Photoresponse two-color dye compound with capability of changing color into color and application of photoresponse two-color dye compound

Abstract

The invention discloses a photoresponse double-color dye compound with the capacity of changing color into color, and the structural general formula is selected from one of the following structures: the compound prepared by the invention can be suitable for double-color photochromic glasses or photochromic glass, the aesthetic degree and designability are greatly improved, and beautification and playability are provided for traditional photochromic lenses; the color-changeable practicability is also provided for the traditional colored lens, and the combination of the advantages of the color-changeable lens and the colored lens is successfully realized.

Description

Technical Field

[0001] This invention belongs to the field of dye preparation technology, specifically, it relates to a class of photoresponsive bicolor dye compounds with the ability to change color and their applications. Background Technology

[0002] Photochromic materials are a class of smart materials that undergo reversible color changes under specific wavelengths of light radiation. The changes in their optical properties are typically closely related to transitions in molecular structure or crystal phase. These materials have significant applications in photosensitive devices, smart windows, information storage, anti-counterfeiting labels, and light-controlled switches.

[0003] Currently, many conventional photochromic materials, such as photochromic naphthylpyran, can transform between a "transparent and colorless" ground state and a "colored" excited state under the influence of light radiation. "Transparent and colorless" means that the photochromic material or its products are essentially colorless, i.e., they do not absorb electromagnetic radiation in the visible light wavelength range (420nm~700nm). Correspondingly, "colored" means that the photochromic material or its products absorb electromagnetic radiation in the visible light wavelength range. However, to achieve this colorless-to-colored transformation, i.e., the conversion between the ground state and the excited state, light radiation with wavelengths of 320nm~390nm is required. This characteristic means that these materials can only exhibit the colorless state of the ground state under weak light or weak ultraviolet light environments, failing to provide good color performance and limiting many application scenarios. Summary of the Invention

[0004] The purpose of this invention is to provide a class of photoresponsive dual-color dye compounds with the ability to change color.

[0005] Another object of the present invention is to provide the application of the aforementioned photoresponsive two-color dye compound in the preparation of two-color photochromic aqueous dyes.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a class of photoresponsive bicolor dye compounds possessing the ability to change color, wherein the general structural formula is selected from one of the following structures:

[0008] ;

[0009] in,

[0010] R1 is selected from C1~C10 alkoxy groups, hydrogen, ;

[0011] R2 is selected from C1~C10 alkoxy groups and hydrogen;

[0012] R3 is selected from C1~C10 alkoxy groups and hydrogen;

[0013] R4 is selected from C1~C15 alkyl groups;

[0014] R5 is selected from C1~C15 alkyl groups;

[0015] R6 is selected from hydrogen, -CF3, ;

[0016] R7 is selected from C1~C10 alkyl, C1~C10 alkoxy, ;

[0017] R8 is selected from hydrogen, C1~C10 alkyl, C1~C10 alkoxy, ;

[0018] R9 is selected from hydrogen, C1~C10 alkyl, C1~C10 alkoxy, ;

[0019] R 10 Selected from hydrogen, -CF3, ;

[0020] R 11 Selected from C1~C15 alkyl groups;

[0021] R 12 Selected from C1~C15 alkyl groups;

[0022] R 13 Selected from ;

[0023] R 14 Selected from C1~C10 alkyl and hydrogen;

[0024] R 15 Selected from C1~C10 alkyl and hydrogen;

[0025] R 16 Selected from C1~C10 alkyl groups;

[0026] R 17 Selected from C1~C10 alkyl groups;

[0027] R 18 Selected from C1~C10 alkyl groups;

[0028] R 19 Selected from ;

[0029] R 20 Selected from C1~C10 alkyl and hydrogen;

[0030] R 21 Selected from C1~C10 alkyl and hydrogen;

[0031] R 22 Selected from C1~C10 alkyl groups;

[0032] R 23 Selected from C1~C10 alkyl groups;

[0033] R 24 Selected from C1~C10 alkyl groups;

[0034] R 25 Selected from C1~C10 alkoxy groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0035] R 26 Selected from hydrogen, halogens (fluorine, chlorine, bromine, iodine), C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0036] R 27 Selected from hydrogen, halogens (fluorine, chlorine, bromine, iodine), C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0037] R 28 Selected from hydrogen, halogens (fluorine, chlorine, bromine, iodine), C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0038] R 29 Selected from hydrogen, halogens (fluorine, chlorine, bromine, iodine), C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0039] R 30 Selected from C1~C15 alkyl groups;

