High-dispersity fluorescent whitening functional aid as well as preparation method and application thereof

Abstract

The invention discloses a high-dispersity fluorescent whitening functional aid as well as a preparation method and application thereof, and relates to the technical field of functional dyes. The high-dispersity fluorescent whitening functional aid comprises the following raw materials in parts by weight: 40-50 parts of a fluorescent whitening agent, 10-15 parts of sodium lignin sulfonate, 5-8 parts of a pH buffer agent, 3-5 parts of an anti-aging agent and 50-70 parts of deionized water. Undecylenic acid and hexaethylene glycol monomethyl ether react to generate an ester group compound, the ester group compound generates an epoxy compound under the action of hydrogen peroxide and formic acid, 4, 4 '-diaminostilbene-2, 2'-disulfonic acid and trimellitic anhydride react to generate a tetracarboxyl compound, and the tetracarboxyl compound and the epoxy compound react to generate an epoxy compound. And reacting the epoxy compound with the tetracarboxyl compound to generate the fluorescent whitening agent. The prepared high-dispersity fluorescent whitening functional aid has excellent dispersity, stability and anti-aging performance, and has important application significance in the field of cotton fiber textiles.

Description

Technical Field

[0001] This invention relates to the field of functional dye technology, specifically to a highly dispersible fluorescent whitening functional additive, its preparation method, and its application. Background Technology

[0002] Optical brighteners, as optical modifiers, are widely used in the textile, paper, plastics, and detergent industries. Cotton fiber, as one of the main raw materials for textiles, accounts for more than 40% of fabric raw materials. However, the molecular structure of cotton fiber oxidizes and yellows under light, greatly affecting the whiteness quality of cotton fabrics. In addition, some fabrics are not white enough on their own and need to be made whiter and brighter. Currently, the solution is mostly to use optical brighteners to whiten cotton fibers. However, existing optical brighteners have insufficient resistance to light aging in practical applications, affecting the product's lifespan. In addition, existing optical brighteners also have poor dispersibility and are prone to stratification during long-term storage, leading to differences in the concentration of brighteners in different batches, resulting in uneven whitening effects between batches and affecting product quality.

[0003] Chinese invention patent CN119913745A discloses a highly dispersed and stable fluorescent whitening agent, its preparation method, and its application method. This fluorescent whitening agent is a dispersion composed of a whitening agent filter cake, a dispersant, a solvent, a thickener, and water. Applying this whitening agent to the whitening process of polyester and its blended fabrics can achieve a uniform whitening effect without forming fluorescent or yellow spots, resulting in high-quality whitened fabrics. However, its anti-aging properties are relatively poor. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a highly dispersible fluorescent whitening functional additive, its preparation method, and its application.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A highly dispersible fluorescent whitening functional additive, comprising the following raw materials in parts by weight: 40-50 parts of fluorescent whitening agent, 10-15 parts of sodium lignosulfonate, 5-8 parts of pH buffer, 3-5 parts of anti-aging agent, and 50-70 parts of deionized water; The fluorescent whitening agent is prepared by the following method: S1: Undecenoic acid reacts with hexaethylene glycol monomethyl ether to form an ester compound, and the reaction equation is shown below:

[0006] S2: Ester compounds react with hydrogen peroxide and formic acid to form epoxides, as illustrated in the following reaction equation:

[0007] S3: 4,4'-Diaminostilbene-2,2'-disulfonic acid reacts with trimellitic anhydride to form a tetracarboxylic compound, as shown in the following schematic equation:

[0008] S4: Epoxides react with tetracarboxylic acid compounds to form fluorescent whitening agents. The reaction equation is shown below:

[0009] In step S1, the molar ratio of undecenoic acid to hexaethylene glycol monomethyl ether is 1:(1.05-1.1).

[0010] In step S2, the molar ratio of the ester compound, hydrogen peroxide and formic acid is 1:(1.5-1.8):(1.2-1.5).

[0011] In step S3, the molar ratio of 4,4'-diaminostilbene-2,2'-disulfonic acid to trimellitic anhydride is 1:(2.1-2.2).

