Ammonium hydrogen fluoride-containing atomized liquid for glass thinning and preparation method thereof

Abstract

The invention discloses an ammonium bifluoride-containing atomized liquid for glass thinning and a preparation method thereof, and belongs to the technical field of atomized liquid preparation. The ammonium hydrogen fluoride-containing atomized liquid for glass thinning is prepared from the following components in parts by weight: 15-30 parts of hydrofluoric acid, 5-20 parts of ammonium hydrogen fluoride, 1-3 parts of sulfuric acid, 10-20 parts of distilled water, 1-2 parts of a surface additive and 0.8-1.1 parts of a modified thickening agent, and the surface additive is prepared from p-tert-butyl aniline, N, N-dimethyl m-hydroxyaniline, epoxy chloropropane, acrylic acid-N, N-dimethyl m-hydroxyaniline, N, N-dimethyl m-hydroxyaniline, N, N-dimethyl m-hydroxyaniline, N, N-dimethyl m-hydroxyaniline, N, N-dimethyl m-hydroxyaniline, N, N-dimethyl m-hydroxyaniline and N, N-dimethyl m-hydroxyaniline. The thickening agent is prepared from N, N-dimethylamino ethyl ester and azodiisobutyronitrile, and the modified thickening agent is prepared from chitin, chloroacetic acid, stearic acid, 1-ethyl-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide. The atomized liquid prepared by the method can effectively improve the optical performance of a glass finished product.

Description

Technical Field

[0001] The invention belongs to the technical field of atomizing liquid preparation, and in particular relates to an atomizing liquid for glass thinning containing ammonium bifluoride and a preparation method thereof. Background Art

[0002] In the field of electronic display devices, especially with the rapid development of TFT-LCD technology, glass substrates, as the main carrier of electronic components, have become increasingly thinner. Since 1996, the thickness of display glass screens has been greatly reduced from about 1.1mm to the current 0.5mm, and in portable designs such as mobile phones, the thickness of glass has been further reduced to less than 0.3mm. This ultra-thin design not only improves the portability and aesthetics of the device, but also puts higher demands on glass manufacturing and processing technology. However, ultra-thin glass is difficult to manufacture, has high costs, and is easy to break during subsequent processing, making glass thinning a key technology. Glass thinning mainly relies on chemical etching methods, in which hydrofluoric acid and ammonium bifluoride are key components and are widely used in the thinning of glass substrates. Hydrofluoric acid reacts with silicon dioxide, the main component of glass, to generate fluorosilicic acid, thereby achieving glass thinning.

[0003] Patent CN 106316143 A discloses an atomizing liquid for anti-glare processing of Gorilla Glass and a preparation method thereof. The atomizing liquid is composed of the following components in parts by weight: 5-10 parts of ammonium fluoride, 15-20 parts of ammonium bifluoride, 17-23 parts of pure water, 47-63 parts of polyol, and 0.01-0.1 parts of surfactant. Compared with the prior art, the atomizing liquid and the polishing process do not contain hydrofluoric acid, and are safe to transport and use, avoiding environmental pollution. The prepared Gorilla Glass has stable properties and high hardness. However, the atomizing liquid prepared by this method still has room for improvement in the optical properties of the glass. Summary of the invention

[0004] The object of the present invention is to provide an atomizing liquid for glass thinning containing ammonium bifluoride and a preparation method thereof, so as to solve the technical problem in the prior art that the optical properties of glass treated with the atomizing liquid are poor.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The invention provides an atomizing liquid for glass thinning containing ammonium bifluoride. The atomizing liquid is composed of the following components in parts by weight: 15-30 parts of hydrofluoric acid, 5-20 parts of ammonium bifluoride, 1-3 parts of sulfuric acid, 10-20 parts of distilled water, 1-2 parts of a surface additive, and 0.8-1.1 parts of a modified thickener. The surface additive is prepared from p-tert-butylaniline, N,N-dimethyl-m-hydroxyaniline, epichlorohydrin, acrylic acid-N,N-dimethylaminoethyl ester and azobisisobutyronitrile, and the modified thickener is prepared from chitin, chloroacetic acid, stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide.

