the peroxide is used at a concentration of 1 to 2 times the oxalate concentration, and when the concentration of the peroxide is less than 1 times the concentration of the oxalate, sufficient chemical energy transfer does not occur so that the chemiluminescence is sufficient. There may be a problem that does not happen, and on the contrary, exceeding twice can also be meaningless waste.

As the organic base of the chemical energy transfer system, sodium benzoate, sodium salicylate, and the like may be used, which is also known to those skilled in the art to be commercially available. Preferably, the organic base is used at a concentration of 1/50 to 1/30 times the concentration of oxalate, and when the concentration of the organic base is used at less than 1/50 of the oxalate concentration, sufficient chemical energy is also transferred. There may be a problem that the chemiluminescence does not occur sufficiently because this does not occur, on the contrary, if it exceeds 1/30, there may be a problem that the light emitting time is shortened due to the speed of light emission start.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Experimental Example 1

Synthesis of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic dianhydride (TCPDA)

A 4,9,10-perylenetetracarboxylic dianhydride 20g (50.97mmol) and 1.9g (7.48mmol) of iodine are dissolved in 750g of 95% sulfuric acid and equipped with a mechanical stirrer, gas inlet and outlet. It injected | threw-in to (1000 mL) and stirred, raising temperature at 35 degreeC. Chlorine gas was injected while maintaining 35 ° C, and the reaction was performed for 2 hours. After the reaction mixture was cooled to room temperature, 350 ml of diluted sulfuric acid diluted to 30% was slowly added dropwise for 2 hours using a dropping funnel. The precipitated orange powder produced was filtered using a Duran P3 glass filter, and then washed continuously with excess water until the wash solution was neutral. The powder obtained was vacuum dried at 80 deg. C to give 25.5 g (94% yield) of the final orange product.

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 3045 (aromatic CH), 1655,1698 (C = 0), 1250, 1010 (C-0).

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.32 (s, 4H, perylene)

The starting material 3,4,9,10-perylenetetracarboxylic dianhydride was poor in solubility, so that the mixture was stirred and dissolved in concentrated sulfuric acid (95%) for several minutes. And when the chlorination reaction by injecting the chlorine gas to the mixture, and installed a bubbler (bubbler) so that the chlorine gas can be evenly dispersed. Since the viscosity of the mixture was high, a mechanical stirrer was used, and in order to increase the efficiency of the reaction, the rotation speed of the mechanical stirrer was set to 250 to 300, followed by vigorous stirring. As the reaction proceeded, the color of the solution changed from dark red to orange, and the completion of the reaction was confirmed using thin layer chromatography (TLC). After the reaction was completed, the temperature was lowered to room temperature and reprecipitated in distilled water, and the concentrated sulfuric acid, a solvent, was used to prevent it because exothermic heat occurred when reprecipitated in distilled water. After filtering out the precipitated product, and washed with a large amount of distilled water several times, the following Experimental Example 2.

Experimental Example 2

Synthesis of N, N'-dipropyl-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide (DTCPDI)

In a round bottom flask (250 ml) equipped with a condenser, a mixture of water / methanol (v / v = 1/1, 145 ml) and 8.49 g (143.6 mmol) of 1-propylamine was stirred, followed by stirring for several minutes. 5.65 mmol) was added to a suspension of 30 ml of methanol, and reacted at room temperature for 6 hours. After that, 10 ml of concentrated hydrochloric acid was slowly added dropwise using a dropping funnel to neutralize it. The suspension was filtered through a Duran P4 glass filter, washed several times with excess distilled water until the wash solution was neutral, and dried in vacuo at 80 ° C. to give 3.2 g of orange final product (yield). 92%) was obtained.

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 1350 (CN), 1655, 1698 (C = 0), 2950, 2870 (aliphatic CH), 3010 (aromatic CH)

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.74 (s, 4H, perylene), 7.14 (d, 8H, -0-Ph- (2, 6)), 6.81 (d, 8H, -0-Ph- (3.5)), 3.38 (t, 4H, = N-CH _2- ), 1.72 (m, 4H, = N-CH ₂ -CH _2- ), 0.9 (m, 4H, = N-CH ₂ -CH ₂ -CH ₃ ).

