Preparation method and application of aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent

Abstract

The present invention provides a multifunctional fluorescent whitening agent made of aminobutyric acid ethyl acrylate, the structural formula of which is shown in Formula 1. The present invention also provides a preparation method and application of the multifunctional fluorescent whitening agent made of aminobutyric acid ethyl acrylate. This multifunctional fluorescent whitening agent has significant whitening and wrinkle-resistant properties for cotton fibers, representing a novel multifunctional fluorescent whitening agent. Its preparation utilizes readily available raw materials and an environmentally friendly process. #imgabs0#

Description

Technical Field

[0001] The invention relates to a multifunctional fluorescent whitening agent and a preparation method and application thereof, and in particular to a preparation method and application of an aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent. Background Art

[0002] Fluorescent brighteners, as functional fluorescent materials, absorb short-wavelength, invisible ultraviolet light and reflect longer-wavelength, visible blue-violet light, thereby brightening and enhancing the color of the substrate. Due to their significant whitening effect and low cost, fluorescent brighteners are commonly used in industries such as printing and dyeing, plastics, papermaking, inks, detergents, coatings, fluorescent probes, and organic transistors.

[0003] In the textile industry, fluorescent brighteners primarily serve a single function, whitening fabrics, and there is a lack of multifunctional fluorescent materials. Traditional fluorescent brighteners suffer from poor affinity with cotton fibers, low dye uptake, poor whitening effects, and limited practicality. During the washing process, cotton fiber molecules become entangled and even break. After repeated washing, cotton fibers lose their inherent smoothness and elasticity, causing the fabric to deform and wrinkle. As an important fine chemical product, fluorescent brighteners, particularly multifunctional fluorescent materials with both whitening and wrinkle-reducing properties, have broad industrial applications and promising market prospects. Summary of the Invention

[0004] One of the objectives of the present invention is to provide a multifunctional fluorescent whitening agent derived from aminobutyric acid ethyl acrylate, which has a simple synthesis method, readily available raw materials, and a green process. Testing of the optical properties of a multifunctional fluorescent whitening agent derived from aminobutyric acid ethyl acrylate clearly demonstrates its strong UV absorption properties. Furthermore, through whitening and wrinkle-resistant treatments on cotton fibers, it was found that the multifunctional fluorescent whitening agent derived from aminobutyric acid ethyl acrylate exhibits significant whitening and wrinkle-resistant properties, demonstrating its potential as a novel multifunctional fluorescent whitening agent with significant potential for promotion and application.

[0005] The second object of the present invention is to provide a method for preparing the above-mentioned aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent.

[0006] The third object of the present invention is to provide the use of the above-mentioned aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent.

[0007] To achieve the first object of the present invention, the present invention adopts the following technical solution: aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent, its structural formula is as shown in Formula 1:

[0008]

[0009] To achieve the first object of the present invention, the present invention adopts the following technical solution: the preparation method of the above-mentioned aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent comprises the following steps:

[0010] (1) adding an aqueous solution of 4,4'-diaminobenzylbenzene-2,2'-disulfonic acid dropwise to a mixture of cyanuric chloride and ice water, and stirring the mixture at 0-5°C to obtain a reaction mixture I;

[0011] (2) The reaction mixture I was heated to 30° C., an aqueous solution of 2-aminoethyl methacrylate hydrochloride was added dropwise, the temperature was raised and maintained at 40-45° C., a small amount of antioxidant was added, the pH of the reaction system was controlled to 6-7 with a saturated aqueous sodium carbonate solution, and the reaction was stirred to obtain a reaction mixture II;

[0012] (3) heating the reaction mixture II to 90° C., adding 4-aminobutyric acid, controlling the temperature at 90-95° C., controlling the pH of the reaction system to 8-9 with a saturated sodium carbonate aqueous solution, and stirring the reaction to obtain a reaction mixture III;

[0013] (4) cooling the reaction mixture III to room temperature, adjusting the pH to 3-4 with dilute acid, and adding an inorganic salt to precipitate the aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent and collecting it;

[0014] The molar ratio of the 4,4'-diaminostilbene-2,2'-disulfonic acid, cyanuric chloride, 2-aminoethyl methacrylate hydrochloride and 4-aminobutyric acid is 1:2:2-2.05:2-2.05.

[0015] In the step (1), in the aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid, every 0.64 mmol of 4,4'-diaminostilbene-2,2'-disulfonic acid corresponds to 20 mL of water; in the cyanuric chloride solution, every 1.28 mmol of cyanuric chloride corresponds to 5 mL of water.

[0016] In the step (1), the pH value of the aqueous solution of 4,4'-diaminobenzylbenzene-2,2'-disulfonic acid is 5-6.

