Preparation method of seven-membered fluorine boron compound containing BF2 and application of seven-membered fluorine boron compound in fluorescent anti-counterfeiting film

Abstract

The invention discloses preparation of a seven-membered fluorine-boron compound containing BF2 and application of the seven-membered fluorine-boron compound to a fluorescent anti-counterfeiting film.According to the dye, 2, 3, 3-trimethylindole and 5-formyl-2, 4-dimethyl-1H-pyrrole-3-carboxylic acid ethyl ester serve as raw materials, under the action of acetic acid, piperidine and methylbenzene, a Knoevenagel condensation reaction is carried out, and the seven-membered fluorine-boron fluorescent dye is generated. The seven-membered fluorine boron fluorescent dye is brominated and then respectively reacts with phenylboronic acid and triphenylamine phenylboronic acid to obtain a final compound. The compound can act with acrylic resin to form a film on a thin film, and can be colored under natural light, and clear fluorescence can be seen under an ultraviolet lamp (365nm). The fluorescent dye is simple and easy to obtain, low in manufacturing cost, high in film forming speed with acrylic resin on a film, high in anti-counterfeiting coefficient and large in counterfeiting difficulty, and has huge potential in the aspects of fluorescent anti-counterfeiting packaging films, OLDE and the like.

Description

Technical Field

[0001] The present invention relates to the field of materials technology, and more specifically, to the preparation of a heptafluoroborate compound containing BF2. Such compounds have high fluorescence intensity and can be widely applied to the field of fluorescent anti-counterfeiting films. Background Art

[0002] Since the fluorescence characteristics of fluorescent inks can only be manifested by specific excitation light sources, and different types of fluorescent inks have unique fluorescent colors and luminescence characteristics and are difficult to imitate, they are widely used in the anti-counterfeiting field, such as the printing of banknotes, certificates, trademarks, etc. The authenticity can be quickly identified by ultraviolet detection.

[0003] It can also be applied to printed matter such as books, magazines, greeting cards, etc. to create some special effects, such as luminous bookmarks, color-changing covers, etc., increasing the interest and added value of the products. In addition, in some scientific research and experiments, fluorescent inks can also be used for purposes such as marking and tracking.

[0004] The present invention designs and synthesizes a novel-structured heptafluoroborate compound containing BF2. As a dye, it has good penetrability and great potential in the fields of fluorescent anti-counterfeiting films and OLDE, etc. Summary of the Invention

[0005] The present invention provides a preparation method of a heptafluoroborate compound containing BF2 and its application research on fluorescent anti-counterfeiting films. This compound is not only simple to obtain, has low manufacturing cost, high fluorescence intensity, but also has little environmental pollution.

[0006] A heptafluoroborate compound containing BF2 and its application on fluorescent anti-counterfeiting films, the chemical structural formula of the compound is:

[0007] The substituent R is any one selected from hydrogen and diphenylamino.

[0008] As a preselected scheme, the chemical structural formula of the compound is: Any one of

[0009] The synthesis method for synthesizing the heptafluoroborate compound containing BF2, the method includes the following synthesis route: 。

[0010] The method specifically includes the following steps: (1) Add the bromine-containing heptafluoroborate compound 1 to the reaction flask at room temperature, then successively add phenylboronic acid or substituted phenylboronic acid compound 2, tetrakis(triphenylphosphine)palladium, and cesium carbonate. Dissolve them with toluene and water, and heat to 100 - 130 °C under nitrogen protection for reaction to obtain the reaction solution. (2) Extract, dry, and rotary evaporate the reaction solution in step (1), then separate it by silica gel column chromatography and rotary dry to obtain the solid product I.

[0011] Compound 1 is a dibromo heptafluoroborate compound, and compound 2 is a phenylboronic acid containing different substituents; the feeding ratio of compound 1 to compound 2 is 1:4 - 8, the feeding ratio of compound 1 to tetrakis(triphenylphosphine)palladium is 1:0.05 - 0.1, and the feeding ratio of compound 1 to cesium carbonate is 1:1 - 2.

[0012] The feeding order in step (1) is compound 1, compound 2, tetrakis(triphenylphosphine)palladium, cesium carbonate. Dissolve them with a small amount of water first, and finally dissolve with toluene.

[0013] The heating temperature in step (1) is 100 - 130 °C, and the heating time is 0.5 - 10 hours.

[0014] Another technical solution of the present invention is the application of the nitrogen-containing heptafluoroborate compound on a fluorescent anti-counterfeiting film. This compound exhibits excellent fluorescence properties and chemical stability, and is suitable for high-security anti-counterfeiting labels. The so-called anti-counterfeiting effect means having a fluorescence effect under ultraviolet light or visible light.

