Preparation method of multifunctional quaternary ammonium salt color fixing agent for textiles

Abstract

The invention relates to the technical field of color fixing agents, and discloses a preparation method of a multifunctional quaternary ammonium salt color fixing agent for textiles, 3, 3 '-imine dipropionitrile, chloropropene, 2, 4-dihydroxybenzophenone, 1, 4-dichloro-2-butene and the like are used as raw materials, a bis-benzophenone gemini quaternary ammonium salt intermediate is prepared through a series of reactions, the preparation method is simple, the cost is low, and the multifunctional quaternary ammonium salt color fixing agent is suitable for industrial production. The multifunctional quaternary ammonium salt color fixing agent for the textile is novel in structure and good in symmetry, the multifunctional quaternary ammonium salt color fixing agent for the textile is obtained under initiation copolymerization of ammonium persulfate, the multifunctional quaternary ammonium salt color fixing agent contains carboxyl and a quaternary ammonium salt structure, and the carboxyl and the quaternary ammonium salt structure can generate hydrogen bonds with the textile and dye to form a cross-linked network structure, so that the color fixing performance of the textile on the dye is improved; as the color fixing agent contains a benzophenone structure, the ultraviolet resistance of the color fixing agent can be improved by introducing the benzophenone structure into the quaternary ammonium salt color fixing agent. The prepared multifunctional quaternary ammonium salt color fixing agent for the textile has good anti-ultraviolet capacity and color fixing performance.

Description

Technical Field

[0001] The invention relates to the technical field of color fixing agents, in particular to a method for preparing a multifunctional quaternary ammonium salt color fixing agent for textiles. Background Art

[0002] When fabrics are dyed with medium and dark colors using reactive dyes, excessive floating color may occur due to the high concentration of reactive dyes, resulting in unqualified color fastness. At this time, a fixing agent is needed to improve the color fastness of the dyed fabrics. At the same time, with the increase in ultraviolet radiation, it has serious harm and impact on human life. Therefore, studying a fixing agent that can absorb ultraviolet rays and has good color fixing performance is one of the research hotspots.

[0003] Quaternary ammonium cationic fixing agents have strong cationicity and can combine with the anionic groups in the dye structure by ionic bonds to form color lakes. As a result, the dyed material can obtain higher soap fastness and wet rubbing fastness. Benzophenone ultraviolet absorbers are low in price and have good ultraviolet absorption performance. They are widely used in coatings, fabrics and other fields.

[0004] For example, the patent with application publication number CN 111254728 A discloses a sun-resistant and UV-proof color fixing agent and a preparation method. The invention uses cyanuric chloride, 2-hydroxypropyltrimethylammonium chloride chitosan, etc. as raw materials, and the prepared color fixing agent has good UV resistance, light fastness, washing resistance, etc. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present invention provides a method for preparing a multifunctional quaternary ammonium salt color fixing agent for textiles. The prepared color fixing agent has good anti-ultraviolet performance and color fixing performance.

[0006] A method for preparing a multifunctional quaternary ammonium salt color fixing agent for textiles, the preparation method is as follows:

[0007] Step (1), under nitrogen conditions, add 3,3'-imidodipropionitrile and allyl chloride to ethanol solvent, stir and disperse, stir and react at 30-40°C for 3-6 hours, and after the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0008] Step (2), under nitrogen, add 2,4-dihydroxybenzophenone to a 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add intermediate 1 thereto, react at 80-90° C. for 3-5 hours, after the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2;

[0009] Step (3), adding intermediate 2 to ethanol solvent, stirring and dispersing, then adding 1,4-dichloro-2-butene thereto, reacting at 90-110° C. for 20-48 hours, and after the reaction is completed, distilling under reduced pressure, recrystallizing, and drying to obtain intermediate 3.

[0010] Step (4), adding intermediate 3 and potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 100-120° C. for 12-24 hours, cooling to room temperature after the reaction, adding deionized water and hydrochloric acid, adjusting the pH to 1-2, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate.

[0011] Step (5), adding the dibenzophenone gemini quaternary ammonium salt intermediate and ammonium persulfate to deionized water, reacting at 40-50° C. for 2-4 hours, heating to 55-65° C. for 1-2 hours, and further heating to 70-75° C. for 1-2 hours. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

[0012] Preferably, in step (1), the molar ratio of 3,3'-imidodipropionitrile to allyl chloride is 1:1-1.5.