[0012] In step S4, the molar ratio of the epoxy compound to the tetracarboxylic compound is (4.1-4.2):1.

[0013] The anti-aging agent is prepared by the following method: N1: Cyanurium chloride reacts with 2,2,6,6-tetramethyl-4-aminopiperidine to form a monosubstituted product, and the reaction equation is shown below:

[0014] N2: The monosubstituted product reacts with 2,5-diaminobenzenesulfonic acid to form the disubstituted product, as shown in the following schematic equation:

[0015] N3: The disubstituted product reacts with polyoxyethylene hexyl ether to form an anti-aging agent. The reaction equation is shown below:

[0016] In step N1, the molar ratio of cyanuric chloride to 2,2,6,6-tetramethyl-4-aminopiperidine is 1:1.05; in step N2, the molar ratio of the monosubstituted product to 2,5-diaminobenzenesulfonic acid is 2.1:1; in step N3, the molar ratio of the disubstituted product to polyoxyethylene hexyl ether is 1:2.2.

[0017] The pH buffer is a mixture of citric acid and sodium citrate.

[0018] A method for preparing a highly dispersible fluorescent whitening functional additive, characterized by comprising the following steps: (1) Weigh out the following by weight: 40-50 parts of fluorescent whitening agent, 10-15 parts of sodium lignosulfonate, 5-8 parts of pH buffer, 3-5 parts of anti-aging agent, and 50-70 parts of deionized water. (2) Mix sodium lignosulfonate with deionized water, heat and stir until uniform, cool naturally to room temperature, add fluorescent whitening agent, stir, add pH buffer and anti-aging agent, shear at high speed, and sieve to obtain highly dispersible fluorescent whitening functional additive.

[0019] Application of a highly dispersible fluorescent whitening functional additive in cotton fiber textiles.

[0020] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The highly dispersible fluorescent whitening functional additive prepared by this invention has excellent dispersibility, stability and anti-aging properties, and has important application significance in the field of cotton fiber textiles. Detailed Implementation