[0040] R 31 Selected from C1~C15 alkyl groups;

[0041] R 32 Selected from C1~C15 alkyl and C1~C15 alkoxy groups;

[0042] R 33 Selected from hydrogen, C1~C15 alkoxy groups, ;

[0043] R 34 Selected from hydrogen, C1~C15 alkoxy groups, ;

[0044] R 35 Selected from C1~C15 alkyl groups;

[0045] R 36 Selected from C1~C15 alkyl groups;

[0046] R 37 Selected from -CF3, -NHCH3, -N(CH3)2, -N(CH2CH3)2, -N(CH2CH2CH3)2;

[0047] R 38 Selected from hydrogen and C1-C15 alkyl groups;

[0048] R 39 Selected from hydrogen and C1-C15 alkyl groups;

[0049] R 40 Selected from hydrogen and C1-C15 alkyl groups;

[0050] R 41 Selected from C1~C10 alkoxy groups;

[0051] R 42 Selected from hydrogen, -CF3;

[0052] R 43 Selected from hydrogen, -CF3;

[0053] R 44 Selected from C1~C10 alkoxy groups;

[0054] R 45 Selected from C1~C15 alkyl groups;

[0055] R 46 Selected from C1~C15 alkyl groups;

[0056] R 47 Selected from ;

[0057] R 48 Selected from hydrogen and C1~C10 alkoxy groups;

[0058] R 49 Selected from hydrogen and C1~C10 alkoxy groups;

[0059] R 50 Selected from C1~C10 alkyl groups;

[0060] R 51 Selected from C1~C10 alkyl groups;

[0061] R 52 Selected from ;

[0062] R 53 Selected from ;

[0063] R 54 Selected from hydrogen and C1~C15 alkoxy groups;

[0064] R 55 Selected from hydrogen and C1~C15 alkoxy groups;

[0065] R 56 Selected from hydrogen and C1~C15 alkoxy groups;

[0066] R 57 Selected from C1~C15 alkyl groups;

[0067] R 58 Selected from C1~C15 alkyl groups;

[0068] R 59 Selected from ;

[0069] R 60 Selected from hydrogen and C1~C15 alkoxy groups;

[0070] R 61 Selected from hydrogen and C1~C15 alkoxy groups;

[0071] R 62 Selected from C1~C15 alkyl groups;

[0072] R 63 Selected from C1~C15 alkyl groups;

[0073] R 64 Selected from hydrogen and C1~C15 alkoxy groups.

[0074] Preferably, in the photoresponsive dual-color dye compound,

[0075] R1 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, hydrogen, ;

[0076] R2 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, and hydrogen;

[0077] R3 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, and hydrogen;

[0078] R4 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0079] R5 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0080] R6 is selected from hydrogen, -CF3, ;

[0081] R7 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ;

[0082] R8 is selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ;

[0083] R9 is selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ;

[0084] R 10 Selected from hydrogen, -CF3, ;

[0085] R 11 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0086] R 12 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0087] R 13 Selected from ;

[0088] R 14 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen;

[0089] R 15 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen;

[0090] R 16 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0091] R 17 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0092] R 18 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0093] R 19 Selected from ;

[0094] R 20 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen;

[0095] R 21 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen;

[0096] R 22 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0097] R 23 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0098] R 24 Selected from methyl, ethyl, n-propyl, and isopropyl;

[0099] R 25 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0100] R 26 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0101] R 27 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0102] R 28 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0103] R 29 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3;

[0104] R30 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0105] R 31 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0106] R 32 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0107] R 33 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, ;

[0108] R 34 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, ;

[0109] R 35 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0110] R 36 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0111] R 37 Selected from -CF3, -NHCH3, -N(CH3)2, -N(CH2CH3)2, -N(CH2CH2CH3)2;

[0112] R 38 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0113] R 39 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0114] R 40 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0115] R 41 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0116] R 42 Selected from hydrogen, -CF3;

[0117] R 43 Selected from hydrogen, -CF3;

[0118] R 44 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0119] R 45 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0120] R 46 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0121] R 47 Selected from ;

[0122] R 48 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0123] R 49 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0124] R 50 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0125] R 51 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl;

[0126] R 52 Selected from ;

[0127] R 53 Selected from ;

[0128] R 54 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0129] R 55 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0130] R 56 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0131] R 57 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0132] R58 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0133] R 59 Selected from ;

[0134] R 60 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0135] R 61 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy;

[0136] R 62 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0137] R 63 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl;

[0138] R 64 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy.