[0007] Preferably, the method for preparing the surface additive comprises the following steps:

[0008] Q1: Add p-tert-butylaniline and dichloromethane to a container, stir at room temperature, add an aqueous solution of potassium peroxymonosulfonate, stir vigorously after the addition, wash, dry, filter, and distill under reduced pressure to obtain compound 1. Add compound 1, p-aminobenzoic acid and glacial acetic acid to a container, stir, wash, filter, and recrystallize to obtain compound 2;

[0009] Q2: Add compound 2, N,N-dimethyl-m-hydroxyaniline, p-toluenesulfonic acid and tetrahydrofuran to a container, heat and stir to react, distill under reduced pressure, and recrystallize to obtain compound 3; add compound 3, concentrated hydrochloric acid and anhydrous ethanol to a container, stir, dropwise add epichlorohydrin, heat to react, and after the reaction is completed, distill under reduced pressure and recrystallize to obtain compound 4;

[0010] Q3: Add compound 4, N,N-dimethylaminoethyl acrylate, phenothiazine and anhydrous ethanol into a container, heat to react under nitrogen protection, and after the reaction is completed, distill under reduced pressure, wash, and recrystallize to obtain compound 5; add compound 5 and chloroform into a container, evacuate, introduce nitrogen, heat up, and drop a mixed solution of azobisisobutyronitrile and chloroform. After the addition is complete, heat up to react, cool, distill under reduced pressure, precipitate, and dry to obtain a surface additive.

[0011] In the above process, the synthetic reaction formula of the surface additive is as follows:

[0012]

[0013] Preferably, in Q1, the dosage ratio of p-tert-butylaniline and dichloromethane is (0.19-0.38) g: (20-40) mL, the concentration of the aqueous solution of potassium peroxymonosulfonate is 0.076 g / mL, the vigorous stirring time is 8-10 h, washed with ultrapure water, and dried with anhydrous magnesium sulfate, the dosage ratio of compound 1, p-aminobenzoic acid and glacial acetic acid is (0.11-0.22) g: (0.16-0.32) g: (20-40) mL, the stirring time is 20-24 h, washed with ultrapure water, and recrystallized with ethyl acetate.

[0014] Preferably, in Q2, the amount ratio of compound 2, N,N-dimethyl-m-hydroxyaniline, p-toluenesulfonic acid and tetrahydrofuran is (1.13-2.26) g: (0.69-1.38) g: (0.03-0.06) g: (25-50) mL, the heating temperature is 60-100°C, the reaction time is 8-10h, and recrystallization is carried out with acetone. The amount ratio of compound 3, concentrated hydrochloric acid, anhydrous ethanol and epichlorohydrin is (9.16-18.32) g: (1.08-2.16) mL: (50-100) mL: (6.94-13.88) g, the stirring time is 25-30 min, the heating reaction temperature is 60-70°C, the reaction time is 2-4h, and recrystallization is carried out with acetone.

[0015] Preferably, in Q3, the amount ratio of compound 4, N,N-dimethylaminoethyl acrylate, phenothiazine and anhydrous ethanol is (24.77-49.54) g: (7.45-14.9) g: (0.3-0.6) g: (100-200) mL, the heating reaction temperature is 60-80°C, the time is 30-40 h, washed with anhydrous ether, recrystallized with acetone and ethyl acetate, the amount ratio of compound 5 and azobisisobutyronitrile is (6.39-12.78) g: (0.063-0.126) g, the heating temperature is 50-60°C, the heating reaction temperature is 70-75°C, the time is 20-24 h, and precipitated with acetone.

[0016] Preferably, the preparation method of the modified thickener comprises the following steps:

[0017] S1: After chitosan is crushed and sieved, it is added into isopropanol for swelling, and then sodium hydroxide solution is slowly added, stirred, and treated at low temperature to obtain a chitosan solution, chloroacetic acid and isopropanol are mixed, and then added dropwise into the chitosan solution, heated for reaction, centrifuged, supernatant removed, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan;

[0018] S2: Add the modified chitosan to a container containing distilled water, stir thoroughly, and heat to obtain a modified chitosan solution; add stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide to ethanol, heat and stir to obtain a mixed solution; add the mixed solution dropwise to the modified chitosan solution, stir, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

[0019] In the above process, chitosan is mixed with sodium hydroxide solution and chloroacetic acid, and then deacetylation and esterification reactions are carried out to obtain modified chitosan. Then, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are used as catalysts to graft stearic acid into the modified chitosan through acylation reaction to prepare a modified thickener.

[0020] Preferably, in S1, the amount ratio of chitosan, isopropanol and sodium hydroxide solution is (5-7.5) g: (50-75) mL: (30-45) mL, the mass fraction of the sodium hydroxide solution is 50wt%, the swelling time is 2-4h, the low-temperature treatment temperature is -10 to -15°C, the time is 10-12h, the amount ratio of chloroacetic acid and isopropanol is (10-15) g: (10-15) mL, the heating reaction temperature is 50-70°C, and the time is 4-6h.