In order to synthesize DTTBPDI, a model compound, imidization was performed using 1-propylamine in both anhydride groups to prevent esterification of 4-t-butylphenoxy to both anhydride groups. When the synthesized TCPDA was dissolved in a mixed solution of distilled water and methanol to proceed with the reaction, TCPDA was not dissolved and the yield was not good. Thus, TCPDA was dispersed in a small amount of methanol and then dissolved in a mixture of distilled water and methanol. Excess 1-propylamine was dissolved and added to the stirred solution for several minutes, followed by reaction at room temperature for 6 hours to obtain an orange product. The reaction formed a suspension upon the addition of TCPDA, completely dissolved in a brown solution after about 30 minutes and then again forming a suspension of an orange solid after 2 hours. It can be seen that the ring of the anhydride group is converted into amic acid in the salt form to dissolve, which is insoluble in the solvent, forming an imide ring again, and becomes a suspension. The suspension was filtered, washed with a small amount of methanol and dried. The synthesis was confirmed by Fourier-transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy. Potassium bromide (KBr) for the after creating the pellets was measured using Fourier-transform infrared spectroscopy to determine the absorption peak of carbonyl group (C = 0) in the CN absorption peak, 1655, 1698cm ^-1 1350cm ^-1 in there was. Proton-nuclear magnetic resonance spectroscopy confirmed the hydrogen of perylene ring at 8.74ppm and the hydrogen of phenoxy group at 7.14ppm and 6.81ppm. In addition, the hydrogen of the propyl group connected to the imide ring was confirmed at 3.38, 1.72 and 0.9 ppm, thereby confirming synthesis.

Experimental Example 3

Synthesis of N, N'-dipropyl-1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic acid diimide (DTTBPDI)

1.6g (11.6mmol) of potassium carbonate and 1.74g (11.6mmol) of 4-t-butylphenol were pulverized with a mortar in a round bottom flask (100ml) equipped with a condenser. To 10 ml of pig (1-methyl-2-pyrrolidone) was added and stirred at room temperature for 30 minutes. Then, a solution of 1.5 g (2.32 mmol) of DTCPDI dissolved in 10 ml of 1-methyl-2-pyrrolidone was added thereto. Heated to ℃, and reacted for 12 hours. After the reaction solution was filtered, the solution was reprecipitated in 800 ml of distilled water / oxalic acid / ethanol (w / w / w = 1/1/1), and the resulting mixture was filtered and dried in vacuo at 80 ° C. The dried product was packed into a 3 cm diameter column by 15 cm silica gel and eluted with 200 mL of chloroform. Then purified by elution with chloroform / ethyl acetate (v / v = 9/1) successively (yield 23%).

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 1250, 1010 (C-0), 1350 (CN), 1655, 1698 (C = 0), 2950, 2870 (aliphatic CH), 3010 (aromatic CH)

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.32 (s, 4H, perylene), 7.12 (d, 8H, -O-Ph- (2, 6)), 6.81 (d, 8H, -O-Ph- (3.5)), 3.8 (t, 4H, = N-CH _2- ), 1.95 (m, 4H, = N-CH ₂ -CH _2- ), 0.89 (m, 6H, = N-CH ₂ -CH ₂ -CH ₃ ), 1.27 (s, 36H, 4-C (CH ₃ ) ₃ ).