[0139] Most preferably, the structure of the photoresponsive dual-color dye compound is selected from one of the following structures:

[0140] ;

[0141] .

[0142] In a second aspect, the present invention provides the application of the aforementioned photoresponsive two-color dye compound in the preparation of two-color photochromic aqueous dyes.

[0143] The dual-color photochromic aqueous dye is made from the following components by weight percentage:

[0144] The composition includes: 1-10% photoresponsive dual-color dye compound; 1-10% dispersant; 0.5-2% thickener; 0.01-1.5% synergistic thickener; 0.1-3% wetting agent; 0.1-5% fixing agent; 0.5-20% cosolvent; 40-86.79% deionized water; and 10-30% pH adjuster.

[0145] The dispersant is selected from Tween 80.

[0146] The thickener is selected from hydroxypropyl cellulose.

[0147] The synergistic thickener is selected from WT-105A.

[0148] The wetting agent is selected from GZ080A.

[0149] The fixing agent is selected from formaldehyde-free fixing agent Y.

[0150] The co-solvent is selected from methylpyrrolidone.

[0151] The pH adjuster is selected from sodium hydroxide aqueous solution (concentration of 1~3%, preferably 2%) and glacial acetic acid aqueous solution (concentration of 0.5~2%, preferably 1%).

[0152] The dual-color photochromic aqueous dye is made from the following components by weight percentage:

[0153] The composition includes: 1% photoresponsive dual-color dye compound; 5% dispersant; 1.5% thickener; 1% synergistic thickener; 1.5% wetting agent; 2% fixing agent; 10% cosolvent; 58% deionized water; and 20% pH adjuster.

[0154] A third aspect of the present invention provides the application of the aforementioned photoresponsive dual-color dye compound in the preparation of photochromic lenses, photochromic glass, color-changing warning labels, color-changing warning tapes, and color-changing outlines.

[0155] By adopting the above technical solution, the present invention has the following advantages and beneficial effects:

[0156] This invention provides a class of photoresponsive bicolor dye compounds with the ability to change color. These compounds are in a stable ground state under low light conditions, typically displaying striking colors such as fluorescent yellow or bright orange. These colors exhibit excellent recognizability and visibility in low light or even dark environments. Under strong light conditions, these compounds can absorb ultraviolet light and enter an excited state, changing their color from bright yellow or orange to deep purple or dark gray. These darker colors reduce light reflection in strong light environments, lowering visibility and reducing light pollution. The compounds prepared by this invention can remain stable for extended periods in both the ground and excited states. The transition from the ground state to the excited state requires a high activation energy, ensuring the compounds' inertness in low light conditions, remaining in the ground state unaffected by stray light. Conversely, the activation energy for returning from the excited state to the ground state is much lower, ensuring a strong low-light response. This allows the compounds to quickly return to the ground state as light dims, achieving the color change of the compounds prepared by this invention.

[0157] The compounds prepared by this invention can be used in bi-color photochromic glasses or photochromic glass. Most current photochromic glasses change from a colorless state to a colored state, while the compounds provided by this invention can make photochromic glasses change from colored to colored, greatly improving aesthetics and designability, providing aesthetic enhancement and playability to traditional photochromic lenses; it also provides practicality for traditional colored lenses to change color, successfully combining the advantages of both photochromic and colored lenses.

[0158] The compounds prepared in this invention can be used as dual-color dyes, which are well-suited for scenarios requiring "visibility at night and discretion during the day." Furthermore, the conversion between the two colors relies entirely on photochromism, making it energy-efficient and environmentally friendly. By formulating the compounds prepared in this invention into color-changing compositions, various materials can be colored, and these compositions can be applied to color-changing warning signs, warning tapes, and outlining lines.