[0015] The present invention also provides a fluorescent anti-counterfeiting film, which includes the nitrogen-containing heptafluoroborate compound. The preparation of the fluorescent anti-counterfeiting film is to dissolve the compound with a solvent to prepare a mother liquor, then add acrylic resin to prepare a film-forming solution, and finally coat the film-forming solution on the anti-counterfeiting object to form a film to achieve the fluorescent anti-counterfeiting effect. By adjusting the concentration of the mother liquor and the proportion of acrylic resin, the performance of the fluorescent anti-counterfeiting film can be further optimized, such as enhancing the fluorescence adhesion.

[0016] The solvent includes any one or a combination of ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, or toluene.

[0017] The beneficial effects of the present invention are as follows: (1) The BF₂-containing heptafluoroborate compound synthesized by the present invention has high fluorescence intensity, is simple to obtain, has low manufacturing cost, and low pollution.

[0018] (2) Mix the compound provided by the present invention with an acrylic resin, which can quickly form a film on a glass plate, present a color under natural light, and exhibit clear fluorescence under an ultraviolet lamp. The best effect is achieved when the volume ratio of the mother liquor to the acrylic resin is 1:1 to 1.5. It is particularly suitable for fluorescent anti-counterfeiting packaging films, or can be used in OLEDs after being combined with anodes, cathodes, and semiconductor materials. Description of the Drawings

[0019] Figure 1 It is the hydrogen spectrum of compound I-1 obtained in Example 1.

[0020] Figure 2 It is the hydrogen spectrum of compound I-2 obtained in Example 8.

[0021] Figure 3 It is a clear fluorescence image obtained by filming the film formed by compound I-1 and acrylic resin on a glass plate under an ultraviolet lamp (365 nm) with a Huawei nova 12 mobile phone in Example 9-1.

[0022] Figure 4 It is a clear fluorescence image obtained by filming the film formed by compound I-1 and acrylic resin on a glass plate under an ultraviolet lamp (365 nm) with a Huawei nova 12 mobile phone in Example 9-2.

[0023] Figure 5 It is a clear fluorescence image obtained by filming the film formed by compound I-1 and acrylic resin on a glass plate under an ultraviolet lamp (365 nm) with a Huawei nova 12 mobile phone in Example 9-3.

[0024] Figure 6 It is a clear fluorescence image obtained by filming the film formed by compound I-2 and acrylic resin on a glass plate under an ultraviolet lamp (365 nm) with a Huawei nova 12 mobile phone in Example 9-4.

[0025] Figure 7 It is a fluorescence image obtained by filming the film formed by compound I-2 and acrylic resin on a glass plate, wiping it with toilet paper, and then filming it under an ultraviolet lamp (365 nm) with a Huawei nova 12 mobile phone in Example 9-4. Detailed Embodiments

[0026] The present invention will be further described below in conjunction with embodiments, but the scope claimed by the present invention is not limited to the scope described in the embodiments.

[0027] Example 1 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (463.9 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (731.4 mg, 6 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol). After dissolving with a small amount of water, add 15 mL of toluene to dissolve it. Protect it with nitrogen, heat and stir the reaction at 120˚C for 1 hour, and the reaction is complete. After extracting the reactants and rotary evaporation, and column chromatography, an orange-yellow solid compound I-1 is obtained, with a yield of 78.8%.

[0028]

[0029] Example 2 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (731.4 mg, 6 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol). After dissolving with a small amount of water, add 15 mL of toluene to dissolve it. Protect it with nitrogen, heat and stir the reaction at 100˚C for 3 hours. Compared with Example 1, the temperature is reduced by 20˚C, the raw materials do not react completely, and a small amount of by-products are produced. After extracting the reactants and rotary evaporation, and column chromatography, an orange-yellow solid compound I-1 is obtained, and the yield is reduced by 16.2%.

[0030]

[0031] Example 3 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (731.4 mg, 6 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol). After dissolving with a small amount of water, add 15 mL of toluene to dissolve it. Protect it with nitrogen, heat and stir the reaction at 130˚C for 2 hours. Compared with Example 1, the temperature is increased by 10˚C, the reaction is complete, but there are more by-products. After extracting the reactants and rotary evaporation, and column chromatography, the product is obtained, and the yield is reduced by 19.7%.

[0032]

[0033] Example 4 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (975.2 mg, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol). After dissolving in a small amount of water, add 15 mL of toluene to dissolve. Under nitrogen protection, heat and stir the reaction at 120˚C for 0.5 hour until the reaction is complete. Compared with Example 1, the equivalent amount of Compound 2 is doubled, and the yield increases by 14.1%.