N, N'-dipropyl-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide (DTCPDI) has a poor solubility because it is a planar structure. Solubility was enhanced by replacing 4-t-butylphenol. First, DTCPDI was dissolved in a small amount of 1-methyl-3-pyrrolidone (NMP) and sodium carbonate, insoluble in 1-methyl-3-pyrrolidone, reduced the surface area. After crushing using a mortar and pestle, the mixture was poured into 1-methyl-3-pyrrolidone with excess 4-t-butylphenol, stirred for 10 minutes, and then DTCPDI was added to 1-methyl-3-pyrrolidone. The melted solution was added, heated and stirred to proceed with the reaction. Synthesized DTTBPDI was purified twice by column chromatography (SiO ₂ , CHCl ₃ ). It appears as three points on thin layer chromatography, the bottom of which is considered to be the salt form of excess 4-t-butylphenol, and the middle one is considered to be an impurity of monoimide of DTTBPDI. In order to remove the impurities of the above form, column chromatography was used. The structure of the purified product was confirmed by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy. And the carbonyl absorption bands at 1655, 1698cm ^-1 in the Fourier transform infrared spectroscopy, can see the CN absorption peak at 1350cm ^-1, the proton-nuclear magnetic resonance for spectroscopy, and 4 of the perylene ring at 8.32ppm Hydrogens and 16 aromatic hydrogens of 4-t-butylphenoxy appeared as doublets at 7.12 and 6.79 ppm. And hydrogen in the 12 methyl group of 4-t- butylphenoxy was confirmed by a very large single line at 1.27ppm, it was confirmed the synthesis.

Experimental Example 4

Synthesis of 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride (TTBPDA)

In a round bottom flask (100 ml) equipped with a condenser, 3.75 g (3.5 mmol) of DTTBPDI was added 650 ml of isopropanol / water (v / v = 10/1) and 75 g of potassium hydroxide, followed by stirring at room temperature for several minutes. The reaction mixture was then heated to 120 ° C. and the reaction proceeded for 48 hours. Thereafter, the mixture was cooled to room temperature, dissolved in methylene chloride, and neutralized with hydrochloric acid diluted to 10%. After removing the solvent, the wash was washed with excess distilled water until neutral and dried in vacuo at 80 ° C. to give 3.30 g of a reddish brown final product. The dried product was packed into a 3 cm diameter column by 15 cm silica gel and eluted with 200 ml of chloroform. Then purified by elution with hexane / ethyl acetate (v / v = 6/1) successively (yield 88%).

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 1250, 1010 (CO), 1659, 1698 (C = O), 2950, 2870 (aliphatic CH), 3010 (aromatic CH)

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.32 (s, 4H, perylene), 7.21 (d, 8H, -O-Ph- (2,6)), 6.81 (d, 8H, -O-Ph- (3.5)), 1.3 (s, 36H, 4-C (CH ₃ ) ₃ ).

To synthesize 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride to be used as a monomer of the red polymer phosphor, a small amount of DTTBPDI was first used. After dissolving in isopropanol, distilled water and isopropan were dissolved in a mixed solution of excess potassium hydroxide and added to a stirred solution for several minutes, and reacted at 120 ° C. for 48 hours to obtain a reddish brown product. The reaction formed a red suspension when DTTBPDI was added, completely dissolved in a pale green solution after about 10 minutes, and formed a dark green suspension after 48 hours. It was converted to amic acid and dissolved as the imide bond was opened. At this time, the amide bond was decomposed to form an acid. As the diacid dehydrates to form an anhydride ring, the diacid is again insoluble in the solvent and becomes a suspension. The suspension was dissolved in methylene chloride, neutralized with 10% hydrochloric acid solution, and then the organic layer was recovered to remove the solvent, washed with excess distilled water several times, and dried. The dried product was purified by column chromatography (SiO ₂ , CHCl ₃ ). In the Fourier transform infrared spectroscopy, the absorption peak of the carbonyl group was observed at 1655 and 1698 cm ^-1 . In the proton-nuclear magnetic resonance spectroscopy, four hydrogens of the perylene ring were observed at 8.22 ppm and 4-t-butyl The 16 aromatic hydrogens of phenoxy appeared as doublets at 7.14 and 6.81 ppm. Hydrogen in the 12 methyl group of 4-t-butylphenoxy was found to be a very large singlet at 1.3 ppm, and no peak of the propyl group was observed, indicating that the diimide was decomposed.

Example 1

Synthesis of Polymer Phosphor 1

In a round bottom flask (100 ml) equipped with a condenser, 2 g (2.0 mmol) of TTBPDA and 0.24 g (0.40 mmol) of benzoic acid were dissolved in 30 ml of m-cresol by stirring for several minutes under a nitrogen atmosphere. 0.57 g (2.0 mmol) of 2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-dipropamine was dissolved in 5 ml of m-cresol, and then added to the solution at 190 캜. The reaction was carried out under nitrogen atmosphere for 8 hours. A solution of 0.52 g (4.0 mmol) of isoquinoline dissolved in 5 ml of m-cresol was added to the reaction, followed by stirring at 190 ° C. for 48 hours to complete the reaction.

