A pyridone azo dye and preparation method thereof

Abstract

The present invention discloses a pyridone azo dye and a preparation method thereof, belonging to the field of fine chemical technology. The general structural formula of the pyridone azo dye is as follows: wherein X1, X2, X3, X4, and X5 are each independently selected from one of nitro, hydrogen, fluorine, chlorine, bromine, cyano, and substituted or unsubstituted phenyl; the R substituent is selected from one of the following structures: By introducing an R substituent at the N position of pyridone, the problem of low solubility of pyridone azo dye in organic solvents can be effectively solved. The solubility of the pyridone azo dye disclosed in the present invention in organic solvents is between 5-9 g / 100 mL, and the molar absorption coefficient of this type of dye is between 20,000-120,000 L·mol ‑1 cm ‑1 It has excellent light and heat stability within the range and is feasible for preparing optical devices and full-color high-stable display materials.

Description

Technical Field

[0001] The invention relates to a pyridone azo dye and a preparation method thereof, belonging to the technical field of fine chemicals. Background Art

[0002] Colorants are one of the important components of color filters and directly determine the quality of color images. Ideal colorants for color filters should have a narrow and sharp absorption peak in a specific spectral range, a high molar absorption coefficient, good light stability before and after ultraviolet light irradiation (△E≤3), good thermal stability before and after heat baking (△E≤3), and good stability in industrial solvents such as propylene glycol methyl ether acetate (PGMEA) or N,N- It has good solubility in dimethylformamide (DMF) (S≥5g / 100mL).

[0003] Pyridone derivatives, as important components of heterocyclic azo dyes, are mostly used as coupling components to produce brightly colored dyes. Compared to traditional dyes, they have higher molar absorption coefficients and superior fastness properties. They are commonly used as disperse dyes for textile coloring (CN 105504858 A). Disperse dyes are characterized by being insoluble in water and containing fat-soluble substituents, properties that precisely meet our requirements for filter dyes. However, a fundamental problem with pyridone azo dyes is their low solubility in organic solvents.

[0004] To address this deficiency, researchers have introduced aliphatic, aryl, heterocyclic, carbamoyl, aliphatic carbonyl, aryloxycarbonyl, acyl, aliphatic sulfonyl, arylsulfonyl, and sulfamoyl substituents at the N-position of pyridone. The resulting yellow filter dyes exhibited good color and brightness, but solubility was not specifically described (CN102483479 A). Another study introduced a hydroxyethyl group at the N-position of pyridone and coupled it with aniline diazonium salts containing methyl, hydroxyl, methyl formate, and tert-butyl groups in the diazo component to produce nine dyes. The results showed that the solubility of three of the nine dyes in N-methylpyrrolidone (NMP) was greater than 4 wt%, one dye was greater than 3 wt%, and the solubility of the remaining dyes was less than 3 wt% (Coloration Technology, 133, 158-164, 2016). Later, researchers (Molecules, 2022, 27, 6601.) used N-methylpyridone as a coupling component and coupled it with aniline diazonium salts containing methyl, fluorine, chlorine, and bromine as the diazo component to prepare four dyes. The results showed that the dye with the highest solubility among the four dyes was only 0.5wt% (Molecules, 2022, 27, 6601.). This shows that the introduction of conventional low-carbon alkyl, hydroxyl, and ester substituents cannot effectively improve the low solubility of pyridone azo dyes. Therefore, researchers invented a class of pyridones with C1~C20 substituted alkyl, *-C(=O)OR1 or *-OC(=O)R1 at the N position, and the diazo component is a terminal containing Aniline, whose middle section consists of a long-chain alkane polymer, produces a dye with a solubility greater than 20 wt%, demonstrating excellent solubility properties (CN 105801477 A). However, the introduction of long-chain polymers into the molecule inevitably leads to a decrease in the molar absorptivity of the dye. Therefore, effectively increasing the solubility of pyridone azo dyes in organic solvents while ensuring that the molar absorptivity of the dye remains unaffected has become an urgent problem to be solved. Summary of the Invention

[0005] To address the above issues, the present invention provides a pyridone azo dye with excellent solubility and a preparation method thereof. The diazo component of this dye is an aromatic primary amine containing a group that inactivates the benzene ring, and the coupling component is a pyridone substituted at the N position with a silane coupling agent (RSiX3), a 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane derivative, or a caged polysilsesquioxane (POSS). The electron-withdrawing group in the diazo component of this dye synergistically interacts with the hydroxyl group on the pyridone ring of the coupling component to reduce the electron cloud density around the azo bond, thereby improving the dye's photostability. Compared to conventional CO bonds, the Si-O bond inherently has a higher bond energy and larger bond angle, which can improve the dye's thermal stability.

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

[0007] In a first aspect, the present invention provides a pyridone azo dye having excellent solubility. The general structural formula of the pyridone azo dye is shown in Formula I:

[0008]

[0009] Formula I

[0010] In formula I, X1, X2, X3, X4, and X5 are each independently selected from nitro, hydrogen, fluorine, chlorine, bromine, cyano, and substituted or unsubstituted phenyl; and R is one of I-1, I-2, or I-3:

[0011]

[0012] Wherein, 0<n<100, n is an integer;

[0013] M1 and M2 are independently selected from one of the following structural formulas:

[0014] 、 、 、 、 、 、 、 、 、 、 、

[0015] -H, -F, -Cl, -Br, -I;

[0016] Wherein, 0<m<22, m is an integer.

