Pyridone azo dye and preparation method thereof

Abstract

The invention discloses a pyridone azo dye and a preparation method thereof, and belongs to the technical field of fine chemical engineering. The structural general formula of the pyridone azo dye is as follows: # imgabs0 #, wherein X1, X2, X3, X4 and X5 are respectively and independently selected from one of nitro, hydrogen, fluorine, chlorine, bromine, cyano and substituted or unsubstituted phenyl; the R substituent group is selected from one of the following structures: # imgabs 1 #. By introducing the R substituent group to the N site of pyridone, the problem of low solubility of the pyridone azo dye in an organic solvent can be effectively solved. The solubility of the pyridone azo dye disclosed by the invention in an organic solvent is 5-9g / 100mL, the molar absorption coefficient of the dye is in a range of 20000-120000 L.mol <-1 >. Cm <-1 >, and the pyridone azo dye is excellent in light and heat resistance stability and has the feasibility of preparing optical devices and full-color high-stability 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 chemical industry. Background Art

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

[0003] As an important component of heterocyclic azo dyes, pyridone derivatives are mostly used as coupling components to prepare brightly colored dyes. Compared with traditional dyes, they have higher molar absorption coefficients and higher fastness properties. They are usually used as disperse dyes for coloring textiles (CN 105504858 A). Disperse dyes are characterized by being insoluble in water and containing fat-soluble substituents in the molecules, which just meets our requirements for filter dyes. However, a fundamental problem with pyridone azo dyes is their low solubility in organic solvents.

[0004] In order to improve this deficiency, some researchers have introduced aliphatic, aryl, heterocyclic, carbamoyl, aliphatic carbonyl, aryloxycarbonyl, acyl, aliphatic sulfonyl, arylsulfonyl, sulfamoyl and other substituents at the N position of pyridone, and the prepared yellow filter dye has good color and brightness, but no specific description of solubility is given (CN102483479 A). Another researcher introduced hydroxyethyl at the N position of pyridone, and coupled with aniline diazonium salt containing methyl, hydroxyl, methyl formate and tert-butyl in the diazo component to prepare nine dyes. The results show that the solubility of three of the nine dyes in N-methylpyrrolidone (NMP) is greater than 4wt%, one dye is greater than 3wt%, and the solubility of the other dyes is less than 3wt% (Coloration Technology, 133, 158-164, 2016.). Later, some 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.). It can be seen that the introduction of conventional low-carbon alkyl, hydroxyl, and ester substituents cannot effectively improve the low solubility of pyridone azo dyes. Therefore, some researchers invented a class of alkyl substituted with C1~C20 at the N position, *-C(=O)OR 1 or *-OC(=O)R 1 The pyridone, the diazo component is a terminal containing The aniline with a middle section composed of a long-chain alkane polymer has a solubility of more than 20wt% and excellent solubility performance (CN 105801477 A). However, the introduction of a long-chain polymer into the molecule will inevitably lead to a decrease in the molar absorption coefficient of the dye. Therefore, it has become an urgent problem to be solved to effectively improve the solubility of pyridone azo dyes in organic solvents while ensuring that the molar absorption coefficient of the dye is not affected. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a pyridone azo dye with excellent solubility and a preparation method thereof. The diazo component of the dye is an aromatic primary amine containing a group that makes the benzene ring passivated, and the coupling component is a silane coupling agent (RSiX 3), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane derivatives or cage-type polysilsesquioxane (POSS) substituted pyridone. The electron-withdrawing group contained in the diazo component of this type of dye synergistically acts 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 photostability of the dye; compared with the conventional CO bond, the Si-O bond itself has a higher bond energy and a larger bond angle, which can improve the thermal stability of the dye.

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

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

[0008]

[0009] In Formula I, X 1 , X 2 , X 3 , X 4 , X 5 Each is independently selected from one of nitro, hydrogen, fluorine, chlorine, bromine, cyano, substituted or unsubstituted phenyl; R is one of Ⅰ-1, Ⅰ-2 or Ⅰ-3:

[0010]

[0011] Wherein, 0<n<100, n is an integer;

[0012] M 1 、M 2 Independently selected from one of the following structural formulas:

[0013]

[0014] -H, -F, -Cl, -Br, -I;

[0015] Wherein, 0<m<22, m is an integer.