The reaction solution was washed with 1000 ml of aqueous sodium hydrogen carbonate solution, dissolved in chloroform, reprecipitated in diethyl ether, and dried in vacuo at 80 ° C. to obtain a final product (yield 75%).

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 3010 (aromatic CH), 2950, 2870 (aliphatic CH), 1659, 1698 (C = O), 1250, 1010 (CO).

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.32 (s, 4H, perylene), 7.2 (d 8H, 4 -O-Ph (2,6)-), 6.82 (d, 8H, 4 -O-Ph (3,5)-), 3.92 (t , 4H, 2 = N-CH _2- ), 4.51 (s, 2H, 2 -CH (-O-)-O-), 3.5 (br, 8H, 4 -O-CH _2- ), 1.7 (m, _{4H, 2 = N-CH 2} - CH 2 -), 1.5 (m, 4H, 2 = N-CH 2 - CH 2 -CH 2 -), 1.3 (s, 36H, 4 C (CH 3) 3).

Elemental Analysis: Theoretical C ₇₇ H ₇₆ N ₂ O ₁₂ (Mw, 1221.45): C, 75.72%; H, 6. 27%; N, 2.29%. Found: C, 75.67%, H, 6.29%; N, 2.24%.

Example 2

Synthesis of Polymer Phosphor 2

2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-dipropamine instead of 0.57 g (2.0 mmol) polytetrahydrofuran, bis (3-aminophyl) terminal (polytetrahydrofuran, bis (3-aminoproyl) terminated) was performed in the same manner as in Example 1, except that 0.71 g (2.0 mmol) was used (yield 76%).

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 3010 (aromatic CH), 2950, 2870 (aliphatic CH), 1659, 1698 (C = O), 1350, 1040 (CN), 1250 (CO).

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.3 (s, 4H, perylene), 7.2 (d, 8H, 4 -O-Ph (2, 6)-), 6.8 (d, 8H, 4-O-Ph (3,5)-), 4, 2 (t 4H, 2 = N-CH _2- ), 3.6 (br, 16H, 4-CH ₂ -O-CH _2- ), 3.4-3.5 (br, 4H, 2 = N- CH ₂ -CH _{2- CH 2 -), 1.8 (m} , 12H, 3 -CH 2 -CH 2 -), 1.5 (m, 4H, 2 = N-CH 2 - CH 2 -CH 2 -), 1.3 (s, 36H, 4 C (CH ₃ ) ₃ ).

Elemental Analysis: Theoretical C ₈₂ H ₉₂ N ₂ O ₂ (Mw, 1297.63): C, 75.90%, H, 7.15%; N, 2.16%. Found: C, 75.82%; H, 7.20%; N, 2.18%.

Example 3

Synthesis of Polymer Phosphor 3

Poly (propyleneglycol) -bis (2-aminopropylether) instead of 0.57 g (2.0 mmol) of 2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-dipropamine propylene glycol) -bis (2-aminopropylether)) 0.46g (2.0mmol) was used in the same manner as in Example 1 (yield 87%).

The main peaks of the analysis results of the obtained product by Fourier transform infrared spectroscopy and proton-nuclear magnetic resonance spectroscopy are as follows;

Fourier transform infrared spectroscopy (KBr, cm ^-1 ); 3010 (aromatic CH), 2950, 2870 (aliphatic CH), 1659, 1698 (C = O), 1350, 1040 (CN), 1250 (CO).

Proton-nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm); 8.3 (s, 4H, perylene), 7.2 (d, 8H, 4 -O-Ph (2,6)-), 6.8 (d, 8H, 4 -O-Ph (3,5)-), 3.8 ( t, 4H, 2 = N-CH (CH ₃ )-), 3.53.7 (br, 2H, 2 -CH (CH ₃ ) O-), 3.5 (br, 8H, 4 -CH ₂ -O-), 1.3-1.4 (s, 12H, 4 -CH ₃ ), 1.3 (m, 12H, 4 C (CH ₃ ) ₃ ).