[0021] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0022] Example 1: Preparation of fluorescent whitening agent: S1: Add 300 ml toluene, 0.1 mol undecenoic acid, 0.105 mol hexaethylene glycol monomethyl ether, and 0.3 g p-toluenesulfonic acid to a reaction vessel, stir and mix well, heat to 90 °C, and maintain the temperature for 9 h (during the reaction, remove the water produced by the reaction using a water separator). Cool to room temperature, adjust the pH to 7 using saturated sodium bicarbonate, and separate the layers. Wash the organic phase successively with saturated brine (2 × 80 ml) and deionized water (2 × 80 ml). Dry the organic phase with 10 g anhydrous magnesium sulfate for 1 h, filter, and distill under reduced pressure at 60 °C for 3 h to obtain the ester compound; its 1H NMR data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 5.87 -5.67 (m, 1H), 5.19 - 4.89 (m, 2H), 4.33 (t, J = 5.3 Hz, 2H), 3.80 - 3.53 (m,22H), 3.38 (s, 3H), 2.31 (t, J = 8.5 Hz, 2H), 2.03 (tdt, J = 8.1, 6.8, 1.4Hz, 2H), 1.65 - 1.49 (m, 2H), 1.43 - 1.20 (m, 10H); S2: 300 ml DMF, 5 g strong acid cation exchange resin, and 0.1 mol ester compound were added to a reaction vessel and stirred until homogeneous. The mixture was heated to 50 °C, and a mixed solution of 17 g 30 wt% hydrogen peroxide and 5.5 g formic acid was added dropwise over 30 min. The reaction was allowed to proceed for 8 h, cooled to room temperature, filtered, and extracted with dichloromethane (3 × 200 ml). The combined organic phases were washed with deionized water (3 × 80 ml), dried with 10 g anhydrous sodium sulfate for 1 h, filtered, and distilled under reduced pressure at 30 °C for 2 h to obtain the epoxide compound. Its 1H NMR spectrum data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 4.33 (t, J = 5.3 Hz, 2H), 3.78 - 3.53(m, 22H), 3.38 (s, 3H), 3.03 (tt, J = 4.7, 2.5 Hz, 1H), 2.88 (d, J = 2.5 Hz,2H), 2.31 (t, J = 8.5 Hz, 2H), 1.66 - 1.49 (m, 4H), 1.46 - 1.19 (m, 10H); S3: Add 300 ml of DMF and 0.21 mol of trimellitic anhydride to a reaction vessel. Add 200 ml of a DMF solution containing 0.1 mol of 4,4'-diaminostilbene-2,2'-disulfonic acid dropwise at room temperature. The addition is completed in 1 hour, and the reaction is allowed to proceed for 6 hours. After cooling to room temperature, slowly pour the reaction solution into 800 ml of cold acetone. Stir to precipitate a solid, filter, and recrystallize using 250 ml of a mixed solution of acetone and DMF (acetone to DMF volume ratio 9:1). Filter, and dry under vacuum at 70 °C for 10 hours to obtain a tetracarboxylic compound. Its 1H NMR spectrum data are as follows: 1 H NMR (300 MHz, DMSO- d 6) δ 13.47 (s, 2H), 12.94 (s, 2H), 12.36 (s, 2H), 8.34 (d, J = 2.2 Hz, 2H), 7.99 - 7.90 (m, 4H), 7.86 - 7.74 (m, 4H), 7.68 (d,J = 0.6 Hz, 2H), 7.62 (dd, J = 8.2, 2.2 Hz, 2H), 6.33 (s, 2H); S4: Add 1000 ml DMF, 0.1 mol tetracarboxylic acid compound, and 0.41 mol epoxy compound to a reaction vessel, stir to mix, heat to 80 °C, react for 15 h, cool to room temperature, distill under reduced pressure at 70 °C for 3 h, pour the reaction solution into 750 ml cold diethyl ether, stir to precipitate, filter, recrystallize using 800 ml acetone, filter, and dry under vacuum at 50 °C for 10 h to obtain the fluorescent whitening agent. Its 1H NMR data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 11.91 (s, 2H), 8.46 (d, J =1.9 Hz, 2H), 8.04 - 7.91 (m, 6H), 7.75 (d, J = 0.6 Hz, 2H), 7.69 (d, J = 0.7Hz, 2H), 7.57 (dd, J = 8.3, 2.1 Hz, 2H), 6.57 (s, 2H), 4.42 - 4.02 (m, 16H), 3.90 - 3.52 (m, 92H), 3.40 (d, J = 13.0 Hz, 16H), 2.31 (t, J = 8.5 Hz, 8H), 1.78 - 1.20 (m, 56H).

[0023] Example 2 Preparation of fluorescent whitening agent: S1: Add 300 ml toluene, 0.1 mol undecenoic acid, 0.108 mol hexaethylene glycol monomethyl ether, and 0.3 g p-toluenesulfonic acid to a reaction vessel, stir and mix well, heat to 95 °C, and maintain the temperature for 8 h (during the reaction, the water produced by the reaction is separated by a water separator), cool to room temperature, adjust the pH to 7 using saturated sodium bicarbonate, separate the layers, wash the organic phase successively with saturated brine (2 × 80 ml) and deionized water (2 × 80 ml), dry the organic phase with 10 g anhydrous magnesium sulfate for 1 h, filter, and distill under reduced pressure at 60 °C for 3 h to obtain the ester compound; S2: Add 300ml DMF, 5g strong acid cation exchange resin, and 0.1mol ester compound to a reaction vessel, stir and mix well, heat to 55℃, add dropwise a mixed solution of 18g 30wt% hydrogen peroxide solution and 6.4g formic acid, the addition is completed in 30min, react for 7h, cool to room temperature, filter, extract with dichloromethane (3×200ml), combine organic phases and wash with deionized water (3×80ml), dry with 10g anhydrous sodium sulfate for 1h, filter, distill under reduced pressure at 30℃ for 2h to obtain epoxy compound; S3: Add 300 ml DMF and 0.215 mol trimellitic anhydride to the reaction vessel, and add 200 ml of DMF solution containing 0.1 mol 4,4'-diaminostilbene-2,2'-disulfonic acid dropwise at room temperature. The addition is completed in 1 h, and the reaction is carried out for 5 h. After cooling to room temperature, the reaction solution is slowly poured into 800 ml of cold acetone, stirred to precipitate solid, filtered, and recrystallized using a mixed solution of 250 ml acetone and DMF (the volume ratio of acetone to DMF is 9:1). After filtration, the solution is dried under vacuum at 70 °C for 10 h to obtain a tetracarboxylic compound. S4: Add 1000ml DMF, 0.1mol tetracarboxylic acid compound, and 0.415mol epoxy compound to a reaction vessel, stir and mix well, heat to 85℃, react for 18h, cool to room temperature, distill under reduced pressure at 70℃ for 3h, pour the reaction solution into 750ml cold diethyl ether, stir to precipitate, filter, recrystallize with 800ml acetone, filter, and vacuum dry at 50℃ for 10h to obtain the fluorescent whitening agent.