[0017] In the step (2), the antioxidant is sodium sulfite.

[0018] The reaction time of step (1) is 2 hours; the reaction time of step (2) is 5.5 to 6 hours; and the reaction time of step (3) is 7.5 to 8 hours.

[0019] The dilute acid in step (4) is hydrochloric acid; the inorganic salt is sodium chloride.

[0020] The invention discloses a use of an aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent, and specifically relates to the use of the aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent in whitening and anti-wrinkle finishing of cotton fibers.

[0021] The present invention has the following advantages:

[0022] 1. The synthesis method of the aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent of the present invention is simple, the raw materials are easily available, and the process is green.

[0023] 2. The aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent of the present invention has stronger affinity with cotton fiber surface ions, higher bonding strength, and stronger practicality.

[0024] 3. The multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate of the present invention has significant whitening and anti-wrinkle finishing effects on cotton fibers and is a new multifunctional fluorescent whitening agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the ultraviolet absorption spectrum of the optical property test of the aqueous solution of aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent in Example 1.

[0026] Figure 2 These are scanning electron microscope images of cotton fibers before and after treatment with the aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent of Example 1. Specific embodiments

[0027] The present invention will be further described in detail below with reference to specific embodiments, but this does not constitute any limitation to the present invention. Any limited modifications made within the scope of the claims of the present invention are still within the scope of protection of the claims of the present invention.

[0028] Example 1

[0029] Place a 150ml single-necked round-bottom flask containing 5ml of ice water in an ice-water bath, weigh 1.28mmol of cyanuric chloride into the reaction flask, and stir. Prepare 20ml of a clear aqueous solution containing 0.64mmol of 4,4'-diaminostilbene-2,2'-disulfonic acid with saturated sodium carbonate solution and drip it into the above reactor over 30 minutes. Maintain the temperature at 0-5°C and allow the reaction to complete after 2 hours, yielding reaction mixture I. Warm reaction mixture I to 30°C and dropwise add 4ml of an aqueous solution containing 1.28mmol of 2-aminoethyl methacrylate hydrochloride. Raise the temperature to 40-45°C and maintain the pH of the reaction system at 6-7 with saturated sodium carbonate solution. Add a small amount of sodium sulfite and allow the reaction to complete after 6 hours, yielding reaction mixture II. Warm reaction mixture II to 90°C and dropwise add 5ml of an aqueous solution containing 1.28mmol of 4-aminobutyric acid. Maintain the temperature at 90-95°C and control the pH of the reaction system at 8-9 with saturated sodium carbonate solution. Allow the reaction to complete after 8 hours, yielding reaction mixture III. The reaction mixture was cooled to room temperature, and the pH was adjusted to 3-4 with dilute hydrochloric acid (10%). Sodium chloride solid (10% by weight of the solvent) was added, and stirred for 30 minutes. The mixture was filtered, and the solid was washed with a small amount of ice water and ethanol for purification to obtain aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent as a light yellow solid in a yield of 91%.

[0030] Example 2

[0031] Place a 150ml single-necked round-bottom flask containing 5ml of ice water in an ice-water bath, weigh 1.28mmol of cyanuric chloride into the reaction flask, and stir. Prepare 20ml of a clear aqueous solution containing 0.64mmol of 4,4'-diaminostilbene-2,2'-disulfonic acid with a saturated sodium carbonate solution and drip it into the above reactor. Complete the dripping over 30 minutes, maintain the temperature at 0-5°C, and allow the reaction to complete after 2 hours, yielding Reaction Mixture I. Raise the temperature of Reaction Mixture I to 30°C, add 4ml of an aqueous solution containing 1.31mmol of 2-aminoethyl methacrylate hydrochloride, raise the temperature to and maintain it at 40-45°C, control the pH of the reaction system to 6-7 with a saturated sodium carbonate solution, add a small amount of sodium sulfite, and allow the reaction to complete after 5.5 hours, yielding Reaction Mixture II. The reaction mixture II was heated to 90°C, and 5 ml of an aqueous solution containing 1.31 mmol of 4-aminobutyric acid was added dropwise. The temperature was controlled at 90-95°C, and the pH of the reaction system was controlled to 8-9 with a saturated aqueous sodium carbonate solution. The reaction was allowed to complete for 7.5 hours to obtain a reaction mixture III. The reaction mixture was cooled to room temperature, and the pH was adjusted to 3-4 with dilute hydrochloric acid (10%). Solid sodium chloride (10% by weight of the solvent) was added, stirred for 30 minutes, and filtered. The solid was washed and purified with a small amount of ice water and ethanol to obtain aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent as a light yellow solid in a yield of 92%.