[0159] The compounds prepared in this invention have the ability to change color from one color to another under light. The color before light exposure is typically a bright, striking color such as orange, yellow, or bright green, but after exposure to light, it transforms into a darker color such as dark green, blue-violet, or grayish-black. Upon exposure to light, the compounds of this invention complete the color change in just 30 seconds, and after the light is removed, more than 90% of the color fades, restoring the original bright color, in about 3 minutes, demonstrating a very fast fading speed. Detailed Implementation

[0160] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0161] Example 1

[0162]

[0163] In a three-necked flask, dried compound 1a (5.60 g, 10.00 mmol) (the preparation method of compound 1a is described in reference US20120145973A1) was dissolved in 50 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out under nitrogen protection at 80 °C for 5 hours, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 30 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate = 100:1 as eluent to give 5.66 g of grayish-white compound 1b, with a yield of 93%.

[0164]

[0165] In a three-necked flask, compound 1b (6.06 g, 10.00 mmol) was dissolved in 60 g tetrahydrofuran and 12 g pure water. Compound 1c (1.18 g, 4.00 mmol), potassium carbonate (2.76 g, 20.00 mmol), and tetraphenylphosphine palladium (0.24 g, 0.2 mmol) were added sequentially. The mixture was stirred at 85 °C for 5 hours under nitrogen protection, and then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 3.13 g of yellow compound 1, with a yield of 71.6%.

[0166]

[0167] Example 2

[0168]

[0169] In a three-necked flask, dried compound 2a (prepared according to US20120145973A1) (7.70 g, 10.00 mmol) was dissolved in 50 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, and then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 30 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate = 100:1 as eluent to give 5.96 g of grayish-white compound 2b, with a yield of 73%.

[0170]

[0171] In a three-necked flask, purified and dried compound 2b (8.18 g, 10.00 mmol) was dissolved in 60 g tetrahydrofuran and 12 g pure water. Compound 1c (1.18 g, 4.00 mmol), potassium carbonate (2.76 g, 20.00 mmol), and tetra-triphenylphosphine palladium (0.24 g, 0.2 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 20:1) to give 4.06 g of orange compound 2, with a yield of 67.1%.

[0172]

[0173] Example 3

[0174]

[0175] In a three-necked flask, compound 3a (prepared according to US20120145973A1) (6.75 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 5.19 g of grayish-white compound 3b, with a yield of 71.9%.

[0176]

[0177] In a three-necked flask, purified and dried compound 3b (7.98 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 3f (2.50 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 5.59 g of brown compound 3e, with a yield of 78.3%.

[0178]

[0179] In a three-necked flask, compound 3c (prepared according to US20120145973A1) (7.23 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, and then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (50:1) to give 6.73 g of a grayish-white compound 3d (87.4%).

[0180]

[0181] In a three-necked flask, purified and dried compounds 3e (7.93 g, 10.00 mmol) and 3d (7.70 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 6.55 g of bright yellow compound 3, with a yield of 48.3%.

[0182]

[0183] Example 4

[0184]

[0185] In a three-necked flask, dried compound 4a (prepared according to US20120145973A1) (7.50 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 7.06 g of grayish-white compound 4b, with a yield of 88.4%.

[0186]

[0187] In a three-necked flask, purified and dried compound 4b (7.98 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 1c (2.65 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 5.67 g of brown compound 4e, with a yield of 71.1%.

[0188]

[0189] In a three-necked flask, dried compound 4c (prepared according to US20120145973A1) (7.38 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.54 g of grayish-white compound 4d, with a yield of 83.2%.

[0190]

[0191] In a three-necked flask, purified and dried compounds 4e (8.85 g, 10.00 mmol) and 4d (7.86 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 7.97 g of yellow compound 4, with a yield of 54.4%.

[0192]

[0193] Example 5

[0194]

[0195] In a three-necked flask, dried compound 5a (prepared according to US20120145973A1) (6.96 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.43 g of grayish-white compound 5b, with a yield of 86.4%.

[0196]

[0197] In a three-necked flask, dried compound 5c (prepared according to US20120145973A1) (7.84 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to obtain 7.54 g of grayish-white compound 5d, with a yield of 90.7%.

[0198]

[0199] In a three-necked flask, purified and dried compound 5b (7.43 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 5f (2.62 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 5.50 g of brown compound 5e, with a yield of 73.8%.

[0200]

[0201] In a three-necked flask, purified and dried compounds 5e (8.27 g, 10.00 mmol) and 5d (7.86 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 6.92 g of green compound 5, with a yield of 47.7%.