[0013] Preferably, in step (2), the molar ratio of 2,4-dihydroxybenzophenone to intermediate 1 is 1-1.5:1.

[0014] Preferably, in step (3), the molar ratio of the intermediate 2 to 1,4-dichloro-2-butene is 2-2.5:1.

[0015] Preferably, in step (4), the concentration of hydrochloric acid is 30%.

[0016] Preferably, in step (4), the molar ratio of intermediate 3 to potassium hydroxide is 1:10-15.

[0017] Preferably, in step (4), the amount of ammonium persulfate used is 4-9% of the mass of the bis(benzophenone) gemini quaternary ammonium salt intermediate.

[0018] (III) Beneficial technical effects

[0019] The invention uses 3,3'-iminodipropionitrile, allyl chloride, 2,4-dihydroxybenzophenone, 1,4-dichloro-2-butene and the like as raw materials, and prepares a bisbenzophenone gemini quaternary ammonium salt intermediate through a series of reactions. The preparation method is simple, the structure is novel, and the intermediate has good symmetry. Under the initiation copolymerization of ammonium persulfate, a multifunctional quaternary ammonium salt color fixing agent for textiles is obtained.

[0020] The carboxyl group and the quaternary ammonium salt group contained in the quaternary ammonium salt color fixing agent prepared by the present invention can both generate hydrogen bonds with the hydroxyl group in the fabric fiber and the active group of the active dye, play a "bridging" role, and thus form a highly three-dimensional stereo cross-linking system, so that the fabric fiber and the dye are more firmly combined through the cross-linking effect, and the dye is prevented from falling off the fiber to cause the phenomenon of fading, thereby increasing the color fastness of the dye. In addition, the color fixing agent molecular chain prepared by the present invention contains a large number of reactive groups, and after reacting with the fabric, a three-dimensional network structure is formed on the fiber surface of the fabric, and the dye is enclosed therein, thereby further increasing the color fastness.

[0021] In addition, the benzophenone structure contained in the quaternary ammonium salt color fixing agent prepared by the present invention has good ultraviolet resistance. When the benzophenone structure is introduced into the color fixing agent, the color fixing agent exhibits a good absorption effect on ultraviolet rays. When the benzophenone structure is applied to fabrics, the ultraviolet resistance of the fabrics can be improved. The multifunctional quaternary ammonium salt color fixing agent for textiles prepared by the present invention has good ultraviolet resistance and color fixing performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a reaction route for the intermediate of bis(benzophenone) gemini quaternary ammonium salt. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0024] Example 1

[0025] Step (1), under nitrogen conditions, add 0.1 mol of 3,3'-imidodipropionitrile and 0.1 mol of allyl chloride to ethanol solvent, stir and disperse, and react at 35°C for 4 hours. After the reaction is completed, evaporate under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0026] Step (2), under nitrogen conditions, add 25 mmol of 2,4-dihydroxybenzophenone to 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add 20 mmol of intermediate 1 thereto, react at 90° C. for 5 h, after the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2.

[0027] Step (3), add 80 mmol of intermediate 2 to ethanol solvent, stir and disperse, then add 40 mmol of 1,4-dichloro-2-butene thereto, react at 110° C. for 24 h, and after the reaction is completed, perform vacuum distillation, recrystallize, and dry to obtain intermediate 3.

[0028] Step (4), adding 20 mmol of intermediate 3 and 300 mmol of potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 110° C. for 18 h, cooling to room temperature after the reaction, adding deionized water and 30% hydrochloric acid, adjusting the pH to 2, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate, and testing the product purity by high performance liquid chromatography, the purity is 76.2%.

[0029] Step (5), adding 20 mmol of the dibenzophenone gemini quaternary ammonium salt intermediate and 1 g of ammonium persulfate to deionized water, reacting at 45° C. for 4 h, heating to 65° C. for 2 h, and further heating to 75° C. for 2 h. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

[0030] Example 2

[0031] Step (1), under nitrogen conditions, add 0.1 mol of 3,3'-imidodipropionitrile and 0.12 mol of allyl chloride to ethanol solvent, stir and disperse, and react at 40° C. for 6 hours. After the reaction is completed, evaporate under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0032] Step (2), under nitrogen conditions, add 20 mmol of 2,4-dihydroxybenzophenone to 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add 20 mmol of intermediate 1 thereto, react at 85° C. for 4 h, after the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2.