[0021] Preferably, in S2, the dosage ratio of modified chitosan and distilled water is (2-4) g: (200-400) mL, the molar ratio of stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is (1-3): (1.5-4.5): (1.5-3), the heating and stirring temperature is 60-70°C, the time is 30-45 min, the volume ratio of the mixed solution and the modified chitosan solution is (10-20): (10-20), and the stirring time is 20-24 h.

[0022] Preferably, the method for preparing the atomized liquid for glass thinning containing ammonium bifluoride comprises the following steps:

[0023] Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution;

[0024] Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

[0025] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0026] 1. The present invention first uses p-tert-butylaniline, p-aminobenzoic acid, N,N-dimethyl-m-hydroxyaniline, epichlorohydrin and acrylic acid-N,N-dimethylaminoethyl ester as raw materials to prepare a surface additive, then uses chitosan, sodium hydroxide and stearic acid as raw materials to prepare a modified thickener, and adds the surface additive and the modified thickener to an atomizing liquid for glass thinning, thereby effectively improving the thinning efficiency and enhancing the etching uniformity, and at the same time, improving the stability of the atomizing liquid and protecting the non-etching area.

[0027] 2. The present invention uses p-tert-butylaniline, p-aminobenzoic acid, N,N-dimethyl-m-hydroxyaniline, epichlorohydrin and acrylic acid-N,N-dimethylaminoethyl ester as raw materials to prepare a surface additive, which is added to the atomized liquid to reduce the interfacial tension between the atomized liquid and the glass surface, making it easier to wet and spread on the glass surface, so that the etchant can contact the glass surface more evenly, thereby improving the etching efficiency; and the surface additive can form a thin film on the glass surface through physical or chemical adsorption, which can protect the non-etched area from the erosion of the etchant, and can also serve as a medium between the etchant and the glass surface to promote the etching reaction.

[0028] 3. The present invention uses chitosan, sodium hydroxide and stearic acid as raw materials to prepare a modified thickener, which can be added to the atomized liquid to increase its viscosity, improve stability, reduce droplet splashing and uneven atomization during the spraying process, ensure that the etchant such as ammonium bifluoride can be evenly and stably distributed on the glass surface, and improve the uniformity of the thinning effect; the modified thickener can also reduce the interfacial tension between the atomized liquid and the glass surface, making the atomized liquid easier to wet and spread on the glass surface to form a uniform film. The presence of the film helps the etchant to contact the glass surface more fully, improve the etching efficiency, and improve the quality of the glass product. DETAILED DESCRIPTION

[0029] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Embodiment 1

[0031] This embodiment discloses a method for preparing a surface additive, comprising the following steps:

[0032] Q1: 0.29 g of p-tert-butylaniline and 30 mL of dichloromethane were added to a container, stirred at room temperature, and then 20 mL of an aqueous solution of potassium peroxymonosulfonate with a concentration of 0.076 g / mL was added. After the addition was completed, the mixture was vigorously stirred for 8 h, washed with ultrapure water, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain compound 1. 0.16 g of compound 1, 0.24 g of p-aminobenzoic acid, and 30 mL of glacial acetic acid were added to a container, stirred for 24 h, washed with ultrapure water, filtered, and recrystallized with ethyl acetate to obtain compound 2;

[0033] Q2: 1.70g of compound 2, 1.04g of N,N-dimethyl-m-hydroxyaniline, 0.045g of p-toluenesulfonic acid and 36mL of tetrahydrofuran were added to a container, stirred at 80°C for 10h, distilled under reduced pressure, and recrystallized with acetone to obtain compound 3; 13.74g of compound 3, 1.62mL of concentrated hydrochloric acid and 75mL of anhydrous ethanol were added to a container, stirred for 25min, 10.41g of epichlorohydrin was added dropwise, and reacted at 70°C for 4h. After the reaction was completed, distilled under reduced pressure and recrystallized with acetone to obtain compound 4;

[0034] Q3: 37.16g of compound 4, 11.18g of N,N-dimethylaminoethyl acrylate, 0.45g of phenothiazine and 150mL of anhydrous ethanol were added to a container, and the reaction was carried out at 80°C for 36h under nitrogen protection. After the reaction, the compound was distilled under reduced pressure, washed with anhydrous ether, and recrystallized with acetone and ethyl acetate to obtain compound 5. 9.59g of compound 5 and 25mL of chloroform were added to a container, evacuated, nitrogen was introduced, the temperature was raised to 60°C, and a mixed solution of 0.09g of azobisisobutyronitrile and 10mL of chloroform was added dropwise. After the addition was complete, the reaction was carried out at 75°C for 24h, cooled, distilled under reduced pressure, precipitated with acetone, and dried to obtain a surface additive.