[0202]

[0203] Example 6

[0204]

[0205] In a three-necked flask, dried compound 6a (prepared according to US20120145973A1) (6.85 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to obtain 6.43 g of grayish-white compound 6b, with a yield of 86.4%.

[0206]

[0207] In a three-necked flask, dried compound 6c (prepared according to US20120145973A1) (7.70 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.02 g of grayish-white compound 6d, with a yield of 73.6%.

[0208]

[0209] In a three-necked flask, purified and dried compound 6b (7.32 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 6f (2.49 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 40:1) to give 5.20 g of brown compound 6e, with a yield of 64.8%.

[0210]

[0211] In a three-necked flask, purified and dried compounds 6e (8.02 g, 10.00 mmol) and 6d (8.19 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 6.37 g of brown compound 6, with a yield of 45.0%.

[0212]

[0213] Example 7

[0214]

[0215] In a three-necked flask, dried compound 7a (prepared according to US20120145973A1) (6.56 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.03 g of grayish-white compound 7b, with a yield of 85.8%.

[0216]

[0217] In a three-necked flask, dried compound 7c (prepared according to US20120145973A1) (6.72 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to obtain 5.68 g of grayish-white compound 7d, with a yield of 78.9%.

[0218]

[0219] In a three-necked flask, purified and dried compound 7b (7.03 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 5f (2.62 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 5.26 g of reddish-brown compound 7e, with a yield of 66.9%.

[0220]

[0221] In a three-necked flask, purified and dried compounds 7e (7.85 g, 10.00 mmol) and 7d (7.20 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 5.71 g of gray compound 7, with a yield of 47.7%.

[0222]

[0223] Example 8

[0224]

[0225] In a three-necked flask, dried compound 8a (prepared according to US20120145973A1) (6.98 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 5.85 g of grayish-white compound 8b, with a yield of 78.4%.

[0226]

[0227] In a three-necked flask, dried compound 8c (prepared according to US20120145973A1) (8.15 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.17 g of grayish-white compound 8d, with a yield of 71.7%.

[0228]

[0229] In a three-necked flask, purified and dried compound 8b (7.47 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 8f (2.50 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 80:1). 5.80 g of brown compound 8e was obtained, with a yield of 70.8%.

[0230]

[0231] In a three-necked flask, purified and dried compounds 8e (8.18 g, 10.00 mmol) and 8d (8.62 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 7.32 g of brown compound 8, with a yield of 49.7%.

[0232]

[0233] Example 9

[0234]

[0235] In a three-necked flask, dried compound 9a (prepared according to US20120145973A1) (7.54 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.66 g of grayish-white compound 9b, with a yield of 83.1%.

[0236]

[0237] In a three-necked flask, dried compound 9c (prepared according to US20120145973A1) (7.69 g, 10.00 mmol) was dissolved in 80 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 40 g of distilled water was added, and the mixture was stirred for 5 minutes before filtration. The filtered solid product was purified by column chromatography using toluene:ethyl acetate (100:1) as eluent to give 6.16 g of grayish-white compound 9d, with a yield of 75.6%.

[0238]

[0239] In a three-necked flask, purified and dried compound 9b (8.01 g, 10.00 mmol) was dissolved in 60 g of tetrahydrofuran and 12 g of pure water. Compound 9f (2.61 g, 9.00 mmol), potassium carbonate (1.38 g, 10.00 mmol), and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 5.40 g of brown compound 9e, with a yield of 61.1%.

[0240]

[0241] In a three-necked flask, purified and dried compounds 9e (8.85 g, 10.00 mmol) and 9d (8.15 g, 10.00 mmol) were dissolved in 150 g of tetrahydrofuran and 30 g of pure water. Potassium carbonate (1.38 g, 10.00 mmol) and tetra-triphenylphosphine palladium (0.12 g, 0.1 mmol) were added sequentially. The reaction was carried out under nitrogen protection at 85 °C for 5 hours, and then gradually cooled to room temperature for 12 hours. The solid product gradually precipitated out. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 10:1) to give 6.92 g of brown compound 8, with a yield of 46.3%.