[0017] In a second aspect, the present invention provides a method for preparing the above-mentioned pyridone azo dye, comprising the following steps:

[0018] (1) Using an aromatic primary amine containing a benzene ring-inactivating group as the diazo component, the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid are added to a reaction vessel. After cooling to 0-5°C, nitrosyl sulfuric acid is added dropwise to carry out a diazotization reaction. After the reaction is completed, aminosulfonic acid is added to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0019] (2) Using the pyridone substituted with R at the N position as the coupling component, the coupling component, ethanol and water are added to a reaction vessel, stirred at room temperature to dissolve the coupling component, cooled to 0-5°C, and the diazonium salt solution obtained in step (1) is added under stirring, and the reaction is gradually heated to room temperature to carry out the coupling reaction;

[0020] (3) After the reaction is completed, water is added to precipitate the solid, and alkali is added to the resulting dye mixture to adjust the pH value of the solution to neutral;

[0021] (4) After post-processing, it is obtained.

[0022] Furthermore, the structural formula of the diazo component is shown in Formula II:

[0023] .

[0024] Formula II

[0025] Furthermore, the structural formula of the coupling component is shown in III:

[0026] .

[0027] Formula III

[0028] Furthermore, in step (1), the molar ratio of the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid is 1:1:1 to 1:3:3, more preferably 1:3:3.

[0029] Furthermore, in step (1), the concentration of the nitrosyl sulfuric acid is 25 wt% to 40 wt%, more preferably 40 wt%.

[0030] Furthermore, in step (1), the diazotization reaction time is 0.2 h to 8 h, more preferably 0.5 h.

[0031] Furthermore, in step (2), the ratio of the coupling component, ethanol and water is 1:50:50 to 1:500:500.

[0032] Furthermore, in step (2), the time for adding the diazonium salt solution to the coupling component is 1 to 60 minutes, more preferably 30 minutes.

[0033] Furthermore, in step (2), the coupling reaction time is 1 h to 24 h, more preferably 8 h.

[0034] Furthermore, in step (4), the post-treatment includes: filtering the dye mixture obtained in step (3) and washing with water until the filtrate is clear, drying to obtain a crude product; and purifying the crude product by column chromatography and gradient eluting with an organic solvent.

[0035] Furthermore, the organic solvent is an ethyl acetate-petroleum ether mixed solvent, and the volume ratio of the solvent used is ethyl acetate:petroleum ether=1:1~1:5, more preferably ethyl acetate:petroleum ether=1:1.

[0036] The beneficial effects of the present invention are as follows: the pyridone azo dye of the present invention has a high molar absorption coefficient and exhibits bright color and high brightness in a solvent; the dye has excellent light and heat stability; the color difference of a colored film prepared with the dye before and after irradiation under ultraviolet light is less than 1.5, and the color difference of the colored film before and after baking at 220°C is less than 3 (except for Dye2); at the same time, the dye has good thermal stability in propylene glycol methyl ether acetate (PGMEA) and N,N -The solubility of the azopyridine in organic solvents such as dimethylformamide (DMF) can reach 5-9g / 100mL, which improves the utilization rate of the dye during use and effectively solves the problem of low solubility of pyridone azo dyes in organic solvents. In addition, its synthesis is relatively easy, which is conducive to its production and application in industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 Schematic diagram of N-substitution of pyridone.

[0038] Figure 2 The molecular structure of Dye1, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0039] Figure 3 The molecular structure of Dye2, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0040] Figure 4 The molecular structure of Dye3, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0041] Figure 5 The molecular structure of Dye4, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0042] Figure 6 The molecular structure of Dye7, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0043] Figure 7 The molecular structure of Dye9, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0044] Figure 8 The molecular structure of Dye17, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0045] Figure 9 The molecular structure of Dye25, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0046] Figure 10 The molecular structure of Dye35, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0047] Figure 11 The molecular structure of Dye43, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0048] Figure 12 The molecular structure of Dye49, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF) are displayed.

[0049] Figure 13 Color film images of dyes Dye1 a), Dye2 b), Dye3 c), Dye9 d), and Dye17 e).

[0050] Figure 14 Comparison of transmittance spectra of Dye1 film (a) before and after thermal baking and (b) before and after illumination.

[0051] Figure 15 Comparison of transmittance spectra of Dye2 film (a) before and after thermal baking and (b) before and after illumination.

[0052] Figure 16 Comparison of transmittance spectra of Dye3 film before and after thermal baking (a) and before and after illumination (b).

[0053] Figure 17 Comparison of transmittance spectra of Dye9 film before and after thermal baking (a) and before and after illumination (b).

[0054] Figure 18 Comparison of transmittance spectra of Dye17 film before and after thermal baking (a) and before and after illumination (b).

[0055] Figure 19 Comparison of the UV maximum absorption spectra of Dye1 dye solution before and after illumination.

[0056] Figure 20 Comparison of the UV maximum absorption spectra of Dye2 dye solution before and after illumination.

[0057] Figure 21 Comparison of the UV maximum absorption spectra of Dye3 dye solution before and after illumination.

[0058] Figure 22 Comparison of the UV maximum absorption spectra of Dye9 dye solution before and after illumination.

[0059] Figure 23 Comparison of the UV maximum absorption spectra of Dye17 dye solution before and after illumination. DETAILED DESCRIPTION

[0060] The following is a further detailed description of the present invention in conjunction with specific implementation methods. However, the following embodiments are only a part of the present invention and cannot be used as a basis for limiting the present invention. Non-essential changes based on the present invention still fall within the scope of protection of the present invention.

[0061] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 1 to 8 are shown in Table 1.