Elemental Analysis Value: Theoretical C ₇₆ H ₈₀ N ₂ O ₁₁ (Mw, 1197.47): C, 76.23%; H, 6.73%; N, 2.34%. Experimental Value: C, 76.31%, H, 6.69%; N, 2.30%.

In the polymer phosphors of Examples 1 to 3, in the Fourier transform infrared spectroscopy, absorption peaks of CN bonds were observed in the region of 1350 to 1040 cm ⁻¹ . In proton-nuclear magnetic resonance spectroscopy, the synthesis was confirmed by confirming the characteristic peaks of the derivative units of methyl hydrogen and diamine of 4-t-butylphenoxide group, which are the characteristic peaks of perylene-containing units in the polymers.

Experimental Example 5

0.01 g of each of the polymer phosphors including the perylene unit phosphors synthesized in Experimental Example 4 and the perylene unit phosphors synthesized in Examples 1 to 3 were taken, respectively, to form tetrahydrofuran, dibutylphthalate (DBP; dibutylphthalate), and chloroform. The solubility was measured by dissolving in 10 ml, and the melting point was investigated using a conventional melting point apparatus. Also, the polymer phosphors containing the perylene unit phosphor and the perylene unit phosphor were dissolved in chloroform. Optical properties are obtained by dissolving organic phosphors in dibutylphthalate and chloroform, respectively, for UV / Vis spectrophotometer (Hewlet Packard, UV / Vis spectrophotometer HP8454, USA) and photoluminescence spectrophotometer RF. -5301 PC, Japan) The elemental analyzer is CHN-element analyzer (Yanaco). MT-3, Japan).

The results are shown in Table 1 (melting point, intrinsic viscosity, molecular weight, molecular weight distribution, glass transition temperature and yield) and Table 2 (solubility in various solvents).

TABLE 1

TABLE 2

In addition, the maximum absorption wavelength of ultraviolet-visible light absorption, photoluminescence and chemiluminescence was investigated, and the results are shown in Table 3 below.

TABLE 3

The synthesized DTCPDI showed poor solubility in most organic solvents.

However, it was observed that DTTBPDI, the perylene unit phosphor of Experimental Example 3, was easily dissolved in chloroform, tetrahydrofuran, and dibutylphthalate. This is due to the free rotation of the 4-t-butylphenoxy substituent, which is linked to the dense crystal structure due to the planar structure of perylene, which is a single bond at the 1, 6, 7, and 12 positions of perylene. This can be explained by the fact that there is enough space to penetrate and the solubility increases. The solubility of the polymeric phosphors containing the perylene unit phosphors of Examples 1 to 3 was found to melt when heated in chloroform, tetrahydrofuran, dibutyl phthalate. It is observed that the polymer phosphors generally exhibit poor solubility in organic solvents, but the synthesized polymer phosphors were observed to have increased solubility due to the introduction of flexible groups such as propyl groups and ethers. The polymer phosphors including the perylene unit phosphor of Experimental Example 4 synthesized and the perylene unit phosphors of Examples 1 to 3 showed reddish brown color on the solid, and the color of the solid state of the polymer was light brown. Perylene unit phosphors appeared reddish violet in solution, and the polymeric phosphors had a light brown color.

In addition, the perylene unit phosphor and the polymeric fluorescent substance including the perylene unit phosphor showed maximum absorption wavelengths near 585 nm in the ultraviolet / visible absorption spectrum as shown in FIG. 1. In the case of photoluminescence, as shown in FIG. 2, the perylene unit phosphor exhibits a maximum emission wavelength in the red fluorescent region at about 621 nm, and the polymer phosphors at about 615 to 618 nm as shown in FIG. 2. Maximum emission wavelength was observed.