[0242]

[0243] Example 10

[0244]

[0245] In a three-necked flask, dried compound 10a (7.66 g, 10.00 mmol) (prepared according to US20120145973A1) was dissolved in 50 g of 1,4-dioxane. Then, pinacol diboronate (4.48 g, 20.00 mmol), potassium acetate (1.47 g, 15.00 mmol), 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.073 g, 0.1 mmol), and 10 g of pure water were added sequentially. The reaction was carried out at 80 °C for 5 hours under nitrogen protection, then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. After the reaction solution cooled to room temperature, 30 g of distilled water was added, and the mixture was stirred for 5 minutes and then filtered. The filtered solid product was purified by column chromatography using toluene:ethyl acetate = 100:1 as eluent to give 5.90 g of grayish-white compound 10b, with a yield of 72.5%.

[0246]

[0247] In a three-necked flask, compound 10b (8.15 g, 10.00 mmol) was dissolved in 60 g tetrahydrofuran and 12 g pure water. Compound 1c (1.18 g, 4.00 mmol), potassium carbonate (2.76 g, 20.00 mmol), and tetra-triphenylphosphine palladium (0.24 g, 0.2 mmol) were added sequentially. The mixture was stirred at 85 °C for 5 hours under nitrogen protection, and then gradually cooled to room temperature for 12 hours. A solid product gradually precipitated. The reaction solution was filtered through a Buchner funnel, and the solid obtained was separated by column chromatography using an eluent (toluene:ethyl acetate = 50:1) to give 4.14 g of yellow compound 10, with a yield of 68.6%.

[0248]

[0249] Example 11

[0250] The method for preparing a mother liquor of a two-color photochromic aqueous dye using the compound prepared in this invention is as follows:

[0251] First, 5g of Tween 80 was added to 30g of deionized water and stirred to dissolve at 50°C. Then, 1g of the compound powder prepared according to this invention was dissolved in 10g of methylpyrrolidone, and then slowly added dropwise to the aforementioned deionized water containing Tween 80 to obtain a mixed solution. The mixed solution was emulsified by high-speed shearing (≥2000rpm) for 30 minutes to form a uniform dispersion.

[0252] The second step involves dissolving 1g of polyethylene wax paste thickener WT-105A in 28g of cold water in another container until it swells, then adding 1.5g of hydroxypropyl cellulose and mixing to obtain the thickener component.

[0253] The third step is to mix the thickener component prepared in the second step with the uniform dispersion prepared in the first step, and stir at high speed for 30 minutes until the consistency is uniform.

[0254] Fourth step: Add 1.5g of GZ080A wetting agent and adjust the pH to 8 with 5g of 2% sodium hydroxide aqueous solution to activate its wetting function. Add 2g of formaldehyde-free fixing agent Y and stir for 1 hour. Slowly adjust the pH to 6-7 with 15g of 1% glacial acetic acid aqueous solution, stir for 10 minutes, and let stand for 24 hours to ensure no solute precipitation and no stratification, thus obtaining the mother liquor of the two-color photochromic aqueous dye.

[0255] Formula of mother liquor for dual-color photochromic aqueous dye (mass percentage): color-changing dye (compound prepared in this invention) 1%; dispersant (Tween 80, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.) 5%; thickener (hydroxypropyl cellulose, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.) 1.5%; synergistic thickener (WT-105A, purchased from Shanghai Haiming Sideqian Chemical Co., Ltd.) 1%; wetting agent (GZ080A, main component polyethylene glycol glycerol condensate, purchased from Guangzhou Guanzhi New Material Technology Co., Ltd.) 1.5%; fixing agent (formaldehyde-free fixing agent Y, purchased from Wuhan Jiyesheng Chemical Co., Ltd.) 2%; cosolvent (methylpyrrolidone) 10%; deionized water 58%; pH adjuster: sodium hydroxide aqueous solution 5%, glacial acetic acid aqueous solution 15%.

[0256] The above percentages represent the percentage of a single component relative to the total mass of all components (color-changing dye, dispersant, thickener, synergistic thickener, wetting agent, fixing agent, cosolvent, deionized water, pH adjuster).

[0257] A 4-inch blended cleanroom fabric was dyed in a two-color photochromic aqueous dye masterbatch to obtain dyed fabric. Three types of photochromic dyes purchased from the market (Shenzhen Tianjinli New Material Technology Co., Ltd.) were used to prepare dyed fabrics using the same method. These fabrics were used as control samples for color change tests before and after light exposure. The results are shown in Table 1. The light source was natural light, and the exposure time was 90 seconds.