[0062] Table 1 Structural formula of dyes corresponding to pyridone substituted by silane coupling agent KH-550 as coupling component

[0063]

[0064] Example 1

[0065] The method for synthesizing the dye Dye1 in this embodiment comprises the following steps:

[0066] (1) Preparation of coupling component: A solution of ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and silane coupling agent KH-550 (22.14 g 0.1 mol) was added to a single-necked flask, stirred, heated, and refluxed for 12 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction, the solution turned from colorless to yellow, and pyridone substituted with silane coupling agent KH-550 was obtained. The product was extracted with ethyl acetate and recrystallized from ethanol with a yield of 78%.

[0067] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add pentachloroaniline (0.8 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5°C, add 40% nitrosyl sulfuric acid (1 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 30 minutes, pentachloroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0068] (3) Coupling reaction: The silane coupling agent KH-550 substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 5°C to 30°C. After 8 hours, sodium hydroxide was added to the mixture to adjust the pH to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain the yellow dye Dye1.

[0069] The structure of pyridone substituted by silane coupling agent KH-550 characterized by mass spectrometry, MS (API-ES): m / z = 353 ([MH] - ), 176([M-2H] 2- / 2), indicating that the structure of the pyridone substituted by the synthesized silane coupling agent KH-550 is correct; the structure of the dye Dye1 was characterized by mass spectrometry, MS (API-ES): m / z = 627 ([MH] - ), 313([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0070] FT-IR (KBr, cm -1 ):3369cm -1 ,3117cm -1 ,2982cm -1 ,2182cm -1 ,1714cm -1 ,1528cm -1 ,1466cm -1 ,1349cm -1 ,1305cm -1 ,1250cm -1 ,1188cm -1 ,1017cm -1 ,954cm -1 ,852cm -1 ,783cm -1 ,662cm -1 ,611cm -1 .

[0071] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye1 was correct.

[0072] Figure 2 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye1 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 418nm, which meets the color requirements of yellow filter dyes.

[0073] Example 2

[0074] The method for synthesizing the dye Dye2 in this embodiment comprises the following steps:

[0075] (1) The preparation method of the coupling component is the same as that in Example 1.

[0076] (2) Diazotization reaction: Concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) were placed in a 250 mL beaker and stirred. 2-cyano-4-nitro-6-bromoaniline (0.73 g 3 mmol) was added and stirred in an ice bath until completely dissolved. When the solution temperature dropped to 0-5 °C, 30% nitrosyl sulfuric acid (1.33 g 3.15 mmol) was added dropwise to the solution for diazotization reaction. After 60 minutes, 2-cyano-4-nitro-6-bromoaniline diazonium salt was generated. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0077] (3) Coupling reaction: The silane coupling agent KH-550 substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 5°C to 30°C. After 22 hours, sodium carbonate was added to the mixture and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain the red dye Dye2.

[0078] The structure of Dye2 was characterized by mass spectrometry, MS (API-ES): m / z = 605 ([MH] - ), 302([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0079] FT-IR (KBr, cm -1 ):3066cm -1 ,2978cm -1 ,2938cm -1 ,2226cm -1 ,1685cm -1 ,1659cm -1 ,1590cm -1 ,1521cm -1 ,1334cm -1 ,1301cm -1 ,1218cm -1 ,1148cm -1 ,1089cm -1 ,1017cm -1 ,889cm -1 ,845cm -1 ,739cm -1 ,586cm -1 .

[0080] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye2 was correct.

[0081] Figure 3The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye2 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 509nm, which meets the color requirements of red filter dyes.

[0082] Example 3

[0083] The method for synthesizing the dye Dye3 in this embodiment comprises the following steps:

[0084] (1) The preparation method of the coupling component is the same as that in Example 1.

[0085] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add 2-chloro-4-nitroaniline (0.52 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5 °C, add 40% nitrosylsulfuric acid (1 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 30 minutes, 2-chloro-4-nitroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosylsulfuric acid to obtain a diazonium salt solution.

[0086] (3) Coupling reaction: The silane coupling agent KH-550 substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 3°C to 30°C. After 15 hours, sodium bicarbonate was added to the mixture and the pH was adjusted to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain the magenta dye Dye3.

[0087] The structure of Dye3 was characterized by mass spectrometry. MS (API-ES): m / z = 536 ([MH] - ), 267.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0088] FT-IR (KBr, cm -1 ):3369cm -1 ,3157cm -1 ,3084cm -1 ,2982cm -1 ,2934cm -1 ,2441cm -1 ,2214cm -1 ,1689cm -1 ,1586cm -1 ,1528cm -1 ,1338cm -1,1305cm -1 ,1225cm -1 ,1177cm -1 ,892cm -1 ,779cm -1 ,725cm -1 ,593cm -1 .

[0089] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye3 was correct.

[0090] Figure 4 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye3 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 535nm, which meets the color requirements of magenta filter dye.

[0091] Examples 4-6

[0092] 4-Nitroaniline, 2-cyano-4-nitroaniline and 4-chloroaniline were used to replace pentachloroaniline in step (2) of Example 1 as the diazo component, respectively, to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 4 to 7 in Table 1.

[0093] The structure of Dye4 was characterized by mass spectrometry. MS (API-ES): m / z = 502 ([MH] - ), 250.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0094] FT-IR (KBr, cm -1 ):3439cm -1 ,2957cm -1 ,2920cm -1 ,2862cm -1 ,1608cm -1 ,1513cm -1 ,1470cm -1 ,1339cm -1 ,1233cm -1 ,1138cm -1 ,1093cm -1 ,837cm -1 ,740cm -1 ,612cm -1 , 561cm -1 .