[0035] This embodiment discloses a method for preparing a modified thickener, comprising the following steps:

[0036] S1: 6.75 g of chitosan was crushed and sieved, and then added to 67.5 mL of isopropanol to swell for 4 h, and then 37.5 mL of 50 wt% sodium hydroxide solution was slowly added, stirred, and treated at -10 ° C for 12 h to obtain a chitosan solution, 12.5 g of chloroacetic acid was mixed with 12.5 mL of isopropanol, and then added dropwise to the chitosan solution, reacted at 70 ° C for 6 h, centrifuged, removed the supernatant, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan;

[0037] S2: Add 3 g of modified chitosan to a container containing 300 mL of distilled water, stir thoroughly, and heat to obtain a modified chitosan solution. Add 2 g of stearic acid, 2.02 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.92 g of N-hydroxysuccinimide to 20 mL of ethanol, stir at 70 ° C for 45 min to obtain a mixed solution. Add 15 mL of the mixed solution dropwise to 15 mL of the modified chitosan solution, stir for 24 h, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

[0038] The present embodiment discloses an atomizing liquid for glass thinning containing ammonium bifluoride, which is composed of the following components in parts by weight: 22.5 parts of hydrofluoric acid, 12.5 parts of ammonium bifluoride, 2 parts of sulfuric acid, 15 parts of distilled water, 1.5 parts of a surface additive, and 0.95 parts of a modified thickener.

[0039] This embodiment discloses a method for preparing an atomized liquid for glass thinning containing ammonium bifluoride, comprising the following steps:

[0040] Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution;

[0041] Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

[0042] Embodiment 2

[0043] This embodiment discloses a method for preparing a surface additive, comprising the following steps:

[0044] Q1: 0.19 g of p-tert-butylaniline and 20 mL of dichloromethane were added to a container, stirred at room temperature, and then 20 mL of an aqueous solution of potassium peroxymonosulfonate with a concentration of 0.076 g / mL was added. After the addition was completed, the mixture was vigorously stirred for 8 h, washed with ultrapure water, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain compound 1. 0.11 g of compound 1, 0.16 g of p-aminobenzoic acid, and 20 mL of glacial acetic acid were added to a container, stirred for 24 h, washed with ultrapure water, filtered, and recrystallized with ethyl acetate to obtain compound 2;

[0045] Q2: 1.13g of compound 2, 0.69g of N,N-dimethyl-m-hydroxyaniline, 0.03g of p-toluenesulfonic acid and 25mL of tetrahydrofuran were added to a container, stirred at 80°C for 10h, distilled under reduced pressure, and recrystallized with acetone to obtain compound 3; 9.16g of compound 3, 1.08mL of concentrated hydrochloric acid and 50mL of anhydrous ethanol were added to a container, stirred for 25min, and 6.94g of epichlorohydrin was added dropwise, reacted at 70°C for 4h, and after the reaction was completed, distilled under reduced pressure and recrystallized with acetone to obtain compound 4;

[0046] Q3: 24.77g of compound 4, 7.45g of N,N-dimethylaminoethyl acrylate, 0.3g of phenothiazine and 100mL of anhydrous ethanol were added to a container, and the reaction was carried out at 80°C for 36h under nitrogen protection. After the reaction, the compound was distilled under reduced pressure, washed with anhydrous ether, and recrystallized with acetone and ethyl acetate to obtain compound 5. 6.39g of compound 5 and 25mL of chloroform were added to a container, evacuated, nitrogen was introduced, the temperature was raised to 60°C, and a mixed solution of 0.063g of azobisisobutyronitrile and 10mL of chloroform was added dropwise. After the addition was complete, the reaction was carried out at 75°C for 24h, cooled, distilled under reduced pressure, precipitated with acetone, and dried to obtain a surface additive.