Experimental Example 6

Chemiluminescence Measurement

After dissolving the di-butyl phthalate in CPPO at a concentration of 1 * 10 ^-3 M, where the concentration of the fluorescent substance by dissolving in a range of 1 * ^10-4 to 1 * 10 ^-3 M to prepare a fluorescent solution. The catalyst solution was dissolved in 200 g of hydrogen peroxide and 80 g of t-butanol in 700 g of dimethylphthalate, and 100 ml of the solution was dissolved in 0.01 g, 0.05 g, and 0.1 g of sodium salicylate at 50 ° C., respectively, and the concentration was 6.24 * 10 ⁻⁶ M, 3.12 * 10 ^-6 M, and 3.02 * 10 ^-7 M. 0.9 ml of the fluorescent solution was added to a 2 ml container, and then 0.3 ml of a catalyst solution having a different amount of sodium salicylate was added and sealed, shaken for a predetermined time, and then a lux meter equipped with a probe capable of loading the container (Minolta Chroma Meter CS- 100, Japan) and immediately investigated the luminance and color coordinates of chemiluminescence at predetermined time intervals, the results are shown in Table 4 below.

TABLE 4

Chemiluminescent reactions begin with the reaction of CPPO with hydrogen peroxide, and not only intermediates that can produce chemiluminescence, but also reactions of chemiluminescent products that can cause decomposition. Hydrogen peroxide used in the peroxyoxalate chemiluminescence (POCL) reaction was concentrated using anhydrous magnesium sulfate. The effect of a small amount of water added to the hydrogen peroxide can suppress the reaction rate to lengthen the light duration, but when the excess amount of water is added to the concentration of hydrogen peroxide, the total amount of emitted light decreases drastically. In chemiluminescence, bis (2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate (CPPO) was used in this study because aromatic derivatives with electron attracting groups showed the most efficient luminescence. Using ester of 5,6-trichlorosalicylic acid and 1-pentanol as titanium (IV) isopropoxide as a catalyst to synthesize esters by dehydration condensation, the resulting ester intermediate is oxalyl CPPO synthesized by reacting with oxalyl chloride was used. The concentration of the phosphor was used in the range of 0.3 to 0.5% by weight, which is the most efficient concentration through the repeated experiments, and the amount of CPPO was used to prepare a fluorescent solution using 1 * 10 ^-3 M. The catalyst solution was prepared by adding hydrogen peroxide and sodium salicylate to dimethyl phthalate. The amount of hydrogen peroxide was fixed at 1.5 * 10 ^-3 M, and the catalyst solution was prepared by changing the amount of sodium salicylate as a catalyst to 6.24 * 10 ^-6 M, 3.12 * 10 ^-6 M and 3.02 * 10 ^-7 M. The chemiluminescence mechanism is based on the reaction intermediate I (1,2-dioxetanedione), the complex of I and the phosphor, and the emission in time (t) assuming that the lifetime of the phosphor in the excited state is short and their steady state concentration is low. The intensity is proportional to the concentration of CPPO and hydrogen peroxide, ie the concentration of their products.

The energy transfer process between the intermediate and the phosphor in chemiluminescence appears as the excitation of the phosphor by the charge transfer reaction, and the investigation of changes in the concentrations of CPPO, hydrogen peroxide and the phosphor is shown in many literatures. In the applicability evaluation, the amount of CPPO and hydrogen peroxide were fixed at the amount generally used, and the experiment was performed by changing the concentration of sodium salicylate as a catalyst. As the effect of sodium salicylate concentration on chemiluminescence, the intensity of luminescence decreased after reaching the maximum value in a short time. Increasing the concentration of sodium salicylate shortened the time for the chemiluminescence to reach the maximum value, showing a rapid decrease rate, but the intensity of the initial emission of light was found to show a phenomenon. Sodium salicylate, a base catalyst, was able to control the intensity and duration of light of chemiluminescence. In the case of chemiluminescence, as shown in FIG. 3, the polymer phosphors of Examples 1 to 3 were also moved up to longer wavelengths than the ultraviolet / visible absorption spectrum, and the polymer phosphors of Examples 1 to 3 were maximized in the long wavelength region of 600 to 700 nm. It was confirmed that the emission wavelength appeared.