[0095] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye4 was correct.

[0096] Figure 5 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye4 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 385nm, which meets the color requirements of yellow filter dyes.

[0097] Example 7

[0098] The method for synthesizing the dye Dye7 in this embodiment comprises the following steps:

[0099] (1) The preparation method of the coupling component is the same as that in Example 1.

[0100] (2) Diazotization reaction: Add 4-fluoroaniline (11.11 g 0.1 mol), water (100 mL), and 37% concentrated hydrochloric acid (0.3 mol 25 mL) to a 250 mL beaker and stir in an ice bath. Add 20 mL of an aqueous solution of sodium nitrite (7.24 g 0.105 mol) to the beaker. After 12 minutes, 4-fluoroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess sodium nitrite to obtain a diazonium salt solution.

[0101] (3) Coupling reaction: The silane coupling agent KH-550 substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 4°C to 30°C. After 10 hours, sodium bicarbonate was added to the mixture and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye7.

[0102] The structure of Dye7 was characterized by mass spectrometry. MS (API-ES): m / z=475 ([MH] - ), 237([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0103] FT-IR (KBr, cm -1 ):3355cm -1 ,3214cm -1 ,2892cm -1 ,2242cm -1 ,1747cm -1 ,1514cm -1 ,1454cm -1 ,1378cm -1 ,1298cm -1 ,1223cm -1 ,1093cm-1 ,1005cm -1 ,966cm -1 ,882cm -1 ,751cm -1 ,679cm -1 ,601cm -1 .

[0104] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye7 was correct.

[0105] Figure 6 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye7 in the solvent (DMF) are displayed. The UV maximum absorption wavelength of the dye in the solvent DMF is 390nm, which meets the color requirements of the yellow filter dye.

[0106] Example 8

[0107] Aniline was used instead of 4-fluoroaniline in step (2) of Example 7 as the diazo component to obtain the pyridone azo dye corresponding to the corresponding diazo component in Example 8 in Table 1.

[0108] The structure of Dye8 was characterized by mass spectrometry. MS (API-ES): m / z=457 ([MH] - ), 228([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0109] FT-IR (KBr, cm -1 ):3420cm -1 ,2945cm -1 ,2865cm -1 ,2620cm -1 ,2196cm -1 ,1649cm -1 ,1608cm -1 ,1469cm -1 ,1360cm -1 ,1327cm -1 ,1232cm -1 ,1115cm -1 ,834cm -1 ,746cm -1 ,681cm -1 ,552cm -1 .

[0110] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye8 was correct.

[0111] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 9 to 16 are shown in Table 2.

[0112] Table 2 Dye structures corresponding to pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine as coupling component

[0113]

[0114] Example 9

[0115] The method for synthesizing the dye Dye9 in this embodiment comprises the following steps:

[0116] (1) Preparation of coupling components: Ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (24.85 g 0.1 mol) were added to a single-necked flask, stirred, heated, and refluxed for 12 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the solution turned into a yellow color, and 3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propan-1-amine substituted pyridone was obtained. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 81%.

[0117] (2) Diazotization reaction: Concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) were placed in a 250 mL beaker and stirred. Pentachloroaniline (0.8 g 3 mmol) was added and stirred in an ice bath until completely dissolved. When the solution temperature dropped to 0-5 °C, 40% nitrosyl sulfuric acid (1 g 3.15 mmol) was added dropwise to the solution for diazotization reaction. Pentachloroaniline diazonium salt was generated after 42 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0118] (3) Coupling reaction: The 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 6°C to 30°C. After 12 hours, sodium hydroxide was added to the mixture to adjust the pH to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye9.

[0119] The structure of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane-substituted pyridone characterized by mass spectrometry, MS (API-ES): m / z=380 ([MH] - ), 189.5([M-2H]2- / 2), indicating that the structure of the synthesized 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane-substituted pyridone is correct; the structure of the dye Dye9 was characterized by mass spectrometry, MS (API-ES): m / z=654 ([MH] - ), 327([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0120] FT-IR (KBr, cm -1 ):2946cm -1 ,2931cm -1 ,2865cm -1 ,1703cm -1 ,1532cm -1 ,1462cm -1 ,1364cm -1 ,1323cm -1 ,1232cm -1 ,1104cm -1 ,830cm -1 ,735cm -1 ,575cm -1 .

[0121] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye9 was correct.

[0122] Figure 7 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye9 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 419nm, which meets the color requirements of yellow filter dyes.

[0123] Examples 10-15

[0124] 2-cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used to replace pentachloroaniline in step (2) of Example 9 as the diazo component, respectively, to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 10 to 15.

[0125] The structure of dye Dye10 was characterized by mass spectrometry, MS (API-ES): m / z=632 ([MH] - ), 315.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0126] FT-IR (KBr, cm-1 ):3173cm -1 ,2936cm -1 ,2910cm -1 ,2197cm -1 ,1862cm -1 ,1634cm -1 ,1557cm -1 ,1503cm -1 ,1342cm -1 ,1300cm -1 ,1212cm -1 ,1176cm -1 ,1084cm -1 ,1010cm -1 ,884cm -1 ,835cm -1 ,747cm -1 ,579cm -1 .

[0127] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye10 was correct.

[0128] Example 16

[0129] The steps were the same as those in Example 7, except that the diazo component remained unchanged and the coupling component was the pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine prepared in Example 9 to obtain the pyridone azo dye Dye16.