[0047] This embodiment discloses a method for preparing a modified thickener, comprising the following steps:

[0048] S1: 5 g of chitosan was crushed and sieved, and then added to 50 mL of isopropanol to swell for 4 h, and then 30 mL of 50 wt% sodium hydroxide solution was slowly added, stirred, and treated at -10 ° C for 12 h to obtain a chitosan solution, 10 g of chloroacetic acid was mixed with 15 mL of isopropanol, and then added dropwise to the chitosan solution, reacted at 70 ° C for 6 h, centrifuged, removed the supernatant, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan;

[0049] S2: Add 2 g of modified chitosan to a container containing 200 mL of distilled water, stir thoroughly, and heat to obtain a modified chitosan solution. Add 1 g of stearic acid, 1.01 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.61 g of N-hydroxysuccinimide to 20 mL of ethanol, and stir at 70 ° C for 45 min to obtain a mixed solution. Add 10 mL of the mixed solution dropwise to 20 mL of the modified chitosan solution, stir for 24 h, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

[0050] The present embodiment discloses an atomizing liquid for glass thinning containing ammonium bifluoride, which is composed of the following components in parts by weight: 15 parts of hydrofluoric acid, 5 parts of ammonium bifluoride, 1 part of sulfuric acid, 10 parts of distilled water, 1 part of a surface additive, and 0.8 parts of a modified thickener.

[0051] This embodiment discloses a method for preparing an atomized liquid for glass thinning containing ammonium bifluoride, comprising the following steps:

[0052] Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution;

[0053] Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

[0054] Embodiment 3

[0055] This embodiment discloses a method for preparing a surface additive, comprising the following steps:

[0056] Q1: 0.38 g of p-tert-butylaniline and 40 mL of dichloromethane were added to a container, stirred at room temperature, and then 20 mL of an aqueous solution of potassium peroxymonosulfonate with a concentration of 0.076 g / mL was added. After the addition was completed, the mixture was vigorously stirred for 8 h, washed with ultrapure water, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain compound 1. 0.22 g of compound 1, 0.32 g of p-aminobenzoic acid, and 40 mL of glacial acetic acid were added to a container, stirred for 24 h, washed with ultrapure water, filtered, and recrystallized with ethyl acetate to obtain compound 2;

[0057] Q2: 2.26 g of compound 2, 1.38 g of N,N-dimethyl-m-hydroxyaniline, 0.06 g of p-toluenesulfonic acid and 50 mL of tetrahydrofuran were added to a container, stirred at 80°C for 10 h, distilled under reduced pressure, and recrystallized with acetone to obtain compound 3; 18.32 g of compound 3, 2.16 mL of concentrated hydrochloric acid and 100 mL of anhydrous ethanol were added to a container, stirred for 25 min, 13.88 g of epichlorohydrin was added dropwise, and reacted at 70°C for 4 h. After the reaction was completed, distilled under reduced pressure and recrystallized with acetone to obtain compound 4;

[0058] Q3: 49.54g of compound 4, 14.9g of N,N-dimethylaminoethyl acrylate, 0.6g of phenothiazine and 200mL of anhydrous ethanol were added to a container, and the reaction was carried out at 80°C for 36h under nitrogen protection. After the reaction, the compound was distilled under reduced pressure, washed with anhydrous ether, and recrystallized with acetone and ethyl acetate to obtain compound 5. 12.78g of compound 5 and 25mL of chloroform were added to a container, evacuated, nitrogen was introduced, the temperature was raised to 60°C, and a mixed solution of 0.126g of azobisisobutyronitrile and 10mL of chloroform was added dropwise. After the addition was complete, the reaction was carried out at 75°C for 24h, cooled, distilled under reduced pressure, precipitated with acetone, and dried to obtain a surface additive.

[0059] This embodiment discloses a method for preparing a modified thickener, comprising the following steps:

[0060] S1: 7.5 g of chitosan was crushed and sieved, and then added to 75 mL of isopropanol to swell for 4 h, and then 45 mL of 50 wt% sodium hydroxide solution was slowly added, stirred, and treated at -10 ° C for 12 h to obtain a chitosan solution. 15 g of chloroacetic acid was mixed with 10 mL of isopropanol, and then added dropwise to the chitosan solution, reacted at 70 ° C for 6 h, centrifuged, removed the supernatant, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan;

[0061] S2: Add 4 g of modified chitosan to a container containing 400 mL of distilled water, stir thoroughly, and heat to obtain a modified chitosan solution. Add 3 g of stearic acid, 3.03 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 1.22 g of N-hydroxysuccinimide to 20 mL of ethanol, and stir at 70 ° C for 45 min to obtain a mixed solution. Add 20 mL of the mixed solution dropwise to 10 mL of the modified chitosan solution, stir for 24 h, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

[0062] The present embodiment discloses an atomizing liquid for glass thinning containing ammonium bifluoride, which is composed of the following components in parts by weight: 30 parts of hydrofluoric acid, 20 parts of ammonium bifluoride, 3 parts of sulfuric acid, 20 parts of distilled water, 2 parts of a surface additive, and 1.1 parts of a modified thickener.