In the case of the above experiment in the present invention, the intensity and emission duration of the chemiluminescence of the perylene unit phosphor of Experimental Example 3 is 38,000 to 40,000 mcd / cm 2 after mixing the samples, as shown in FIG. After 30 minutes, the strength of 5,000 to 6,000 mcd / ㎠, and after 1 hour was confirmed to show the intensity of 1,000 to 1,500 mcd / ㎠. However, in the case of the polymer phosphors of Examples 1 to 3, when the chemiluminescence experiment was performed under the same conditions, the emission intensity was initially lower than that of the perylene unit phosphor of Experiment 4, but after 30 minutes Showed an intensity of 7,000 to 8,000 mcd / cm 2, and after 1 hour, it showed an intensity of 2,500 to 3,000 mcd / cm 2, indicating that the emission duration was better in the polymer phosphors than in the case of Experimental Example 4, which is a monomer. I could confirm it.

Therefore, according to the present invention, the perylene unit phosphor is introduced into the polymer backbone, which is less harmful than the conventional monomer phosphor when the phosphor is leaked, and the perylene unit phosphor as a fluorescent material is regularly distributed to transfer energy converted from chemical energy. There is an effect of providing a polymer fluorescent substance comprising a perylene unit phosphor having an advantage to effectively, a method for producing the same and a chemiluminescent composition comprising the polymer fluorescent substance.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (3)

1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride (1,6,7, 12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride (hereinafter referred to as 'TTBPDA') is reacted with a diamine having a soft group to polycondensate with an imide bond. A polymeric fluorescent substance comprising a perylene unit phosphor; Formula 1 In the conventional method for producing a polymeric phosphor, (1) 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride (1,6) as a perylene unit phosphor of formula (1) (7,12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride; hereafter referred to as 'TTBPDA'); (2) a first dissolving step of dissolving the TTBPDA in an inert organic solvent such as meta-cresol under a nitrogen atmosphere to prepare a first reaction solution; (3) a second dissolution step of preparing a second reaction solution by dissolving a diamine having a soft group in an inert organic solvent such as meta-cresol; (4) a first reaction step of mixing the first reaction solution and the second reaction solution with each other and reacting at 170 to 210 ° C. for 6 to 10 hours under a nitrogen atmosphere; (5) A third reaction solution in which isoquinoline is dissolved in an inert organic solvent such as meta-cresol is added to the reaction mixture of the first reaction step, and stirred for 40 to 56 hours at the same temperature range to react. Two reaction stages; (6) washing the reaction mixture in which the second reaction step is completed with an aqueous sodium hydrogen carbonate solution, recrystallization, and then vacuum drying at 70 to 90 ° C. to obtain a final product, and a post-treatment step; Method for producing a polymer phosphor comprising a perylene unit phosphor, characterized in that comprises; Formula 1 1,6,7,12-tetrakis (4-t-butylphenoxy) -3,4,9,10-perylenetetracarboxylic dianhydride (1,6,7, Perylene unit phosphor formed by reacting 12-tetrakis (4-tert-butylphenoxy) -3,4,9,10-perylene tetracarboxylic dianhydride (hereinafter referred to as 'TTBPDA') with a diamine having a flexible group and polycondensing it with an imide bond 1 to 10g of a polymeric fluorescent substance comprising a, comprising a chemical energy transfer system consisting of oxalate / peroxide / organic base for supplying chemical energy for light emission to the polymeric fluorescent substance, the chemical energy transfer system is bis (2,4 -Dinitrophenyl) oxalate, bis (pentafluorophenyl) oxalate, bis (2,4,6-trichlorophenyl) oxalate, bis [2,4,5-trichloro-6- (pentyloxycarbo Yl) phenyl] oxalate or bis (2-carbopentyloxy-3,5,6-trichlorophenyl) oxalate (CPPO) 10 to 30 mM oxalate selected from the group consisting of 1 to 2 times the concentration of oxalate such as hydrogen peroxide and 1/50 to 1/30 times the concentration of oxalate such as sodium benzoate and sodium salicylate A chemiluminescent composition comprising a polymeric fluorescent substance comprising a perylene unit phosphor, characterized in that the organic base has a concentration; Formula 1