[0130] The structure of dye Dye16 was characterized by mass spectrometry, MS (API-ES): m / z=484 ([MH] - ), 241.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0131] FT-IR (KBr, cm -1 ):3446cm -1 ,2933cm -1 ,2869cm -1 ,2614cm -1 ,2178cm -1 ,1652cm -1 ,1603cm -1 ,1479cm -1 ,1347cm -1 ,1325cm -1 ,1229cm -1 ,1112cm -1 ,835cm -1,756cm -1 ,692cm -1 ,548cm -1 .

[0132] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye16 was correct.

[0133] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 17 to 24 are shown in Table 3.

[0134] Table 3 Dye structures corresponding to propylheptyl-cage polysilsesquioxane-substituted pyridone as coupling component

[0135]

[0136] Example 17

[0137] The method for synthesizing the dye Dye17 in this embodiment comprises the following steps:

[0138] (1) Preparation of coupling components: Ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and aminopropylheptyl-cage polysilsesquioxane (87.46 g 0.1 mol) were added to a single-necked flask, stirred, heated, and refluxed for 12 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the solution turned yellow, and propylheptyl-cage polysilsesquioxane-substituted pyridone was obtained. The solution was extracted with ethyl acetate and recrystallized from ethanol with a yield of 85%.

[0139] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add pentachloroaniline (0.8 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5 °C, add 40% nitrosyl sulfuric acid (1 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 25 minutes, pentachloroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosyl sulfuric acid.

[0140] (3) Coupling reaction: The propylheptyl-cage polysilsesquioxane-substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 5°C to 30°C. After 12 hours, sodium hydroxide was added to the mixture to adjust the pH to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain the yellow dye Dye17.

[0141] The structure of dye Dye17 was characterized by mass spectrometry, MS (API-ES): m / z=1279 ([MH] - ), 639([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0142] FT-IR (KBr, cm -1 ):3446cm -1 ,2960cm -1 ,2902cm -1 ,1642cm -1 ,1547cm -1 ,1411cm -1 ,1254cm -1 ,1086cm -1 ,1024cm -1 ,867cm -1 ,797cm -1 ,691cm -1 .

[0143] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye17 was correct.

[0144] Figure 8 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye17 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 417nm, which meets the color requirements of yellow filter dyes.

[0145] Examples 18 to 23

[0146] 2-cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used to replace pentachloroaniline in step (2) of Example 17 as the diazo component, respectively, to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 18 to 23.

[0147] Example 24

[0148] The steps were the same as those in Example 7, except that the diazo component remained unchanged and the coupling component was the propylheptyl-cage polysilsesquioxane-substituted pyridone prepared in Example 17, to obtain the pyridone azo dye Dye24.

[0149] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 25 to 32 are shown in Table 4.

[0150] Table 4 Dye structures corresponding to 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-dipropyl-1-propylamine-substituted pyridone as coupling component

[0151]

[0152] Example 25

[0153] The method for synthesizing the dye Dye25 in this embodiment comprises the following steps:

[0154] (1) Preparation of coupling components: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol), bromopropane (13.53 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N 1-Dimethylformamide (100 mL) was added to a single-necked flask, stirred, and heated under reflux for 8 hours. The reaction progress was monitored by thin-layer chromatography. After completion of the reaction, an orange solution was obtained, yielding 3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)-N,N-dipropyl-1-propylamine-substituted pyridone. Extraction with ethyl acetate and recrystallization from ethanol yielded 71%.

[0155] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add pentachloroaniline (0.8 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5°C, add 40% nitrosyl sulfuric acid (1 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 22 minutes, pentachloroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0156] (3) Coupling reaction: The 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-dipropyl-1-propylamine-substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 2°C to 30°C. After 11 hours, sodium carbonate was added to the mixture to adjust the pH to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain the yellow dye Dye25.

[0157] The structure of dye Dye25 was characterized by mass spectrometry, MS (API-ES): m / z=738 ([MH] - ), 369([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0158] FT-IR (KBr, cm -1 ):3464cm -1 ,3362cm -1 ,2949cm -1 ,2872cm -1 ,2222cm -1 ,1677cm -1 ,1642cm -1 ,1594cm -1 ,1503cm -1 ,1418cm -1 ,1360cm -1 ,1247cm -1 ,1181cm -1 ,1054cm -1 ,830cm -1 ,794cm -1 , 673cm -1 .

[0159] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye25 was correct.

[0160] Figure 9 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye25 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 417nm, which meets the color requirements of yellow filter dyes.

[0161] Examples 26-31

[0162] 2-cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used to replace pentachloroaniline in step (2) of Example 25 as the diazo component, respectively, to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 26 to 31.

[0163] Example 32

[0164] The steps were the same as those in Example 7, except that the diazo component remained unchanged and the coupling component was the pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-dipropyl-1-propylamine prepared in Example 25 to obtain the pyridone azo dye Dye32.

[0165] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 33 to 40 are shown in Table 5.

[0166] Table 5 Dye structures corresponding to pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-bis(2-methoxyethyl)propan-1-amine as coupling component

[0167]

[0168] Example 33

[0169] The method for synthesizing the dye Dye35 in this embodiment comprises the following steps:

[0170] (1) Preparation of coupling components: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol), chloroethyl methyl ether (10.40 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N 1-Dimethylformamide (100 mL) was added to a single-necked flask, stirred, and heated under reflux for 8 hours. The reaction progress was monitored by thin-layer chromatography. After completion of the reaction, the solution turned orange-yellow, yielding a pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)-N,N-bis(2-methoxyethyl)propan-1-amine. Extraction with ethyl acetate and recrystallization from ethanol yielded a 69% yield.