[0063] This embodiment discloses a method for preparing an atomized liquid for glass thinning containing ammonium bifluoride, comprising the following steps:

[0064] Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution;

[0065] Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

[0066] Embodiment 4

[0067] This embodiment discloses a method for preparing a surface additive, comprising the following steps:

[0068] Q1: 0.24 g of p-tert-butylaniline and 25 mL of dichloromethane were added to a container, stirred at room temperature, and then 20 mL of an aqueous solution of potassium peroxymonosulfonate with a concentration of 0.076 g / mL was added. After the addition was completed, the mixture was vigorously stirred for 8 h, washed with ultrapure water, dried with anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain compound 1. 0.14 g of compound 1, 0.20 g of p-aminobenzoic acid, and 25 mL of glacial acetic acid were added to a container, stirred for 24 h, washed with ultrapure water, filtered, and recrystallized with ethyl acetate to obtain compound 2;

[0069] Q2: 1.41 g of compound 2, 0.82 g of N,N-dimethyl-m-hydroxyaniline, 0.04 g of p-toluenesulfonic acid and 30 mL of tetrahydrofuran were added to a container, stirred at 80°C for 10 h, distilled under reduced pressure, and recrystallized with acetone to obtain compound 3; 11.45 g of compound 3, 1.35 mL of concentrated hydrochloric acid and 80 mL of anhydrous ethanol were added to a container, stirred for 25 min, and 8.67 g of epichlorohydrin was added dropwise, reacted at 70°C for 4 h, and after the reaction was completed, distilled under reduced pressure and recrystallized with acetone to obtain compound 4;

[0070] Q3: 30.97g of compound 4, 9.24g of N,N-dimethylaminoethyl acrylate, 0.4g of phenothiazine and 120mL of anhydrous ethanol were added to a container, and the reaction was carried out at 80°C for 36h under nitrogen protection. After the reaction, the compound was distilled under reduced pressure, washed with anhydrous ether, and recrystallized with acetone and ethyl acetate to obtain compound 5. 7.99g of compound 5 and 25mL of chloroform were added to a container, evacuated, nitrogen was introduced, the temperature was raised to 60°C, and a mixed solution of 0.07g of azobisisobutyronitrile and 10mL of chloroform was added dropwise. After the addition was complete, the reaction was carried out at 75°C for 24h, cooled, distilled under reduced pressure, precipitated with acetone, and dried to obtain a surface additive.

[0071] This embodiment discloses a method for preparing a modified thickener, comprising the following steps:

[0072] S1: 5.5 g of chitosan was crushed and sieved, and then added to 55 mL of isopropanol to swell for 4 h, and then 32 mL of 50 wt% sodium hydroxide solution was slowly added, stirred, and treated at -10 ° C for 12 h to obtain a chitosan solution. 11 g of chloroacetic acid was mixed with 14 mL of isopropanol, and then added dropwise to the chitosan solution, reacted at 70 ° C for 6 h, centrifuged, removed the supernatant, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan;

[0073] S2: Add 2.5 g of modified chitosan to a container containing 250 mL of distilled water, stir thoroughly, and heat to obtain a modified chitosan solution. Add 1.5 g of stearic acid, 1.51 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.75 g of N-hydroxysuccinimide to 20 mL of ethanol, and stir at 70 ° C for 45 min to obtain a mixed solution. Add 12 mL of the mixed solution dropwise to 18 mL of the modified chitosan solution, stir for 24 h, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

[0074] The present embodiment discloses an atomizing liquid for glass thinning containing ammonium bifluoride, which is composed of the following components in parts by weight: 20 parts of hydrofluoric acid, 10 parts of ammonium bifluoride, 1.5 parts of sulfuric acid, 12 parts of distilled water, 1.2 parts of a surface additive, and 0.9 parts of a modified thickener.

[0075] This embodiment discloses a method for preparing an atomized liquid for glass thinning containing ammonium bifluoride, comprising the following steps:

[0076] Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution;

[0077] Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

[0078] Comparative Example 1

[0079] Comparative Example 1 Compared with Example 1, in the process of preparing the surface additive in Comparative Example 1, no N,N-dimethylaminoethyl acrylate was added, and other conditions remained unchanged.