[0016] In a second aspect, the present invention provides a method for preparing the above-mentioned pyridone azo dye, comprising the following steps:

[0017] (1) An aromatic primary amine containing a group that can inactivate a benzene ring is used as a diazo component, and the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid are added to a reaction vessel. After the temperature is lowered 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;

[0018] (2) using the pyridone substituted with R at the N position as the coupling component, adding the coupling component, ethanol and water into a reaction vessel, stirring at room temperature to dissolve the coupling component, cooling to 0-5° C., adding the diazonium salt solution obtained in step (1) under stirring, and gradually warming the temperature to room temperature to carry out the coupling reaction;

[0019] (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;

[0020] (4) After post-processing, the product is obtained.

[0021] Furthermore, the structural formula of the diazo component is shown in Formula II:

[0022]

[0023] Furthermore, the structural formula of the coupling component is shown in III:

[0024]

[0025] 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.

[0026] Furthermore, in step (1), the concentration of nitrosyl sulfuric acid is 25 wt% to 40 wt%, more preferably 40 wt%.

[0027] Furthermore, in step (1), the diazotization reaction time is 0.2 h to 8 h, more preferably 0.5 h.

[0028] Furthermore, in step (2), the ratio of the coupling component, ethanol and water is 1:50:50 to 1:500:500.

[0029] 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.

[0030] Furthermore, in step (2), the coupling reaction time is 1 h to 24 h, more preferably 8 h.

[0031] 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 obtained crude product by column chromatography and eluting with an organic solvent gradient.

[0032] 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.

[0033] The beneficial effects of the present invention are as follows: the pyridone azo dye of the present invention has a high molar absorption coefficient, presents bright color and high brightness in a solvent; the dye has excellent light and heat stability, the color difference of a color film prepared with the dye before and after being illuminated under an ultraviolet lamp is less than 1.5, and the color difference of the color film before and after being baked at 220°C is less than 3 (except for Dye2); at the same time, the solubility of the dye in organic solvents such as propylene glycol methyl ether acetate (PGMEA) and N,N-dimethylformamide (DMF) can reach 5-9g / 100mL, so that the utilization rate of the dye is improved during use, and the problem of low solubility of the pyridone azo dye in organic solvents is well solved, and the synthesis thereof is relatively easy, which is conducive to its production and application in industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of N-position substitution of pyridone.

[0035] Figure 2 The molecular structure of Dye1, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF).

[0036] Figure 3 The molecular structure of Dye2, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF).

[0037] 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.

[0038] 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.

[0039] 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.

[0040] Figure 7 The molecular structure of Dye9, the maximum UV absorption spectrum (DMF), and the color of the dye in the solvent (DMF).

[0041] 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.

[0042] Fig. 9The molecular structure of Dye25, the maximum UV absorption spectrum (DMF) and the color of the dye in the solvent (DMF) are displayed.

[0043] Fig.10 The molecular structure of Dye35, the maximum UV absorption spectrum (DMF) and the color of the dye in the solvent (DMF) are displayed.

[0044] Fig.11 The molecular structure of Dye43, the maximum UV absorption spectrum (DMF) and the color of the dye in the solvent (DMF) are displayed.

[0045] Fig.12 The molecular structure of Dye49, the maximum UV absorption spectrum (DMF) and the color of the dye in the solvent (DMF) are displayed.

[0046] Fig.13 Color film images of dyes Dye1 (a), Dye2 (b), Dye3 (c), Dye9 (d), and Dye17 (e).

[0047] Fig.14 Comparison of transmittance spectra of Dye1 film before and after thermal baking (a) and before and after illumination (b).

[0048] Fig.15 Comparison of transmittance spectra of Dye2 films before and after thermal baking (a) and before and after illumination (b).

[0049] Fig.16 Comparison of transmittance spectra of Dye3 films before and after thermal baking (a) and before and after illumination (b).

[0050] Fig.17 Comparison of transmittance spectra of Dye9 films before and after thermal baking (a) and before and after illumination (b).

[0051] Fig.18 Comparison of transmittance spectra of Dye17 films before and after thermal baking (a) and before and after illumination (b).

[0052] Fig.19 Comparison of the UV maximum absorption spectra of Dye1 dye solution before and after illumination.