[0171] (2) Diazotization reaction: Concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) were placed in a 250 mL beaker and stirred. 2-chloro-4-nitroaniline (0.52 g 3 mmol) was added and stirred in an ice bath until completely dissolved. When the solution temperature dropped to 0-5 °C, 30% nitrosyl sulfuric acid (1.33 g 3.15 mmol) was added dropwise to the solution for diazotization reaction. Pentachloroaniline diazonium salt was generated after 25 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0172] (3) Coupling reaction: The 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-bis(2-methoxyethyl)propan-1-amine substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 4°C to 32°C. After 10 hours, sodium carbonate was added to the mixture to adjust the pH to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain the magenta dye Dye35.

[0173] The structure of dye Dye35 was characterized by mass spectrometry, MS (API-ES): m / z=679 ([MH] - ), 339.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0174] FT-IR (KBr, cm -1 ):3413cm -1 ,3106cm -1 ,3028cm -1 ,2977cm -1 ,2912cm -1 ,2389cm -1 ,2197cm -1 ,1678cm -1 ,1563cm -1 ,1514cm -1 ,1308cm -1 ,1217cm -1 ,1087cm -1 ,893cm -1 , 792cm -1 ,685cm -1 ,594cm -1 .

[0175] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye35 was correct.

[0176] Figure 10 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye35 in solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 533nm, which meets the color requirements of magenta filter dye.

[0177] Examples 34 to 39

[0178] 2-Cyano-4-nitro-6-bromoaniline, pentachloroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used as diazo components to replace 2-chloro-4-nitroaniline in step (2) of Example 33, respectively, to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 34 to 39.

[0179] Example 40

[0180] The steps are the same as those in Example 7, except that the diazo component remains unchanged and the coupling component is the pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-bis(2-methoxyethyl)propan-1-amine prepared in Example 33 to obtain the pyridone azo dye Dye40.

[0181] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 41 to 48 are shown in Table 6.

[0182] Table 6 Dye structures corresponding to pyridone substituted with N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine as coupling component

[0183]

[0184] Example 41

[0185] The method for synthesizing the dye Dye43 in this embodiment comprises the following steps:

[0186] (1) Preparation of coupling components: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol), benzyl chloride (13.92 g 0.11 mol), cesium carbonate (16.29 g 0.05 mol), N,N 1-Dimethylformamide (100 mL) was added to a single-necked flask, stirred, and heated under reflux for 11 hours. The reaction progress was monitored by thin-layer chromatography. After completion of the reaction, a brown-gray solution was obtained, yielding N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propan-1-amine-substituted pyridone. Extraction with ethyl acetate and recrystallization from ethanol yielded 62%.

[0187] (2) Diazotization reaction: Concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) were placed in a 250 mL beaker and stirred. 2-chloro-4-nitroaniline (0.52 g 3 mmol) was added and stirred in an ice bath until completely dissolved. When the solution temperature dropped to 0-5 °C, 30% nitrosyl sulfuric acid (1.33 g 3.15 mmol) was added dropwise to the solution for diazotization reaction. Pentachloroaniline diazonium salt was generated after 40 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0188] (3) Coupling reaction: The N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 5°C to 28°C. After 12 hours, sodium hydroxide was added to the mixture to adjust the pH to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain the magenta dye Dye43.

[0189] The structure of dye Dye43 was characterized by mass spectrometry, MS (API-ES): m / z=743 ([MH] - ), 371.5([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0190] FT-IR (KBr, cm -1 ):3432cm -1 ,3147cm -1 ,3015cm -1 ,2963cm -1 ,2909cm -1 ,2427cm -1 ,2188cm -1 ,1664cm -1 ,1538cm -1 ,1506cm -1 ,1313cm -1 ,1210cm -1 ,1083cm -1 ,887cm -1 , 783cm -1 ,697cm -1 ,586cm -1 .

[0191] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye43 was correct.

[0192] Figure 11 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye43 in solvent (DMF) are displayed. The UV maximum absorption wavelength of the dye in solvent DMF is 536nm, which meets the color requirements of magenta filter dye.

[0193] Examples 42 to 47

[0194] 2-Cyano-4-nitro-6-bromoaniline, pentachloroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used as diazo components to replace 2-chloro-4-nitroaniline in step (2) of Example 41, respectively, to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 42 to 47.

[0195] Example 48

[0196] The steps were the same as those in Example 7, except that the diazo component remained unchanged and the coupling component was the pyridone substituted with N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine prepared in Example 41 to obtain the pyridone azo dye Dye48.

[0197] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 49 to 56 are shown in Table 7.

[0198] Table 7 Dye structures corresponding to pyridone substituted with 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine as coupling component

[0199]

[0200] Example 49

[0201] The method for synthesizing the dye Dye49 in this embodiment comprises the following steps:

[0202] (1) Preparation of coupling components: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol), 1,3-dibromopropane (22.21 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N 1-Dimethylformamide (100 mL) was added to a single-necked flask, stirred, and heated under reflux for 9 hours. The reaction progress was monitored by thin-layer chromatography. After completion of the reaction, a dark green solution was obtained, yielding 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propyl)propan-1-amine-substituted pyridone. Extraction with ethyl acetate and recrystallization from ethanol yielded 77%.

[0203] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add pentachloroaniline (0.8 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5°C, add 30% nitrosyl sulfuric acid (1.33 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 40 minutes, pentachloroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0204] (3) Coupling reaction: The 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 3°C to 31°C. After 8 hours, sodium hydroxide was added to the mixture to adjust the pH to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye49.