[0034]

[0035] Example 5 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (487.6 mg, 4 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (325.8 mg, 1 mmol). After dissolving in a small amount of water, add 15 mL of toluene to dissolve. Under nitrogen protection, heat and stir the reaction at 120˚C for 10 hours. Compared with Example 1, the equivalent amount of Compound 2 is reduced by twofold, and the raw materials do not react completely. After extracting the reactants and rotary evaporation, and column chromatography, an orange-yellow solid compound I-1 is obtained, and the yield is reduced by 23.3%.

[0036]

[0037] Example 6 Weigh the bromine-containing heptafluoroborate fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (975.2 mg, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (651 mg, 2 mmol). After dissolving in a small amount of water, add 15 mL of toluene to dissolve. Under nitrogen protection, heat and stir the reaction at 120˚C for 1 hour until the reaction is complete. Compared with Example 4, the equivalent amount of cesium carbonate is increased by 1 fold. After extracting the reactants and rotary evaporation, and column chromatography, an orange-yellow solid compound I-1 is obtained, and the yield is increased by 25.2%.

[0038]

[0039] Example 7 Weigh the bromine-containing heptacyclic fluoroboron fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add phenylboronic acid of Compound 2 (975.2 mg, 8 mmol), tetrakis(triphenylphosphine)palladium (115.6 mg, 0.1 mmol), cesium carbonate (651 mg, 2 mmol). After dissolving with a small amount of water, add 15 mL of toluene to dissolve it. Protect it with nitrogen, heat and stir at 120˚C for 0.5 hours, and the reaction is complete. Compared with Example 6, the catalyst tetrakis(triphenylphosphine)palladium increases by 0.05 equivalent, and the reaction time is shortened by 0.5 hours. After extracting the reactants and rotary evaporation, orange-yellow solid Compound I-1 is obtained by column chromatography, and the yield remains unchanged.

[0040]

[0041] Example 8 Weigh the bromine-containing heptacyclic fluoroboron fluorescent dye of Compound 1 (436.3 mg, 1 mmol), and then successively add triphenylamine phenylboronic acid of Compound 2 (2.3 g, 8 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), cesium carbonate (651 mg, 2 mmol). After dissolving with a small amount of water, add 15 mL of toluene to dissolve it. Protect it with nitrogen, heat and stir at 120˚C for 0.5 hours, and the reaction is complete. After extracting the reactants and rotary evaporation, orange-red solid Compound I-2 is obtained by column chromatography, and the yield is 63.5%.

[0042]

[0043] Example 9 Preparation of Fluorescent Anti-counterfeiting Film Example 9-1 Weigh Compound I-1 prepared in Example 1 (4.6 mg, 0.01 mmol), take 1 mL of ethyl acetate to dissolve and prepare a mother liquor with a concentration of 0.01 mol / L. Then take 5 μL of the mother liquor and dissolve it in 10 μL of acrylic resin, and evenly brush it twice onto the glass plate with a thickness of about 0.5 cm, and dry it at a temperature of 50˚C. Place the glass plate under a UV lamp (365 nm) and take a photo with a Huawei nova 12 mobile phone to obtain a clear picture, specifically as Figure 3 shown. It can be observed that the surface of the anti-counterfeiting film is uneven and there are bubbles after drying. Since the film formed by the mother liquor and acrylic resin is relatively thin, it is prone to uneven heating in the oven, which is not conducive to the preparation of the anti-counterfeiting film.

[0044] Example 9-2 Weigh compound I-1 in Example 1 (4.6 mg, 0.01 mmol), dissolve it in 1 mL of ethyl acetate to prepare a stock solution with a concentration of 0.01 mol / L. Then take 5 μL of the stock solution and dissolve it in 10 μL of acrylic resin. Use a spin coater to evenly coat it on the glass plate twice, with a thickness of about 0.5 cm. Dry it at 30 °C. Place the glass plate under a UV lamp (365 nm) and take a clear fluorescence image using a Huawei nova 12 mobile phone, as Figure 4 shown. The time required from coating to the start of film formation is 1 min, and the time for stable and uniform film formation is 5 min. Finally, it can be observed that the surface of the anti-counterfeiting film is flat, which is beneficial for the preparation of the anti-counterfeiting film.