[0033] Step (3), add 90 mmol of intermediate 2 to ethanol solvent, stir and disperse, then add 40 mmol of 1,4-dichloro-2-butene thereto, react at 95° C. for 48 hours, and after the reaction is completed, perform vacuum distillation, recrystallize, and dry to obtain intermediate 3.

[0034] Step (4), adding 20 mmol of intermediate 3 and 200 mmol of potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 100° C. for 16 h, cooling to room temperature after the reaction, adding deionized water and 30% hydrochloric acid, adjusting the pH to 1, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate, and testing the product purity by high performance liquid chromatography, the purity is 75.2%.

[0035] Step (5), adding 20 mmol of the dibenzophenone gemini quaternary ammonium salt intermediate and 1.5 g of ammonium persulfate to deionized water, reacting at 40° C. for 3 h, heating to 55° C. for 1 h, and further heating to 70° C. for 1 h. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

[0036] Example 3

[0037] Step (1), under nitrogen conditions, add 0.1 mol of 3,3'-imidodipropionitrile and 0.15 mol of allyl chloride to ethanol solvent, stir and disperse, and react at 30° C. for 3 h. After the reaction is completed, evaporate under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0038] Step (2), under nitrogen conditions, add 25 mmol of 2,4-dihydroxybenzophenone to 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add 20 mmol of intermediate 1 thereto, react at 90° C. for 3 h, after the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2.

[0039] Step (3), add 100 mmol of intermediate 2 to ethanol solvent, stir and disperse, then add 40 mmol of 1,4-dichloro-2-butene thereto, react at 90° C. for 20 h, and after the reaction is completed, perform vacuum distillation, recrystallize, and dry to obtain intermediate 3.

[0040] Step (4), adding 20 mmol of intermediate 3 and 240 mmol of potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 120° C. for 12 h, cooling to room temperature after the reaction, adding deionized water and 30% hydrochloric acid, adjusting the pH to 1, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate, and testing the product purity by high performance liquid chromatography, the purity is 79.0%.

[0041] Step (5), adding 20 mmol of the dibenzophenone gemini quaternary ammonium salt intermediate and 0.7 g of ammonium persulfate to deionized water, reacting at 50° C. for 2 h, heating to 55° C. for 2 h, and further heating to 75° C. for 2 h. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

[0042] Example 4

[0043] Step (1), under nitrogen conditions, add 0.1 mol of 3,3'-imidodipropionitrile and 0.12 mol of allyl chloride to ethanol solvent, stir and disperse, and react at 35°C for 5 hours. After the reaction is completed, evaporate under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0044] Step (2), under nitrogen conditions, add 30 mmol of 2,4-dihydroxybenzophenone to 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add 20 mmol of intermediate 1 thereto, react at 80° C. for 5 h. After the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2.

[0045] Step (3), add 90 mmol of intermediate 2 to ethanol solvent, stir and disperse, then add 40 mmol of 1,4-dichloro-2-butene thereto, react at 100° C. for 36 hours, and after the reaction is completed, perform vacuum distillation, recrystallize, and dry to obtain intermediate 3.

[0046] Step (4), adding 20 mmol of intermediate 3 and 300 mmol of potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 110° C. for 24 h, cooling to room temperature after the reaction, adding deionized water and 30% hydrochloric acid, adjusting the pH to 2, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate, and testing the product purity by high performance liquid chromatography, the purity is 78.2%.

[0047] Step (5), adding 20 mmol of the dibenzophenone gemini quaternary ammonium salt intermediate and 1.2 g of ammonium persulfate to deionized water, reacting at 45° C. for 3 h, heating to 60° C. for 2 h, and further heating to 75° C. for 2 h. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

[0048] Prepare 2g / L reactive blue B-3BF, control the bath ratio to 1:40, add pure cotton fabric into the dye bath at 30°C, gradually heat to 60°C at a rate of 1°C / min, keep warm and dye for 30min, then add 2% multifunctional quaternary ammonium salt fixing agent for textiles, fix the color at 60°C for 30min, take out the fabric after fixing, wash with water, boil with soap and dry to obtain the fixed fabric.

[0049] Refer to GB / T3920-1997 to test the abrasion resistance.