[0205] The structure of dye Dye49 was characterized by mass spectrometry. MS (API-ES): m / z=894 ([MH] -), 447([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0206] FT-IR (KBr, cm -1 ):3482cm -1 ,3384cm -1 ,2946cm -1 ,2219cm -1 ,1645cm -1 ,1594cm -1 ,1536cm -1 ,1503cm -1 ,1418cm -1 ,1383cm -1 ,1250cm -1 ,1166cm -1 ,1061cm -1 ,830cm -1 , 790cm -1 ,710cm -1 ,673cm -1 ,524cm -1 .

[0207] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye49 was correct.

[0208] Figure 12 The molecular structure, UV maximum absorption spectrum (DMF), and color of the pyridone azo dye Dye49 in solvent (DMF) are displayed. The UV maximum absorption wavelength of the dye in solvent DMF is 390nm, which meets the color requirements of yellow filter dyes.

[0209] Examples 50-55

[0210] 2-Cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used respectively instead of pentachloroaniline as the diazo component to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 50 to 55.

[0211] Example 56

[0212] The steps were the same as those in Example 7, except that the diazo component remained unchanged and the coupling component R was the 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propyl)propan-1-amine-substituted pyridone prepared in Example 49 to obtain the pyridone azo dye Dye56.

[0213] The specific structures of the pyridone azo dyes prepared from the same coupling component but different diazo components in Examples 57 to 64 are shown in Table 8.

[0214] Table 8 Dye structures corresponding to pyridone substituted with 3-(4-(tert-butyl)phenoxy)-N-(3-(4-(tert-butyl)phenoxy)propyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine as coupling component

[0215]

[0216] Example 57

[0217] The method for synthesizing the dye Dye57 in this embodiment comprises the following steps:

[0218] (1) Preparation of coupling components: 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine substituted pyridone (24.47 g 0.05 mol), 4-tert-butylphenol (15.01 g 0.1 mol), potassium carbonate (6.91 g 0.05 mol), N,N 1-Dimethylformamide (100 mL) was added to a single-necked flask, stirred, and heated under reflux for 8 hours. The reaction progress was monitored by thin-layer chromatography. After completion of the reaction, the product was extracted with ethyl acetate and recrystallized from ethanol to obtain 3-(4-(tert-butyl)phenoxy)-N-(3-(4-(tert-butyl)phenoxy)propyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propyl)propan-1-amine-substituted pyridone in a 67% yield.

[0219] (2) Diazotization reaction: Place concentrated sulfuric acid (20 mL) and concentrated phosphoric acid (20 mL) in a 250 mL beaker and stir. Add pentachloroaniline (0.8 g 3 mmol) and continue stirring in an ice bath until it is completely dissolved. When the solution temperature drops to 0-5°C, add 30% nitrosyl sulfuric acid (1.33 g 3.15 mmol) dropwise to the solution for diazotization reaction. After 40 minutes, pentachloroaniline diazonium salt is generated. Add a small amount of aminosulfonic acid to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0220] (3) Coupling reaction: The 3-(4-(tert-butyl)phenoxy)-N-(3-(4-(tert-butyl)phenoxy)propyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine substituted pyridone obtained in step (1) was dissolved in a mixed solvent of water (50 mL) and ethanol (50 mL) and stirred until completely dissolved. The diazonium salt solution obtained in step (2) was added dropwise to the coupling component. The reaction temperature was gradually increased from 2°C to 26°C. After 8 hours, sodium hydroxide was added to the mixture to adjust the pH to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye57.

[0221] The structure of dye Dye57 was characterized by mass spectrometry, MS (API-ES): m / z=1034 ([MH] - ), 517([M-2H] 2- / 2), characterizing that the molecular weight of the synthesized molecule is consistent with that of the target molecule.

[0222] FT-IR (KBr, cm -1 ):3412cm -1 ,3127cm -1 ,2979cm -1 ,2173cm -1 ,1735cm -1 ,1559cm -1 ,1436cm -1 ,1325cm -1 ,1300cm -1 ,1279cm -1 ,1168cm -1 ,1076cm -1 ,936cm -1 ,872cm -1 ,794cm -1 ,653cm -1 ,598cm -1 .

[0223] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye57 was correct.

[0224] Examples 58-63

[0225] 2-cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, and 4-trifluoromethylaniline were used to replace pentachloroaniline in step (2) of Example 57 as the diazo component to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 58 to 63.

[0226] Example 64

[0227] The steps are the same as those in Example 7, except that the diazo component remains unchanged and the coupling component is the pyridone substituted with 3-(4-(tert-butyl)phenoxy)-N-(3-(4-(tert-butyl)phenoxy)propyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine prepared in Example 57 to obtain the pyridone azo dye Dye64.

[0228] Example 65

[0229] Five dyes, Dye1, Dye2, Dye3, Dye9 and Dye17, were selected as representatives to prepare dye resins, and the dyes were tested for ultraviolet maximum absorption spectrum, photostability, thermal stability and solubility; the prepared dye resins were tested for photostability, thermal stability and chromaticity.

[0230] Accurately weigh 0.1g of dye to prepare a 1μM solution, then mix dye: acrylic resin: N,N -dimethylformamide (DMF) = 1:20:100 (volume ratio) to prepare a dye resin solution, which was spin-coated on a glass slide to prepare a resin sheet. The measured UV maximum absorption wavelength, molar absorption coefficient, solubility, solution transmittance, and transmittance of the prepared dye resin are shown in Table 9 below; the values ​​of the prepared dye resin before and after heat baking and the calculated color difference are shown in Table 10 below; the values ​​of the prepared dye resin before and after light irradiation and the calculated color difference are shown in Table 11 below; the transmittance spectra of the prepared dye resin film before and after heat baking and before and after light irradiation are compared. Figure 14-18 As shown; the UV maximum absorption spectrum of the prepared dye resin before and after illumination is as shown Figure 19-23 shown.