[0024] Example 3 Preparation of fluorescent whitening agent: S1: Add 300 ml toluene, 0.1 mol undecenoic acid, 0.11 mol hexaethylene glycol monomethyl ether, and 0.3 g p-toluenesulfonic acid to a reaction vessel, stir and mix well, heat to 100 °C, and maintain the temperature for 7 h (during the reaction, separate the water produced by the reaction through a water separator), cool to room temperature, adjust the pH to 7 using saturated sodium bicarbonate, separate the layers, wash the organic phase successively with saturated brine (2 × 80 ml) and deionized water (2 × 80 ml), dry the organic phase with 10 g anhydrous magnesium sulfate for 1 h, filter, and distill under reduced pressure at 60 °C for 3 h to obtain the ester compound; S2: Add 300ml DMF, 5g strong acid cation exchange resin, and 0.1mol ester compound to a reaction vessel, stir and mix well, heat to 60℃, add dropwise a mixed solution of 20g 30wt% hydrogen peroxide solution and 6.9g formic acid, the addition is completed in 30min, react for 6h, cool to room temperature, filter, extract with dichloromethane (3×200ml), combine organic phases and wash with deionized water (3×80ml), dry with 10g anhydrous sodium sulfate for 1h, filter, distill under reduced pressure at 30℃ for 2h to obtain epoxy compound; S3: Add 300 ml DMF and 0.22 mol trimellitic anhydride to the reaction vessel, and add 200 ml of DMF solution containing 0.1 mol 4,4'-diaminostilbene-2,2'-disulfonic acid dropwise at room temperature. The addition is completed in 1 h, and the reaction is carried out for 4 h. After cooling to room temperature, the reaction solution is slowly poured into 800 ml of cold acetone, stirred to precipitate solid, filtered, and recrystallized using a mixed solution of 250 ml acetone and DMF (the volume ratio of acetone to DMF is 9:1). After filtration, the solution is dried under vacuum at 70 °C for 10 h to obtain a tetracarboxylic compound. S4: Add 1000ml DMF, 0.1mol tetracarboxylic acid compound, and 0.42mol epoxy compound to a reaction vessel, stir and mix well, heat to 90℃, react for 20h, cool to room temperature, distill under reduced pressure at 70℃ for 3h, pour the reaction solution into 750ml cold diethyl ether, stir to precipitate, filter, recrystallize with 800ml acetone, filter, and dry under vacuum at 50℃ for 10h to obtain the fluorescent whitening agent.