[0053] Fig. 20 Comparison of the UV maximum absorption spectra of Dye2 dye solution before and after illumination.

[0054] Fig.21 Comparison of the UV maximum absorption spectra of Dye3 dye solution before and after illumination.

[0055] Fig. 22 Comparison of the UV maximum absorption spectra of Dye9 dye solution before and after illumination.

[0056] Fig.23 Comparison of the UV maximum absorption spectra of Dye17 dye solution before and after illumination. DETAILED DESCRIPTION

[0057] The following is a further detailed description of the present invention in conjunction with specific implementation methods, but the following embodiments are only some examples 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.

[0058] The specific structures of the pyridone azo dyes prepared from the same coupling component and different diazo components in Examples 1 to 8 are shown in Table 1.

[0059] Table 1 Structural formula of dyes corresponding to pyridone substituted by silane coupling agent KH-550 as coupling component

[0060]

[0061] Example 1

[0062] The method for synthesizing the dye Dye1 in this embodiment comprises the following steps:

[0063] (1) Preparation of coupling component: 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) were added to a single-necked flask, stirred, heated and refluxed for 12 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solution turned from colorless to yellow, and pyridone substituted by silane coupling agent KH-550 was obtained. The product was extracted with ethyl acetate and recrystallized from ethanol, with a yield of 78%.

[0064] (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 stirring was continued in an ice bath until it was 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, and pentachloroaniline diazonium salt was generated after 30 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0065] (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, and the reaction temperature was gradually increased from 5°C to 30°C. After 8 hours, sodium hydroxide was added to the mixed solution, and the pH was adjusted to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain the yellow dye Dye1.

[0066] 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 is 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 the molecular weight of the target molecule.

[0067] 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 .

[0068] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye1 was correct.

[0069] Figure 2 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye1 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 418nm, which meets the color requirements of the yellow filter dye.

[0070] Example 2

[0071] The method for synthesizing dye Dye2 in this embodiment comprises the following steps:

[0072] (1) The preparation method of the coupling component is the same as that of Example 1.

[0073] (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 stirring was continued in an ice bath until it was 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, and 2-cyano-4-nitro-6-bromoaniline diazonium salt was generated after 60 minutes, and a small amount of aminosulfonic acid was added to eliminate excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0074] (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, and the reaction temperature was gradually increased from 5°C to 30°C. After 22 hours, sodium carbonate was added to the mixed solution, 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.

[0075] 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 the molecular weight of the target molecule.

[0076] 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 .

[0077] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye2 was correct.

[0078] Figure 3 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye2 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 509nm, which meets the color requirements of the red filter dye.

[0079] Example 3

[0080] The method for synthesizing dye Dye3 in this embodiment comprises the following steps:

[0081] (1) The preparation method of the coupling component is the same as that of Example 1.

[0082] (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 stirring was continued in an ice bath until it was 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, and 2-chloro-4-nitroaniline diazonium salt was generated after 30 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid to obtain a diazonium salt solution.

[0083] (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, and the reaction temperature was gradually increased from 3°C to 30°C. After 15 hours, sodium bicarbonate was added to the mixed solution, and the pH was adjusted to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain a magenta dye Dye3.

[0084] 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 the molecular weight of the target molecule.

[0085] 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 .

[0086] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye3 was correct.

[0087] Figure 4 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye3 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 535nm, which meets the color requirements of the magenta filter dye.

[0088] Embodiments 4 to 6

[0089] 4-nitroaniline, 2-cyano-4-nitroaniline and 4-chloroaniline were used to replace pentachloroaniline in step (2) of Example 1 as diazo components to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 4 to 7 in Table 1.

[0090] 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 the molecular weight of the target molecule.

[0091] 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 .

[0092] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye4 was correct.

[0093] Figure 5 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye4 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 385nm, which meets the color requirements of the yellow filter dye.

[0094] Example 7

[0095] The method for synthesizing dye Dye7 in this embodiment comprises the following steps:

[0096] (1) The preparation method of the coupling component is the same as that of Example 1.