[0080] Comparative Example 2

[0081] Comparative Example 2 Compared with Example 1, in the process of preparing the modified thickener in Comparative Example 2, no chloroacetic acid was added, and other conditions remained unchanged.

[0082] Comparative Example 3

[0083] Comparative Example 3 Compared with Example 1, in the process of preparing the atomizing liquid for glass thinning containing ammonium bifluoride in Comparative Example 3, no surface additive is added, and other conditions remain unchanged.

[0084] Comparative Example 4

[0085] Comparative Example 4 Compared with Example 1, in the process of preparing the atomizing liquid for glass thinning containing ammonium bifluoride, in Comparative Example 4, no modified thickener is added, and other conditions remain unchanged.

[0086] Experimental example

[0087] First, the glass to be thinned is cleaned to remove impurities such as oil and dust on the surface, and then the samples prepared according to the embodiments and comparative examples are poured into an atomizer, and the equipment is started to spray them on the glass surface. After the etching is completed, the treated glass is cleaned to remove the residue on the surface. After the cleaning is completed, the glass is dried to obtain a finished glass product, and the optical properties of the finished glass product are tested according to GB / T 37831-2019.

[0088] Table 1

[0089] project Light transmittance / % Haze / % Clarity / % Embodiment 1 92.1 0.94 91.8 Embodiment 2 91.9 0.99 90.9 Embodiment 3 92.0 0.98 91.3 Embodiment 4 91.8 1.01 90.8 Comparative Example 1 88.5 1.14 83.4 Comparative Example 2 88.3 1.19 83.6 Comparative Example 3 88.1 1.18 82.2 Comparative Example 4 88.0 1.21 82.0

[0090] From the test results in Table 1, it can be seen that the atomized liquid prepared in Examples 1 to 4 of the present invention can effectively improve the optical properties of finished glass products. From the comparison between Comparative Example 1 and Examples 1 to 4, it can be seen that the addition of acrylic acid-N,N-dimethylaminoethyl ester can effectively improve the optical properties of finished glass products; from the comparison between Comparative Example 2 and Examples 1 to 4, it can be seen that the addition of chloroacetic acid can effectively improve the optical properties of finished glass products; from the comparison between Comparative Example 3 and Examples 1 to 4, it can be seen that the addition of a surface additive can effectively improve the optical properties of finished glass products; from the comparison between Comparative Example 4 and Examples 1 to 4, it can be seen that the addition of a modified thickener can effectively improve the optical properties of finished glass products.

[0091] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0092] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A glass thinning atomizing liquid containing ammonium bifluoride, characterized in that: The invention is composed of the following components in parts by weight: 15-30 parts of hydrofluoric acid, 5-20 parts of ammonium bifluoride, 1-3 parts of sulfuric acid, 10-20 parts of distilled water, 1-2 parts of surface additives and 0.8-1.1 parts of modified thickeners, wherein the surface additives are prepared from p-tert-butylaniline, N,N-dimethyl-m-hydroxyaniline, epichlorohydrin, acrylic acid-N,N-dimethylaminoethyl ester and azobisisobutyronitrile, and the modified thickener is prepared from chitin, chloroacetic acid, stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide.

2. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 1, characterized in that: The preparation method of the surface additive comprises the following steps: Q1: Add p-tert-butylaniline and dichloromethane to a container, stir at room temperature, add an aqueous solution of potassium peroxymonosulfonate, stir vigorously after the addition, wash, dry, filter, and distill under reduced pressure to obtain compound 1. Add compound 1, p-aminobenzoic acid and glacial acetic acid to a container, stir, wash, filter, and recrystallize to obtain compound 2; Q2: Add compound 2, N,N-dimethyl-m-hydroxyaniline, p-toluenesulfonic acid and tetrahydrofuran to a container, heat and stir to react, distill under reduced pressure, and recrystallize to obtain compound 3; add compound 3, concentrated hydrochloric acid and anhydrous ethanol to a container, stir, dropwise add epichlorohydrin, heat to react, and after the reaction is completed, distill under reduced pressure and recrystallize to obtain compound 4; Q3: Add compound 4, N,N-dimethylaminoethyl acrylate, phenothiazine and anhydrous ethanol into a container, heat to react under nitrogen protection, and after the reaction is completed, distill under reduced pressure, wash, and recrystallize to obtain compound 5; add compound 5 and chloroform into a container, evacuate, introduce nitrogen, heat up, and drop a mixed solution of azobisisobutyronitrile and chloroform. After the addition is complete, heat up to react, cool, distill under reduced pressure, precipitate, and dry to obtain a surface additive.

3. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 2, characterized in that: In Q1, the dosage ratio of p-tert-butylaniline and dichloromethane is (0.19-0.38) g: (20-40) mL, the concentration of the aqueous solution of potassium peroxymonosulfonate is 0.076 g / mL, the vigorous stirring time is 8-10 h, washed with ultrapure water, and dried with anhydrous magnesium sulfate, the dosage ratio of compound 1, p-aminobenzoic acid and glacial acetic acid is (0.11-0.22) g: (0.16-0.32) g: (20-40) mL, the stirring time is 20-24 h, washed with ultrapure water, and recrystallized with ethyl acetate.

4. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 2, characterized in that: In Q2, the amount ratio of compound 2, N,N-dimethyl-m-hydroxyaniline, p-toluenesulfonic acid and tetrahydrofuran is (1.13-2.26) g: (0.69-1.38) g: (0.03-0.06) g: (25-50) mL, the heating temperature is 60-100°C, the reaction time is 8-10 h, and recrystallization is carried out with acetone. The amount ratio of compound 3, concentrated hydrochloric acid, anhydrous ethanol and epichlorohydrin is (9.16-18.32) g: (1.08-2.16) mL: (50-100) mL: (6.94-13.88) g, the stirring time is 25-30 min, the heating reaction temperature is 60-70°C, the reaction time is 2-4 h, and recrystallization is carried out with acetone.

5. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 2, characterized in that: In Q3, the dosage ratio of compound 4, N,N-dimethylaminoethyl acrylate, phenothiazine and anhydrous ethanol is (24.77-49.54) g: (7.45-14.9) g: (0.3-0.6) g: (100-200) mL, the heating reaction temperature is 60-80°C, the time is 30-40 h, washed with anhydrous ether, recrystallized with acetone and ethyl acetate, the dosage ratio of compound 5 and azobisisobutyronitrile is (6.39-12.78) g: (0.063-0.126) g, the heating temperature is 50-60°C, the heating reaction temperature is 70-75°C, the time is 20-24 h, and precipitated with acetone.

6. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 1, characterized in that: The preparation method of the modified thickener comprises the following steps: S1: After chitosan is crushed and sieved, it is added into isopropanol for swelling, and then sodium hydroxide solution is slowly added, stirred, and treated at low temperature to obtain a chitosan solution, chloroacetic acid and isopropanol are mixed, and then added dropwise into the chitosan solution, heated for reaction, centrifuged, supernatant removed, dissolved, filtered, precipitated, washed, and dried to obtain modified chitosan; S2: Add the modified chitosan to a container containing distilled water, stir thoroughly, and heat to obtain a modified chitosan solution; add stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide to ethanol, heat and stir to obtain a mixed solution; add the mixed solution dropwise to the modified chitosan solution, stir, centrifuge, wash, dialyze, and freeze-dry to obtain a modified thickener.

7. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 6, characterized in that: In the S1, the amount ratio of chitosan, isopropanol and sodium hydroxide solution is (5-7.5) g: (50-75) mL: (30-45) mL, the mass fraction of the sodium hydroxide solution is 50wt%, the swelling time is 2-4h, the low-temperature treatment temperature is -10 to -15°C, the time is 10-12h, the amount ratio of chloroacetic acid and isopropanol is (10-15) g: (10-15) mL, the heating reaction temperature is 50-70°C, and the time is 4-6h.

8. The atomizing liquid for glass thinning containing ammonium bifluoride according to claim 6, characterized in that: In S2, the dosage ratio of modified chitosan and distilled water is (2-4) g: (200-400) mL, the molar ratio of stearic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is (1-3): (1.5-4.5): (1.5-3), the heating and stirring temperature is 60-70°C, the time is 30-45 min, the volume ratio of the mixed solution and the modified chitosan solution is (10-20): (10-20), and the stirring time is 20-24 h.

9. The method for preparing the atomized liquid for glass thinning containing ammonium bifluoride according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step (1): adding hydrofluoric acid, ammonium bifluoride and sulfuric acid into distilled water to obtain a mixed solution; Step (2): adding a surface additive and a modified thickener to the mixed liquid, stirring evenly, and obtaining an atomized liquid for glass thinning containing ammonium bifluoride.

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