[0025] Example 4: Preparation of anti-aging agent: N1: Under ice bath conditions, 200 ml of toluene and 0.1 mol of cyanuric chloride were added to the reaction vessel and stirred until well mixed. 0.105 mol of 2,2,6,6-tetramethyl-4-aminopiperidine was added dropwise over 30 min. The reaction was maintained at 0 °C for 4 h. The product was washed successively with 50 ml of 5 wt% sodium bicarbonate solution and deionized water (3 × 50 ml). The organic phase was dried over 10 g of anhydrous magnesium sulfate for 1 h, filtered, and distilled under reduced pressure at 60 °C for 3 h to obtain the monosubstituted product. Its 1H NMR data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ5.85 (d, J = 5.9 Hz, 1H), 4.24 – 4.09 (m, 1H), 2.03 (dd, J = 13.6, 5.5 Hz, 2H), 1.77 (dd, J = 13.5, 5.4 Hz, 2H), 1.49 (s, 1H), 1.29 (s, 6H), 1.16 (s, 6H); N2: Add 300 ml of acetone and 0.21 mol of the monosubstituted product to the reaction vessel and stir until homogeneous. Add 0.1 mol of 2,5-diaminobenzenesulfonic acid to 200 ml of deionized water and mix well. Adjust the pH to 7 using 30 wt% NaOH solution and add it dropwise to the reaction vessel over 1 hour. Raise the temperature to 45°C and maintain the reaction temperature for 6 hours (adjusting the pH to 7 using 0.25 M NaOH solution during the reaction). Cool to room temperature and add 100 g of sodium chloride in 5 batches (5 batches, 5 min apart) while stirring. Continue stirring for 1 hour to precipitate. Filter the precipitate and mix it with 200 ml of 50°C warm water. Slowly pour the mixture into 350 ml of anhydrous ethanol. Cool to room temperature to precipitate. Filter the precipitate and wash it with cold anhydrous ethanol (2 × 200 ml). Dry the precipitate under vacuum at 50°C for 12 hours to obtain the disubstituted product. Its 1H NMR data are as follows: 1 H NMR (300 MHz, DMSO- d6) δ 10.23 (s, 1H), 9.68 (s, 1H), 8.63 (d, J =2.1 Hz, 1H), 7.99 - 7.82 (m, 2H), 6.05 (d, J = 6.0 Hz, 2H), 4.26 - 4.10 (m,2H), 2.25 (s, 2H), 1.99 (dd, J = 13.5, 5.4 Hz, 4H), 1.74 (dd, J = 13.5, 5.5Hz, 4H), 1.29 (s, 12H), 1.16 (s, 12H); N3: 500 ml of acetonitrile, 0.1 mol of the disubstituted product, and 0.22 mol of polyoxyethylene hexyl ether were added to a reaction vessel and stirred until homogeneous. 0.25 mol of N,N-diisopropylethylamine was added, and the mixture was refluxed for 6 h. After cooling to 50 °C, the mixture was distilled under reduced pressure for 2 h. 400 ml of deionized water was added and stirred until homogeneous. The mixture was extracted with dichloromethane (3 × 200 ml), and the organic phases were combined. The mixture was washed with saturated brine (2 × 100 ml), dried with 15 g of anhydrous sodium sulfate for 1 h, filtered, and distilled under reduced pressure at 40 °C for 2 h to obtain the anti-aging agent. Its 1H NMR data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 10.77 (s, 1H), 10.09 (s, 1H), 8.74(d, J = 2.1 Hz, 1H), 8.02 - 7.73 (m, 2H), 6.95 (d, J = 6.0 Hz, 2H), 4.52 (t,J = 5.8 Hz, 4H), 4.23 - 4.10 (m, 2H), 3.80 (t, J = 5.8 Hz, 4H), 3.73 - 3.58(m, 32H), 3.50 (t, J = 6.1 Hz, 4H), 2.03 (dd, J = 13.6, 5.5 Hz, 4H), 1.77(dd, J = 13.5, 5.4 Hz, 4H), 1.56 (ttd, J = 6.9, 6.1, 0.8 Hz, 4H), 1.49 (s,2H), 1.42 - 1.26 (m, 24H), 1.16 (s, 12H), 0.95 - 0.83 (m, 6H).

[0026] Example 5: Preparation of highly dispersible fluorescent whitening functional additives: (1) Weigh the following by weight: 40g of fluorescent whitening agent (prepared in Example 1), 10g of sodium lignosulfonate, 5g of pH buffer (1.8g of citric acid and 3.2g of sodium citrate), 3g of anti-aging agent (prepared in Example 4), and 50g of deionized water; (2) Mix sodium lignosulfonate with deionized water, heat to 60°C, stir at 300 rpm for 30 min, cool naturally to room temperature, add fluorescent whitening agent, stir at 800 rpm for 60 min, add pH buffer and anti-aging agent, place in a high shear emulsifier, shear at 10000 rpm for 20 min, pass through a 500-mesh sieve to obtain highly dispersible fluorescent whitening functional additive.