[0097] (2) Diazotization reaction: 4-fluoroaniline (11.11 g 0.1 mol), water (100 mL), and 37% concentrated hydrochloric acid (0.3 mol 25 mL) were added to a 250 mL beaker and stirred in an ice bath. 20 mL of an aqueous solution of sodium nitrite (7.24 g 0.105 mol) was added to the beaker. After 12 minutes, 4-fluoroaniline diazonium salt was generated. A small amount of aminosulfonic acid was added to eliminate excess sodium nitrite to obtain a diazonium salt solution.

[0098] (3) Coupling reaction: The pyridone substituted with the silane coupling agent KH-550 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, and the reaction temperature was gradually increased from 4°C to 30°C. After 10 hours, sodium bicarbonate was added to the mixed solution, and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain the yellow dye Dye7.

[0099] 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 the molecular weight of the target molecule.

[0100] 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 .

[0101] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye7 was correct.

[0102] Figure 6 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye7 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 390nm, which meets the color requirements of the yellow filter dye.

[0103] Example 8

[0104] Aniline is 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.

[0105] The structure of the dye 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 the molecular weight of the target molecule.

[0106] 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 .

[0107] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye8 was correct.

[0108] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 9 to 16 are shown in Table 2.

[0109] Table 2 Dye structures corresponding to pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propane-1-amine as coupling component

[0110]

[0111]

[0112] Example 9

[0113] The method for synthesizing the dye Dye9 in this embodiment comprises the following steps:

[0114] (1) Preparation of coupling component: Ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (24.85 g 0.1 mol) solution was added to a single-necked flask, stirred, heated and refluxed for 12 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, it turned into a yellow solution to obtain 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 81%.

[0115] (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 stirring was continued in an ice bath until it was 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, and 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.

[0116] (3) Coupling reaction: The 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propane-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, and the reaction temperature was gradually increased from 6°C to 30°C. After 12 hours, sodium hydroxide was added to the mixed solution, and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye9.

[0117] 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 the molecular weight of the target molecule.

[0118] 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 .

[0119] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye9 was correct.

[0120] Figure 7 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye9 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 419nm, which meets the color requirements of the yellow filter dye.

[0121] Embodiments 10 to 15

[0122] 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 diazo components to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 10 to 15.

[0123] 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 the molecular weight of the target molecule.

[0124] 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 .

[0125] Combined with the mass spectrum and infrared analysis of the product, it was shown that the structure of the synthesized dye Dye10 was correct.

[0126] Example 16

[0127] 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)propan-1-amine prepared in Example 9 to obtain the pyridone azo dye Dye16.

[0128] 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 the molecular weight of the target molecule.

[0129] 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 .

[0130] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye16 was correct.

[0131] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 17 to 24 are shown in Table 3.

[0132] Table 3 Dye structures corresponding to pyridone substituted by propylheptyl-cage polysilsesquioxane as coupling component

[0133]

[0134]

[0135] Embodiment 17

[0136] The method for synthesizing the dye Dye17 in this embodiment comprises the following steps:

[0137] (1) Preparation of coupling component: Ethyl cyanoacetate (11.31 g 0.1 mol), ethyl acetoacetate (13.01 g 0.1 mol), ethanol (10 ml), piperidine (3 ml), and a solution of aminopropylheptyl-cage polysilsesquioxane (87.46 g 0.1 mol) were added to a single-necked flask, stirred, heated and refluxed for 12 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solution turned into a yellow color, and propylheptyl-cage polysilsesquioxane-substituted pyridone was obtained. It was extracted with ethyl acetate and recrystallized from ethanol, with a yield of 85%.

[0138] (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 stirring was continued in an ice bath until it was 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, and pentachloroaniline diazonium salt was generated after 25 minutes. A small amount of aminosulfonic acid was added to eliminate the excess nitrosyl sulfuric acid.

[0139] (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, and the reaction temperature was gradually increased from 5°C to 30°C. After 12 hours, sodium hydroxide was added to the mixed solution, and the pH was adjusted to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye17.

[0140] 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 the molecular weight of the target molecule.

[0141] 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 .

[0142] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye17 was correct.

[0143] Figure 8 The molecular structure, UV maximum absorption spectrum (DMF) and color of the dye in solvent (DMF) of pyridone azo dye Dye17 are shown. The UV maximum absorption wavelength of the dye in solvent DMF is 417nm, which meets the color requirements of yellow filter dye.