[0045] Example 9-3 Weigh compound I-1 in Example 1 (4.6 mg, 0.01 mmol), dissolve it in 1 mL of ethyl acetate to prepare a stock solution with a concentration of 0.01 mol / L. Then take 5 μL of the stock solution and dissolve it in 5 μL of acrylic resin. Use a spin coater to evenly coat it on the glass plate twice, with a thickness of about 0.5 cm. Dry it at 30 °C. Place the glass plate under a UV lamp (365 nm) and take a clear fluorescence image using a Huawei nova 12 mobile phone, specifically as Figure 5 shown. It can be observed that when the volume ratio of the stock solution to acrylic resin is 1:1, the fluorescence intensity is found to be enhanced compared to Example 9-2, and the film formation speed is relatively fast. Compared with Figure 4 the film formation speed is doubled, Figure 5 the film formation speed is 2 minutes, the time required from coating to the start of film formation is 0.5 min, and the time for stable and uniform film formation is 2.5 min. Also, compared with the film formation speed of 20 - 30 min for the anti-counterfeiting film mentioned in the patent "Fluorescent Anti-Counterfeiting Film with Photochromic Function, Its Preparation Method and Application", it is significantly improved.

[0046] Example 9-4 Weigh compound I-2 in Example 8 (4.4 mg, 0.01 mmol), dissolve it in 1 mL of ethyl acetate to prepare a stock solution with a concentration of 0.01 mol / L. Then take 5 μL of the stock solution and dissolve it in 5 μL of acrylic resin. Use a spin coater to evenly coat it on the glass plate twice, with a thickness of about 0.5 cm. Dry it at 30 °C. It is orange under natural light. Place the glass plate under a UV lamp (365 nm) and take a clear fluorescence image using a Huawei nova 12 mobile phone, as Figure 6 shown.

[0047] Example 9-5 Use sulfuric acid paper to act on the anti-counterfeiting film obtained in Example 9-4. After wiping it forcefully five times, obvious fluorescence can still be seen adhering to the glass sheet, specifically as Figure 7 shown.

[0048] The anti-counterfeiting film described in this patent can also be applied to materials such as fresh-keeping films.

[0049] The above embodiments are only the preferred technical solutions of the present invention and should not be regarded as limitations on the present invention. The embodiments in this application and the features in the embodiments can be arbitrarily combined with each other without conflict. The protection scope of the present invention should be the technical solutions recorded in the claims, including the equivalent replacement solutions of the technical features in the technical solutions recorded in the claims. That is, the equivalent replacement improvements within this scope are also within the protection scope of the present invention.

Claims

1. A heptafluoroborate compound containing BF2, characterized in that, The structural formula of the compound is as follows: Ⅰ Among them, the substituent R is any one selected from hydrogen and diphenylamino.

2. The synthesis method of the seven-membered fluoroboron compound containing BF2 according to claim 1, characterized in that, It is realized by the following method: The method includes the following steps: (1) At room temperature, add compound 1 containing brominated heptafluoroborate fluorescent dye, compound 2 of phenylboronic acid or its substituent, tetrakis(triphenylphosphine)palladium, cesium carbonate, and toluene and water. After dissolution, heat the reaction under the protection of nitrogen to obtain a reaction solution; (2) Extract the reaction solution in step (1) with dichloromethane and water. The extract is dried with anhydrous sodium sulfate and then rotary evaporated. After separation by silica gel column chromatography, solid product I, that is, a heptafluoroborate compound containing BF2, is obtained.

3. The synthesis method of the heptafluoroborate compound containing BF2 according to claim 2, characterized in that, In the step (1), the molar ratio of the feed of compound 1 and compound 2 is 1:4 to 8.

4. The synthesis method of the heptafluoroborate compound containing BF2 according to claim 2, wherein The heating temperature in the step (1) is 100 to 130 °C, and the heating time is 0.5 to 10 hours.

5. The synthesis method of the heptafluoroborate compound containing BF2 according to claim 2, wherein In compound 2 in the step (1), the substituent R is any one selected from hydrogen and diphenylamino.

6. Application of the heptafluoroborate compound containing BF2 according to claim 1 on a fluorescent anti-counterfeiting film.

7. The application according to claim 6, wherein During specific application, dissolve the heptafluoroborate compound with a solvent to prepare a mother liquor, then add an acrylic resin to prepare a film-forming solution, and finally coat the film-forming solution onto the application target to form a film to obtain a fluorescent anti-counterfeiting film material.

8. The application according to claim 7, wherein The solvent is any one or a combination of ethyl acetate, dichloromethane, dimethyl sulfoxide, acetonitrile, toluene, etc.

9. The application according to claim 8, wherein The dosage of the heptafluoroborate compound is 0.01 - 0.1 mol / L.

10. A fluorescent anti-counterfeiting film material, characterized in that, It includes the heptafluoroborate compound containing BF2 according to claim 1.

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