[0027] Example 6: Preparation of highly dispersible fluorescent whitening functional additives: (1) Weigh the following by weight: 45g of fluorescent whitening agent (prepared in Example 2), 12g of sodium lignosulfonate, 6g of pH buffer (2g of citric acid and 4g of sodium citrate), 4g of anti-aging agent (prepared in Example 4), and 60g of deionized water; (2) Mix sodium lignosulfonate with deionized water, heat to 60°C, stir at 300 rpm for 30 min, cool naturally to room temperature, add fluorescent whitening agent, stir at 800 rpm for 60 min, add pH buffer and anti-aging agent, place in a high shear emulsifier, shear at 10000 rpm for 20 min, pass through a 500-mesh sieve to obtain highly dispersible fluorescent whitening functional additive.

[0028] Example 7 Preparation of highly dispersible fluorescent whitening functional additives: (1) Weigh the following by weight: 50g of fluorescent whitening agent (prepared in Example 3), 15g of sodium lignosulfonate, 8g of pH buffer (3g of citric acid and 5g of sodium citrate), 5g of anti-aging agent (prepared in Example 4), and 70g of deionized water; (2) Mix sodium lignosulfonate with deionized water, heat to 60°C, stir at 300 rpm for 30 min, cool naturally to room temperature, add fluorescent whitening agent, stir at 800 rpm for 60 min, add pH buffer and anti-aging agent, place in a high shear emulsifier, shear at 10000 rpm for 20 min, pass through a 500-mesh sieve to obtain highly dispersible fluorescent whitening functional additive.

[0029] Comparative Example 1 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the fluorescent whitening agent is replaced with an equal weight of fluorescent whitening agent prepared by the following method: The preparation method of the fluorescent whitening agent is basically the same as that in Example 2, except that the hexaethylene glycol monomethyl ether in step S1 is replaced with an equimolar amount of nonadecanol.

[0030] Comparative Example 2 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the fluorescent whitening agent is replaced with an equal weight of fluorescent whitening agent prepared by the following method: The preparation method of the fluorescent whitening agent is basically the same as that in Example 2, except that the hexaethylene glycol monomethyl ether in step S1 is replaced with an equimolar amount of polyethylene glycol monomethyl ether (number average molecular weight 1000).

[0031] Comparative Example 3 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the fluorescent whitening agent is replaced with an equal weight of fluorescent whitening agent prepared by the following method: The preparation method of the fluorescent whitening agent is basically the same as that in Example 2, except that undecenoic acid in step S1 is replaced with an equimolar amount of 4-pentenoic acid.

[0032] Comparative Example 4 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the fluorescent whitening agent is replaced with an equal weight of fluorescent whitening agent prepared by the following method: The preparation method of the fluorescent whitening agent is basically the same as that in Example 2, except that trimellitic anhydride in step S3 is replaced with an equimolar amount of phthalic anhydride.

[0033] Comparative Example 5 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6. The difference is that 45g of fluorescent whitening agent is replaced with 32.5g of 17-hydroxy-3,6,9,12,15-pentaoxaheptadecylnonanoate (CAS: 855959-55-6) and 13g of the tetracarboxylic compound prepared in step S3 of Example 2.

[0034] Comparative Example 6 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the anti-aging agent is replaced with an equal weight of an anti-aging agent prepared by the following method: The preparation method of the anti-aging agent is basically the same as that in Example 4, except that 2,5-diaminobenzenesulfonic acid in step N2 is replaced with an equimolar amount of p-phenylenediamine.

[0035] Comparative Example 7 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the anti-aging agent is replaced with 4.5g of anti-aging agent prepared by the following method: The preparation method of the anti-aging agent is basically the same as that in Example 4, except that 2,5-diaminobenzenesulfonic acid in step N2 is replaced with an equimolar amount of p-aminobenzenesulfonic acid.