[0144] Examples 18 to 23

[0145] 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 diazo components to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 18 to 23.

[0146] Embodiment 24

[0147] The steps are the same as those in Example 7, except that the diazo component remains unchanged and the coupling component is the propylheptyl-cage polysilsesquioxane-substituted pyridone prepared in Example 17, to obtain the pyridone azo dye Dye24.

[0148] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 25 to 32 are shown in Table 4.

[0149] Table 4 Dye structures corresponding to pyridone substituted with 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-dipropyl-1-propylamine as coupling component

[0150]

[0151]

[0152] Embodiment 25

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

[0154] (1) Preparation of coupling component: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol) prepared in step (1) of Example 9, bromopropane (13.53 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N-dimethylformamide (100 mL) were added to a single-necked flask, stirred, heated and refluxed for 8 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solution turned into an orange color to obtain 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-dipropyl-1-propylamine substituted pyridone. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 71%.

[0155] (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 stirring was continued in an ice bath until it was 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, and pentachloroaniline diazonium salt was generated after 22 minutes. A small amount of aminosulfonic acid was added to eliminate the 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, and the reaction temperature was gradually increased from 2°C to 30°C. After 11 hours, sodium carbonate was added to the mixed solution, and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain 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 the molecular weight 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] The combination of mass spectrum and infrared analysis of the product showed that the structure of the synthesized dye Dye25 was correct.

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

[0161] Embodiments 26 to 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 diazo components to obtain pyridone azo dyes corresponding to the corresponding diazo components in Examples 26 to 31.

[0163] Embodiment 32

[0164] 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-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 with 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]

[0169] Embodiment 33

[0170] The method for synthesizing dye Dye35 in this embodiment comprises the following steps:

[0171] (1) Preparation of coupling component: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine substituted pyridone (19.08 g 0.05 mol) prepared in step (1) of Example 9, chloroethyl methyl ether (10.40 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N-dimethylformamide (100 mL) were added to a single-necked flask, stirred, heated and refluxed for 8 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solution turned into an orange-yellow solution to obtain 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)-N,N-bis(2-methoxyethyl)propan-1-amine substituted pyridone. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 69%.

[0172] (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 stirring was continued in an ice bath until it was 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, and 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.

[0173] (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, and the reaction temperature was gradually increased from 4°C to 32°C. After 10 hours, sodium carbonate was added to the mixed solution, and the pH was adjusted to 6. The mixture was filtered and washed with water until the filtrate was colorless to obtain a magenta dye Dye35.

[0174] 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 the molecular weight of the target molecule.

[0175] 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 .

[0176] Combined with the mass spectrum and infrared spectroscopy of the product, it was shown that the structure of the synthesized dye Dye35 was correct.

[0177] Fig.10 The molecular structure, UV maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye35 in the solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in the solvent DMF is 533nm, which meets the color requirements of the magenta filter dye.

[0178] Embodiments 34 to 39

[0179] 2-Cyano-4-nitro-6-bromoaniline, pentachloroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline and 4-trifluoromethylaniline were used to replace the 2-chloro-4-nitroaniline in step (2) of Example 33 as the diazo component to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 34 to 39.

[0180] Embodiment 40

[0181] 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.

[0182] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 41 to 48 are shown in Table 6.

[0183] Table 6 Structural formula of dyes corresponding to pyridone substituted with N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propan-1-amine as coupling component

[0184]

[0185] Embodiment 41

[0186] The method for synthesizing dye Dye43 in this embodiment comprises the following steps:

[0187] (1) Preparation of coupling component: 3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propane-1-amine substituted pyridone (19.08 g 0.05 mol) prepared in step (1) of Example 9, benzyl chloride (13.92 g 0.11 mol), cesium carbonate (16.29 g 0.05 mol), N,N-dimethylformamide (100 mL) were added to a single-necked flask, stirred, heated and refluxed for 11 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, it turned into a brown-gray solution to obtain N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propane-1-amine substituted pyridone. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 62%.

[0188] (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 stirring was continued in an ice bath until it was 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, and 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.