[0258] Table 1

[0259]

[0260] As can be seen from the data in the table, the dyed fabric prepared by the bicolor photochromic aqueous dye mother liquor of the present invention has obvious color changes before and after light exposure, and both change from bright colors to dark colors; and the fading time is shorter than that of the control sample, which can achieve faster color change.

[0261] The dyed fabrics prepared above were placed in several dark environments with different light intensities, and their visibility and color were observed with the naked eye. The light intensity was measured using a lux meter. The ambient temperature was uniformly 25℃. The test results are shown in Table 2.

[0262] Table 2

[0263]

[0264] As can be seen from the data in the table, the dyed fabric prepared by the bicolor photochromic aqueous dye mother liquor of the present invention can still maintain a certain degree of visual visibility in a dark environment of 2~0.5 lux, while the control sample no longer has visual visibility in the same environment.

[0265] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A class of photoresponsive bicolor dye compounds possessing the ability to change color, characterized in that, The general structural formula is selected from one of the following structures: ； in, R1 is selected from C1~C10 alkoxy groups, hydrogen, ; R2 is selected from C1~C10 alkoxy groups and hydrogen; R3 is selected from C1~C10 alkoxy groups and hydrogen; R4 is selected from C1~C15 alkyl groups; R5 is selected from C1~C15 alkyl groups; R6 is selected from hydrogen, -CF3, ; R7 is selected from C1~C10 alkyl, C1~C10 alkoxy, ; R8 is selected from hydrogen, C1~C10 alkyl, C1~C10 alkoxy, ; R9 is selected from hydrogen, C1~C10 alkyl, C1~C10 alkoxy, ; R 10 Selected from hydrogen, -CF3, ; R 11 Selected from C1~C15 alkyl groups; R 12 Selected from C1~C15 alkyl groups; R 13 Selected from ; R 14 Selected from C1~C10 alkyl and hydrogen; R 15 Selected from C1~C10 alkyl and hydrogen; R 16 Selected from C1~C10 alkyl groups; R 17 Selected from C1~C10 alkyl groups; R 18 Selected from C1~C10 alkyl groups; R 19 Selected from ; R 20 Selected from C1~C10 alkyl and hydrogen; R 21 Selected from C1~C10 alkyl and hydrogen; R 22 Selected from C1~C10 alkyl groups; R 23 Selected from C1~C10 alkyl groups; R 24 Selected from C1~C10 alkyl groups; R 25 Selected from C1~C10 alkoxy groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 26 Selected from hydrogen, halogens, C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 27 Selected from hydrogen, halogens, C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 28 Selected from hydrogen, halogens, C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 29 Selected from hydrogen, halogens, C1~C15 alkyl groups, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 30 Selected from C1~C15 alkyl groups; R 31 Selected from C1~C15 alkyl groups; R 32 Selected from C1~C15 alkyl and C1~C15 alkoxy groups; R 33 Selected from hydrogen, C1~C15 alkoxy groups, ; R 34 Selected from hydrogen, C1~C15 alkoxy groups, ; R 35 Selected from C1~C15 alkyl groups; R 36 Selected from C1~C15 alkyl groups; R 37 Selected from -CF3, -NHCH3, -N(CH3)2, -N(CH2CH3)2, -N(CH2CH2CH3)2; R 38 Selected from hydrogen and C1-C15 alkyl groups; R 39 Selected from hydrogen and C1-C15 alkyl groups; R 40 Selected from hydrogen and C1-C15 alkyl groups; R 41 Selected from C1~C10 alkoxy groups; R 42 Selected from hydrogen, -CF3; R 43 Selected from hydrogen, -CF3; R 44 Selected from C1~C10 alkoxy groups; R 45 Selected from C1~C15 alkyl groups; R 46 Selected from C1~C15 alkyl groups; R 47 Selected from ; R 48 Selected from hydrogen and C1~C10 alkoxy groups; R 49 Selected from hydrogen and C1~C10 alkoxy groups; R 50 Selected from C1~C10 alkyl groups; R 51 Selected from C1~C10 alkyl groups; R 52 Selected from ; R 53 Selected from ; R 54 Selected from hydrogen and C1~C15 alkoxy groups; R 55 Selected from hydrogen and C1~C15 alkoxy groups; R 56 Selected from hydrogen and C1~C15 alkoxy groups; R 57 Selected from C1~C15 alkyl groups; R 58 Selected from C1~C15 alkyl groups; R 59 Selected from ; R 60 Selected from hydrogen and C1~C15 alkoxy groups; R 61 Selected from hydrogen and C1~C15 alkoxy groups; R 62 Selected from C1~C15 alkyl groups; R 63 Selected from C1~C15 alkyl groups; R 64 Selected from hydrogen and C1~C15 alkoxy groups.