[0036] Comparative Example 8 The raw material composition and preparation method of the highly dispersible fluorescent whitening functional additive are basically the same as those in Example 6, except that the anti-aging agent is replaced with an equal weight of an anti-aging agent prepared by the following method: The preparation method of the anti-aging agent is basically the same as that in Example 4, except that the polyoxyethylene hexyl ether in step N3 is replaced with an equimolar amount of diethylene glycol monohexyl ether.

[0037] The sodium lignosulfonate used in the embodiments and comparative examples of this application is model DA30, produced by Shandong Yiyi Chemical Co., Ltd.; the CAS number of polyoxyethylene hexyl ether is 86674-95-5.

[0038] The dispersion performance and anti-aging performance of the highly dispersible fluorescent whitening functional additives prepared in Examples 5-7 and Comparative Examples 1-5 were tested, and the test results are shown in Table 1.

[0039] Water dispersion performance test: Weigh 200g of water into a 500ml sealed bottle, add 1g of highly dispersible fluorescent whitening functional additive, seal the bottle and place it in an ultrasonic oscillator (frequency 20kHz) for ultrasonic dispersion, record the time it takes for the highly dispersible fluorescent whitening functional additive to be completely dispersed in water (without turbidity); and use a Zeta potential analyzer to test the Zeta potential value of the liquid without turbidity.

[0040] Anti-aging performance test: 1g of the highly dispersible fluorescent whitening functional additive prepared in the examples and comparative examples was mixed with 200ml of deionized water to obtain a dye liquor. Pure cotton fabric (all-cotton combed poplin plain weave natural white, warp density: 110 threads / inch, weft density: 70 threads / inch, warp yarn 40 single count, weft yarn 40 single count; weight per square meter 100g, produced by Jiangsu Linya Textile Technology Co., Ltd.) was completely immersed in the dye liquor (dye liquor to cotton fabric liquor ratio of 50:1), heated to 50℃, soaked for 15min, removed, washed with 200ml of deionized water, and dried at room temperature to obtain dyed cotton fabric. The initial whiteness value of the dyed cotton fabric was measured and recorded using an ST70 spectrophotometer, and then placed in a QUV ultraviolet accelerated aging test chamber with an irradiation power of 8W / m 2 The sample was aged at 60℃ for 500 hours. After aging, it was allowed to cool naturally to room temperature and left for 5 hours before a whiteness test was performed.

[0041] Table 1 Performance Test Data

[0042] As can be seen from the data in Table 1, the highly dispersible fluorescent whitening functional additives prepared in Examples 5-7 of this application have good water dispersibility, stability and anti-aging properties.

[0043] The highly dispersible fluorescent whitening functional additive prepared in this application contains stilbene fluorescent groups, sulfonic acid groups, hydroxyl groups, polyether segments, and alkyl chains connected to them. The stilbene fluorescent groups absorb ultraviolet light and emit blue light, compensating for the yellowing of cotton fibers due to aging and making textiles appear whiter. The sulfonic acid groups provide strong hydrophilicity, ionizing in water to form sulfonate groups, generating electrostatic repulsion to prevent molecular aggregation and precipitation. The hydroxyl groups and polyether segments form hydrogen bonds with water and fibers, improving solubility and stability. The alkyl chains connected to the polyether segments form micro-regions through hydrophobic interactions, preventing excessive aggregation of the polyether chains. The synergistic effect of multiple functional groups in the fluorescent whitening agent improves its dispersibility and dispersion stability in water. The long-chain alkyl groups in the fluorescent whitening agent used in Comparative Example 1 easily aggregate in the aqueous dispersion system, affecting the dispersibility and stability of the fluorescent whitening additive in water. The polyether segments in the fluorescent whitening agent used in Comparative Example 2 are too long, encapsulating the fluorescent groups and weakening its whitening effect.