[0189] (3) Coupling reaction: The N,N-dibenzyl-3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propane-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, and the reaction temperature was gradually increased from 5°C to 28°C. After 12 hours, sodium hydroxide was added to the mixed solution, and the pH was adjusted to 7. The mixture was filtered and washed with water until the filtrate was colorless to obtain a magenta dye Dye43.

[0190] 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 the molecular weight of the target molecule.

[0191] 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 .

[0192] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye43 was correct.

[0193] Fig.11 The molecular structure, UV maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye43 in the solvent (DMF) are shown. The UV maximum absorption wavelength of the dye in the solvent DMF is 536nm, which meets the color requirements of the magenta filter dye.

[0194] Embodiments 42 to 47

[0195] 2-Cyano-4-nitro-6-bromoaniline, pentachloroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline and 4-trifluoromethylaniline were used to replace the 2-chloro-4-nitroaniline in step (2) of Example 41 as the diazo component to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 42 to 47.

[0196] Embodiment 48

[0197] 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 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.

[0198] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 49 to 56 are shown in Table 7.

[0199] 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

[0200]

[0201] Embodiment 49

[0202] The method for synthesizing the dye Dye49 in this embodiment comprises the following steps:

[0203] (1) Preparation of coupling component: 3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propan-1-amine substituted pyridone (19.08 g 0.05 mol) prepared in Example 9, 1,3-dibromopropane (22.21 g 0.11 mol), potassium carbonate (6.91 g 0.05 mol), N,N-dimethylformamide (100 mL) were added to a single-necked flask, stirred, heated and refluxed for 9 hours, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, it turned into a dark green solution to obtain 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propyl)propan-1-amine substituted pyridone. It was extracted with ethyl acetate and recrystallized from ethanol with a yield of 77%.

[0204] (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 stirring was continued in an ice bath until it was 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, and 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.

[0205] (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, and the reaction temperature was gradually increased from 3°C to 31°C. After 8 hours, sodium hydroxide was added to the mixed solution to adjust the pH to 7, and the filtrate was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye49.

[0206] 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 the molecular weight of the target molecule.

[0207] 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 .

[0208] The combination of mass spectrum and infrared analysis of the product showed that the structure of the synthesized dye Dye49 was correct.

[0209] Fig.12 The molecular structure, ultraviolet maximum absorption spectrum (DMF) and color display of the pyridone azo dye Dye49 in the solvent (DMF) are shown. The ultraviolet maximum absorption wavelength of the dye in the solvent DMF is 390nm, which meets the color requirements of the yellow filter dye.

[0210] Embodiments 50 to 55

[0211] 2-Cyano-4-nitro-6-bromoaniline, 2-chloro-4-nitroaniline, 4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline and 4-trifluoromethylaniline were used respectively to replace pentachloroaniline as the diazo component to obtain the pyridone azo dyes corresponding to the corresponding diazo components in Examples 50 to 55.

[0212] Embodiment 56

[0213] The steps are the same as those in Example 7, except that the diazo component remains unchanged and the coupling component R is the 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxane)propyl)propan-1-amine substituted pyridone prepared in Example 49 to obtain the pyridone azo dye Dye56.

[0214] The specific structures of the pyridone azo dyes prepared from the same coupling component with different diazo components in Examples 57 to 64 are shown in Table 8.

[0215] 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

[0216]

[0217] Embodiment 57

[0218] The method for synthesizing dye Dye57 in this embodiment comprises the following steps:

[0219] (1) Preparation of coupling components: 3-bromo-N-(3-bromopropyl)-N-(3-(3-butyl-1,1,3,3-tetramethyldisiloxanyl)propyl)propan-1-amine substituted pyridone (24.47 g 0.05 mol) prepared in Example 49, 4-tert-butylphenol (15.01 g 0.1 mol), potassium carbonate (6.91 g 0.05 mol) and N,N-dimethylformamide (100 mL) were added into a single-necked flask, stirred, heated and refluxed for 8 hours, and the reaction progress was monitored by thin layer chromatography. After 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-tetramethyldisiloxane)propyl)propan-1-amine substituted pyridone with a yield of 67%.

[0220] (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 stirring was continued in an ice bath until it was 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, and 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.