2. The photoresponsive bicolor dye compound with color-changing ability according to claim 1, characterized in that, In the photoresponsive dual-color dye compound R1 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, hydrogen, ; R2 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, and hydrogen; R3 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, and hydrogen; R4 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl. R5 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl. R6 is selected from hydrogen, -CF3, ; R7 is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ; R8 is selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ; R9 is selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl. ; R 10 Selected from hydrogen, -CF3, ; R 11 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 12 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 13 Selected from ; R 14 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen; R 15 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen; R 16 Selected from methyl, ethyl, n-propyl, and isopropyl; R 17 Selected from methyl, ethyl, n-propyl, and isopropyl; R 18 Selected from methyl, ethyl, n-propyl, and isopropyl; R 19 Selected from ; R 20 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen; R 21 Selected from methyl, ethyl, n-propyl, isopropyl, and hydrogen; R 22 Selected from methyl, ethyl, n-propyl, and isopropyl; R 23 Selected from methyl, ethyl, n-propyl, and isopropyl; R 24 Selected from methyl, ethyl, n-propyl, and isopropyl; R 25 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 26 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 27 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 28 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 29 Selected from hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH2CH2CH2CH3, -SCH2CH2CH2CH2CH3; R 30 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 31 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 32 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 33 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, ; R 34 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentoxy, ; R 35 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 36 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 37 Selected from -CF3, -NHCH3, -N(CH3)2, -N(CH2CH3)2, -N(CH2CH2CH3)2; R 38 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 39 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 40 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 41 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 42 Selected from hydrogen, -CF3; R 43 Selected from hydrogen, -CF3; R 44 Selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 45 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 46 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 47 Selected from ; R 48 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 49 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 50 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 51 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl; R 52 Selected from ; R 53 Selected from ; R 54 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 55 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 56 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 57 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 58 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 59 Selected from ; R 60 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 61 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy; R 62 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 63 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; R 64 Selected from hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy.

3. The photoresponsive bicolor dye compound with color-changing ability according to claim 2, characterized in that, The structure of the photoresponsive dual-color dye compound is selected from one of the following structures: ； 。 4. The use of the photoresponsive two-color dye compound according to any one of claims 1 to 3 in the preparation of two-color photochromic aqueous dyes.

5. The application according to claim 4, characterized in that, The dual-color photochromic aqueous dye is made from the following components by weight percentage: The composition includes: 1-10% photoresponsive dual-color dye compound; 1-10% dispersant; 0.5-2% thickener; 0.01-1.5% synergistic thickener; 0.1-3% wetting agent; 0.1-5% fixing agent; 0.5-20% cosolvent; 40-86.79% deionized water; and 10-30% pH adjuster.

6. The application according to claim 5, characterized in that, The dispersant is selected from Tween 80; The thickener is selected from hydroxypropyl cellulose; The synergistic thickener is selected from WT-105A.

7. The application according to claim 5, characterized in that, The wetting agent is selected from GZ080A; The fixing agent is selected from formaldehyde-free fixing agent Y.

8. The application according to claim 5, characterized in that, The co-solvent is selected from methylpyrrolidone; The pH adjuster is selected from sodium hydroxide aqueous solution and glacial acetic acid aqueous solution.

9. The application according to claim 5, characterized in that, The dual-color photochromic aqueous dye is made from the following components by weight percentage: The composition includes: 1% photoresponsive dual-color dye compound; 5% dispersant; 1.5% thickener; 1% synergistic thickener; 1.5% wetting agent; 2% fixing agent; 10% cosolvent; 58% deionized water; and 20% pH adjuster.

10. The use of a photoresponsive bicolor dye compound according to any one of claims 1 to 3 in the preparation of photochromic lenses, photochromic glass, color-changing warning labels, color-changing warning tapes, and color-changing outlines.

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