[0050] Refer to GB / T3921-1997 to test the color fastness to washing.

[0051] The K / S value of dyed fabrics was determined using Datacolor-DF100 colorimeter.

[0052] Table 1: Color fixation performance test results

[0053] Wet rubbing fastness / grade Dry rubbing fastness / grade Soap fastness / grade K / S value Example 1 3 4 2-3 24.31 Example 2 3-4 4-5 3 25.10 Example 3 4 4 3 24.98 Example 4 3-4 4-5 2-3 24.57 Comparative Example 1 2 2 2 12.30

[0054] Comparative Example 1 is a dyed fabric without a dye fixing agent.

[0055] It can be seen from the table that the multifunctional quaternary ammonium salt color fixing agent for textiles prepared by the present invention has good color fixing performance.

[0056] Use a fabric UV tester to test the UV transmittance of fabrics.

[0057] Table 2: Fabric UV transmittance results

[0058] 360nm UV transmittance / % Example 1 9.82 Example 2 9.17 Example 3 9.06 Example 4 9.48 Comparative Example 1 36.04

[0059] Comparative Example 1 is a dyed fabric without a dye fixing agent.

[0060] It can be seen from the table that the multifunctional quaternary ammonium salt color fixing agent for textiles prepared by the present invention has good anti-ultraviolet performance.

[0061] Those skilled in the art will appreciate that the embodiments described herein are intended to help readers understand the implementation methods of the present invention, and should be understood that the protection scope of the present invention is not limited to such special statements and embodiments. Those skilled in the art can make various other specific variations and combinations that do not deviate from the essence of the present invention based on the technical revelations disclosed by the present invention, and these variations and combinations are still within the protection scope of the present invention.

Claims

1. A method for preparing a multifunctional quaternary ammonium salt color fixing agent for textiles, characterized in that: The preparation method is as follows: Step (1), under nitrogen conditions, 3,3'-imidodipropionitrile and allyl chloride are added to an ethanol solvent, stirred and dispersed, stirred and reacted at 30-40° C. for 3-6 hours, and after the reaction is completed, vacuum distillation is performed, the mixture is washed with deionized water, and dried to obtain an intermediate 1; Step (2), under nitrogen, add 2,4-dihydroxybenzophenone to a 2 mol / L sodium hydroxide aqueous solution, stir to dissolve, then add intermediate 1 thereto, react at 80-90° C. for 3-5 hours, after the reaction is completed, wash with deionized water, dry, distill under reduced pressure, recrystallize, and dry to obtain intermediate 2; Step (3), adding intermediate 2 to ethanol solvent, stirring and dispersing, then adding 1,4-dichloro-2-butene thereto, reacting at 90-110° C. for 20-48 hours, and after the reaction is completed, distilling under reduced pressure, recrystallizing, and drying to obtain intermediate 3; Step (4), adding intermediate 3 and potassium hydroxide to an ethanol solvent, stirring and dispersing, reacting at 100-120° C. for 12-24 hours, cooling to room temperature after the reaction, adding deionized water and hydrochloric acid thereto, adjusting the pH to 1-2, washing with deionized water, and drying to obtain a dibenzophenone gemini quaternary ammonium salt intermediate; Step (5), adding the dibenzophenone gemini quaternary ammonium salt intermediate and ammonium persulfate to deionized water, reacting at 40-50° C. for 2-4 hours, heating to 55-65° C. for 1-2 hours, and further heating to 70-75° C. for 1-2 hours. After the reaction is completed, drying is performed to obtain a multifunctional quaternary ammonium salt color fixing agent for textiles.

2. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (1), the molar ratio of 3,3'-imidodipropionitrile to allyl chloride is 1:1-1.

5.

3. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (2), the molar ratio of 2,4-dihydroxybenzophenone to intermediate 1 is 1-1.5:

1.

4. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (3), the molar ratio of the intermediate 2 to 1,4-dichloro-2-butene is 2-2.5:

1.

5. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (4), the concentration of hydrochloric acid is 30%.

6. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (4), the molar ratio of the intermediate 3 to potassium hydroxide is 1:10-15.

7. The method for preparing the multifunctional quaternary ammonium salt color fixing agent for textiles according to claim 1, characterized in that: In the step (4), the amount of ammonium persulfate used is 4-9% of the mass of the dibenzophenone gemini quaternary ammonium salt intermediate.

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