[0221] (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, and the reaction temperature was gradually increased from 2°C to 26°C. After 8 hours, sodium hydroxide was added to the mixed solution to adjust the pH to 6, and the mixture was filtered and washed with water until the filtrate was colorless to obtain yellow dye Dye57.

[0222] 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 the molecular weight of the target molecule.

[0223] 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 .

[0224] Combined with the mass spectrum and infrared of the product, it was shown that the structure of the synthesized dye Dye57 was correct.

[0225] Examples 58 to 63

[0226] 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.

[0227] Embodiment 64

[0228] 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.

[0229] Embodiment 65

[0230] Five dyes, Dye1, Dye2, Dye3, Dye9 and Dye17, were selected as representatives to prepare dye resins, and the ultraviolet maximum absorption spectrum, photostability, thermal stability and solubility of the dyes were tested; the photostability, thermal stability and chromaticity of the prepared dye resins were tested.

[0231] Accurately weigh 0.1g of dye to prepare a 1μM solution, then prepare a dye resin solution with dye: acrylic resin: N,N-dimethylformamide (DMF) = 1:20:100 (volume ratio) and spin-coat it on a glass sheet to prepare a resin sheet. The measured UV maximum absorption wavelength, molar absorption coefficient, solubility, solution transmittance and prepared dye resin transmittance in the solution 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 as shown in Table 12. 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.

[0232] The calculation formula of chromaticity difference is as follows:

[0233] △E=(△L *2 +△a *2 +△b *2 ) 1 / 2

[0234] Where, △L*=L 2 -L 1 ,△a*=a 2 -a 1 ,△b*=b 2 -b 1 .

[0235] L 1 a 1 b 1 is the test value before baking or light exposure, L 2 a 2 b 2 It is the test value after baking or illumination. The change of transmittance of dye resin before and after illumination is calculated by the change of transmission spectrum; the change of solution transmittance is obtained by the transmission spectrum and the maximum ultraviolet absorption spectrum.

[0236] Table 9 Performance of five dyes in solvent N,N-dimethylformamide

[0237]

[0238] Table 10 Chromaticity values ​​of five dyes before and after baking

[0239]

[0240] Table 11 Chromaticity values ​​of five dyes before and after illumination

[0241]

[0242] According to Table 9, the solution transmittance is higher than 94%, which indicates that the synthesized pyridone azo dye molecules substituted by silane coupling agent KH-550, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane derivative and aminopropylheptyl-cage polysilsesquioxane at the N position are not planar, and have certain steric hindrance in the solution, which effectively prevents the aggregation between molecules, so they have good solubility in N,N-dimethylformamide (DMF) solvent, and the solubility is greater than 5wt%; According to Table 10 and Table 11, it can be shown that the dye has good dispersibility in the acrylic resin film material, so that the color film material has good light transmittance; The color difference data of the 5 dye resins before and after baking in Table 10 are all less than 3, indicating that the pyridone azo dye has good thermal stability. Fig.14 (a), 15(a), 16(a), 17(a), and 18(a) 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 corresponds to the color difference of the dye resin before and after baking in Table 10; the data of the color difference 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. Fig.14 (b), 15(b), 16(b), 17(b), and 18(b) 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.

[0243] Figure 19-23 It is a test of the photostability of the dye solution. The UV maximum absorption spectrum of the dye solution was tested before and after irradiation with UV light. It can be seen that it is basically unchanged and the dye has good photostability.

[0244] Fig.13 The digital photos corresponding to the five dye resins show that the prepared dye resins have brighter chromaticity and higher transmittance.

[0245] 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned 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: 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; 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, characterized in that: The steps include: (1) An aromatic primary amine containing a group that can inactivate a benzene ring is used as a diazo component, and the diazo component, concentrated sulfuric acid, and concentrated phosphoric acid are added into a reaction vessel. After the temperature is lowered 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, adding the coupling component, ethanol and water into a reaction vessel, stirring at room temperature to dissolve the coupling component, cooling to 0-5° C., adding the diazonium salt solution obtained in step (1) under stirring, and gradually warming the temperature 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, the product 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:

4. The preparation method according to claim 2, characterized in that: The structural formula of the coupling component is shown in 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 25wt% to 40wt%; and the diazotization reaction time is 0.2h to 8h.

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 used solvent is ethyl acetate: petroleum ether=1:1-1:5.

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