[0032] Optical performance test

[0033] The optical properties of the product of the present invention were tested by UV-visible spectroscopy. Figure 1 shown.

[0034] The multifunctional fluorescent brightener of aminobutyric acid ethyl acrylate was prepared into a concentration of 2×10 -5 The optical performance test of the aqueous solution with a concentration of 500 μg / ml was carried out. The test results showed that the multifunctional fluorescent brightener of aminobutyric acid ethyl acrylate has strong ultraviolet absorption performance.

[0035] Whitening and anti-wrinkle finishing performance test

[0036] Prepare an aqueous solution of 0.10-0.70% (owf) aminobutyric acid ethyl acrylate multifunctional fluorescent brightener and treat a special pure cotton fabric that does not contain the fluorescent brightener. The mass ratio of bath solution to pure cotton fabric is 50:1. Raise the temperature from 20°C to 50°C at a rate of 2°C / minute over 15 minutes. Then, maintain the bath at 50°C for 15 minutes. Remove the dyed cotton fabric, rinse it with cold water, dry it at room temperature, and measure its whiteness.

[0037] Whiteness tests revealed that the multifunctional fluorescent brightener, aminobutyric acid ethyl acrylate, exhibited a significant whitening effect on cotton fabric at various dye concentrations, with the optimal dye concentration being 0.60%. At this optimal dye concentration, the maximum whiteness value of treated cotton fabric was 107.09, a 30.41 improvement compared to the 76.68 whiteness of untreated cotton fibers. Scanning electron microscopy was used to examine the surface structure of both untreated and treated cotton fibers, revealing a rough, uneven surface with noticeable cracks and wrinkles. However, the treated fibers exhibited no wrinkles, resulting in a smoother, flatter surface. These experimental results demonstrate that the multifunctional fluorescent brightener, aminobutyric acid ethyl acrylate, exhibits significant whitening and anti-wrinkle finishing properties, making it a novel multifunctional fluorescent brightener with significant practical value and application prospects.

[0038] The above descriptions are merely embodiments of the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate, characterized in that: Its structural formula is as shown in Formula 1:

2. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 1, characterized in that: The following steps are involved: (1) adding an aqueous solution of 4,4'-diaminobenzylbenzene-2,2'-disulfonic acid dropwise to a mixture of cyanuric chloride and ice water, and stirring the mixture at 0-5°C to obtain a reaction mixture I; (2) The reaction mixture I was heated to 30° C., an aqueous solution of 2-aminoethyl methacrylate hydrochloride was added dropwise, the temperature was raised and maintained at 40-45° C., a small amount of antioxidant was added, the pH of the reaction system was controlled to 6-7 with a saturated aqueous sodium carbonate solution, and the reaction was stirred to obtain a reaction mixture II; (3) heating the reaction mixture II to 90° C., adding 4-aminobutyric acid, controlling the temperature at 90-95° C., controlling the pH of the reaction system to 8-9 with a saturated sodium carbonate aqueous solution, and stirring the reaction to obtain a reaction mixture III; (4) cooling the reaction mixture III to room temperature, adjusting the pH to 3-4 with dilute acid, and adding an inorganic salt to precipitate an aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent and collecting it; The molar ratio of the 4,4'-diaminostilbene-2,2'-disulfonic acid, cyanuric chloride, 2-aminoethyl methacrylate hydrochloride and 4-aminobutyric acid is 1:2:2-2.05:2-2.

05.

3. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 2, wherein: In the step (1), in the aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid, every 0.64 mmol of 4,4'-diaminostilbene-2,2'-disulfonic acid corresponds to 20 mL of water; in the cyanuric chloride solution, every 1.28 mmol of cyanuric chloride corresponds to 5 mL of water.

4. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 2, wherein: In the step (1), the pH value of the aqueous solution of 4,4'-diaminobenzylbenzene-2,2'-disulfonic acid is 5-6.

5. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 2, characterized in that: In the step (2), the antioxidant is sodium sulfite.

6. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 2, characterized in that: The reaction time of step (1) is 2 hours; the reaction time of step (2) is 5.5 to 6 hours; and the reaction time of step (3) is 7.5 to 8 hours.

7. The method for preparing a multifunctional fluorescent whitening agent of aminobutyric acid ethyl acrylate according to claim 2, characterized in that: The dilute acid in step (4) is hydrochloric acid; the inorganic salt is sodium chloride.

8. Use of the aminobutyric acid ethyl acrylate multifunctional fluorescent whitening agent according to claim 1 in whitening and anti-wrinkle finishing of cotton fibers.

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