[0044] The anti-aging agent prepared in this application has a triazine ring as its core and contains multiple hindered amines. The conjugated large π bond of the triazine ring can absorb ultraviolet light and convert light energy into heat energy through electronic transitions, reducing the direct attack of ultraviolet light on fluorescent whitening agents and delaying chromophore degradation. The six hindered amines (including four hindered amines linked by the triazine ring and two hindered amines introduced by 2,2,6,6-tetramethyl-4-aminopiperidine) synergistically improve the anti-aging performance. Furthermore, this anti-aging agent has a high molecular weight and excellent migration resistance. The anti-aging agent also contains sulfonic acid groups and polyether segments. Its hydrophilicity reduces the solid-liquid interfacial tension, and its strong electrostatic repulsion inhibits aggregation. The polyether segments improve water dispersibility by forming hydrogen bonds.

[0045] The anti-aging agent added in Comparative Example 7 has relatively few hindered amine structures. Even with the same amount of hindered amines added as in the examples, its synergistic anti-aging performance is lower than that of the examples. Furthermore, its molecular weight is relatively small, making it less resistant to migration and resulting in poor anti-aging performance. The anti-aging agent used in Comparative Example 8 contains a long alkyl chain, which easily encapsulates anti-aging groups (triazine ring, hindered amine) due to hydrophobicity, thus weakening its anti-aging effect.

[0046] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A highly dispersible fluorescent whitening functional additive, characterized in that, The ingredients include the following parts by weight: 40-50 parts of fluorescent whitening agent, 10-15 parts of sodium lignosulfonate, 5-8 parts of pH buffer, 3-5 parts of anti-aging agent, and 50-70 parts of deionized water; The fluorescent whitening agent is prepared by the following method: S1: Undecenoic acid reacts with hexaethylene glycol monomethyl ether to form an ester compound. S2: Ester compounds react with hydrogen peroxide and formic acid to form epoxide compounds. S3: 4,4'-Diaminostilbene-2,2'-disulfonic acid reacts with trimellitic anhydride to form a tetracarboxylic acid compound. S4: Epoxy compounds react with tetracarboxylic acid compounds to generate fluorescent whitening agents.

2. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, In step S1, the molar ratio of undecenoic acid to hexaethylene glycol monomethyl ether is 1:(1.05-1.1).

3. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, In step S2, the molar ratio of the ester compound, hydrogen peroxide and formic acid is 1:(1.5-1.8):(1.2-1.5).

4. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, In step S3, the molar ratio of 4,4'-diaminostilbene-2,2'-disulfonic acid to trimellitic anhydride is 1:(2.1-2.2).

5. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, In step S4, the molar ratio of the epoxy compound to the tetracarboxylic compound is (4.1-4.2):

1.

6. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, The anti-aging agent is prepared by the following method: N1: Cyanurium chloride reacts with 2,2,6,6-tetramethyl-4-aminopiperidine to form a monosubstituted product. N2: The monosubstituted product reacts with 2,5-diaminobenzenesulfonic acid to form the disubstituted product. N3: The disubstituted product reacts with polyoxyethylene hexyl ether to generate an anti-aging agent.

7. The highly dispersible fluorescent whitening functional additive according to claim 6, characterized in that, In step N1, the molar ratio of cyanuric chloride to 2,2,6,6-tetramethyl-4-aminopiperidine is 1:1.05; in step N2, the molar ratio of the monosubstituted product to 2,5-diaminobenzenesulfonic acid is 2.1:1; in step N3, the molar ratio of the disubstituted product to polyoxyethylene hexyl ether is 1:2.

2.

8. The highly dispersible fluorescent whitening functional additive according to claim 1, characterized in that, The pH buffer is a mixture of citric acid and sodium citrate.

9. A method for preparing the highly dispersible fluorescent whitening functional additive according to any one of claims 1-8, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 40-50 parts of fluorescent whitening agent, 10-15 parts of sodium lignosulfonate, 5-8 parts of pH buffer, 3-5 parts of anti-aging agent, and 50-70 parts of deionized water. (2) Mix sodium lignosulfonate with deionized water, heat and stir until uniform, cool naturally to room temperature, add fluorescent whitening agent, stir, add pH buffer and anti-aging agent, shear at high speed, and sieve to obtain highly dispersible fluorescent whitening functional additive.

10. The application of a highly dispersible fluorescent whitening functional additive as described in any one of claims 1-8 in cotton fiber textiles.

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