[0231] The formula for calculating the chromaticity difference is as follows:

[0232]

[0233] Among them, △L*=L2-L1,△a*=a2-a1,△b*=b2-b1.

[0234] L1a1b1 represents the test value before baking or exposure to light, and L2a2b2 represents the test value after baking or exposure to light. The change in transmittance of the dye resin before and after exposure to light is calculated from the change in the transmission spectrum; the change in solution transmittance is calculated from both the transmission spectrum and the UV maximum absorption spectrum.

[0235] Table 9 Five dyes in solvent N,N- Performance in dimethylformamide

[0236]

[0237] Table 10 Chromaticity values ​​of five dyes before and after baking

[0238]

[0239] Table 11 Chromaticity values ​​of five dyes before and after light exposure

[0240]

[0241] According to the solution transmittance in Table 9, which is higher than 94%, it can be explained that the synthesized pyridone azo dye molecules substituted by silane coupling agent KH-550, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane derivatives and aminopropylheptyl-cage polysilsesquioxane at the N position are not planar, and have a certain steric hindrance in the solution, which effectively prevents the aggregation of molecules. N,N- It has good solubility in dimethylformamide (DMF) solvent, with a solubility greater than 5wt%. Tables 10 and 11 show that the dye has good dispersion in the acrylic resin film material, making the color film material have good light transmittance. The color difference data of the five dye resins before and after baking in Table 10 are all less than 3, indicating that the pyridone azo dye has good thermal stability. Figure 14 a, 15a, 16a, 17a, and 18a correspond to the transmittance spectra of the dye resin films of the five dyes before and after thermal baking. It can be seen that there is a certain change in the transmittance of the film before and after baking, which echoes the color difference of the dye resin before and after baking in Table 10; the color difference data of the dye resin before and after illumination in Table 11 are all less than 2, indicating that the pyridone azo dye molecule has good light stability. Figure 14 b, 15b, 16b, 17b, and 18b correspond to the transmittance spectra of the dye resin films of the five dyes before and after irradiation with ultraviolet light. It can be seen that they are basically unchanged, which is consistent with Table 11, indicating that the five dyes have good light stability.

[0242] Figure 19-23 The light stability of the dye solution is tested. The UV maximum absorption spectrum of the dye solution is tested before and after irradiation with UV light. It can be seen that the spectrum remains basically unchanged, indicating that the dye has good light stability.

[0243] Figure 13 The digital photos corresponding to the five dye resins show that the prepared dye resins have brighter chromaticity and higher transmittance.

[0244] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A pyridone azo dye, characterized in that The general structural formula of the pyridone azo dye is shown in Formula I: Formula I In formula I, X1, X2, X3, X4, and X5 are each independently selected from nitro, hydrogen, fluorine, chlorine, bromine, and cyano; R is one of Ⅰ-1, Ⅰ-2 or Ⅰ-3: Wherein, 0<n<100, n is an integer; M1 and M2 are independently selected from one of the following structural formulas: 、 、 、 、 、 、 、 、 、、 、 、-H、-F、-Cl、-Br、-I; Wherein, 0<m<22, m is an integer.

2. The method for preparing the pyridone azo dye according to claim 1, wherein The steps include: (1) Using an aromatic primary amine containing a benzene ring-inactivating group as the diazo component, the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid are added to a reaction vessel. After cooling to 0-5°C, nitrosyl sulfuric acid is added dropwise to carry out a diazotization reaction. After the reaction is completed, aminosulfonic acid is added to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution. (2) Using the pyridone substituted with R at the N position as the coupling component, the coupling component, ethanol and water are added to a reaction vessel, stirred at room temperature to dissolve the coupling component, cooled to 0-5°C, and the diazonium salt solution obtained in step (1) is added under stirring. The reaction mixture is gradually heated to room temperature to carry out the coupling reaction; (3) After the reaction is completed, water is added to precipitate the solid, and then alkali is added to the resulting dye mixture to adjust the pH value of the solution to neutral; (4) After post-processing, it is obtained.

3. The preparation method according to claim 2, characterized in that The structural formula of the diazo component is shown in Formula II: 。 Formula II 4. The preparation method according to claim 2, wherein The structural formula of the coupling component is shown in III: 。 Formula III 5. The preparation method according to any one of claims 2 to 4, characterized in that In step (1), the molar ratio of the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid is 1:1:1 to 1:3:3; the concentration of the nitrosyl sulfuric acid is 25 wt% to 40 wt%; and the diazotization reaction time is 0.2 h to 8 h.

6. The preparation method according to any one of claims 2 to 4, characterized in that In step (2), the molar ratio of the coupling component, ethanol and water is 1:50:50 to 1:500:

500.

7. The preparation method according to any one of claims 2 to 4, characterized in that In step (2), the time for adding the diazonium salt solution to the coupling component is 1 min to 60 min; and the coupling reaction time is 1 h to 24 h.

8. The preparation method according to any one of claims 2 to 4, characterized in that In step (4), the post-processing includes: The dye mixture obtained in step (3) is filtered and washed with water until the filtrate is clear, and then dried to obtain a crude product; the crude product is purified by column chromatography using an organic solvent gradient elution.

9. The preparation method according to claim 8, characterized in that The organic solvent is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the solvent used is ethyl acetate: petroleum ether=1:1-1:5.

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