A fabric fixing agent for reactive dye dyeing and its application

Abstract

The present invention relates to the technical field of color fixing agents, and discloses a fabric color fixing agent for reactive dyeing and its application. The present invention uses triethanolamine, epichlorohydrin, 1,4-dichloro-2-butene, etc. as raw materials, and prepares modified gemini quaternary ammonium salt through substitution reaction and quaternization reaction. Under the initiation of ammonium persulfate, acrylamide and the alkenyl contained in the modified gemini quaternary ammonium salt are used for copolymerization to prepare a fabric color fixing agent. The present invention prepares a fabric color fixing agent and applies it to dyed fabrics, which can improve the color fastness of dyes and has a good color fixing effect.

Description

Technical Field

[0001] The invention relates to the technical field of color fixing agents, in particular to a color fixing agent for fabric dyeing with reactive dyes and application thereof. Background Art

[0002] Reactive dyes are one of the most widely used dyes. They have the characteristics of bright color, complete color spectrum, good level dyeing, etc., and have been widely used in the printing and dyeing industry. However, since the dyes carry water-soluble groups such as sulfonic acid group and carboxyl group, during washing, the dyes that are not fixed on the fabric and the hydrolyzed dyes fall into the water, which not only causes the waste of dyes, but also increases the difficulty of wastewater treatment. Therefore, the dyed fabrics should also undergo color fixing treatment to meet the requirements of various color fastness for wearing and use.

[0003] Traditional color fixer Y and color fixer M are prohibited from use because they contain free formaldehyde and the N-hydroxymethyl contained in the molecules will release formaldehyde. Therefore, it is necessary to develop a new type of formaldehyde-free green color fixer.

[0004] Quaternary ammonium cationic formaldehyde-free fixing agents have strong cationic properties and can combine with anionic groups in the dye structure by ionic bonds to generate color points, making the dyed product have higher color fastness. Therefore, the research and development of this type of fixing agent is one of the hot topics for researchers. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides a fabric fixing agent for reactive dye dyeing and application thereof. The present invention prepares a modified gemini quaternary ammonium salt through substitution reaction and quaternization reaction, and then applies the modified gemini quaternary ammonium salt to reactive dyes to improve the color fastness of the dyes.

[0007] (II) Technical solution

[0008] A fabric fixing agent for reactive dye dyeing, the preparation method of the fabric fixing agent is:

[0009] (1) Add triethanolamine and potassium hydroxide to dimethyl sulfoxide solvent, stir and disperse, then add epichlorohydrin, react at 180-190° C. for 12-24 hours. After the reaction is completed, filter, wash with dichloromethane, and distill under reduced pressure to obtain intermediate 1.

[0010] (2) Add the intermediate 1, 1,4-dichloro-2-butene to acetonitrile solvent, stir and disperse, react at 55-65° C. for 12-24 hours, filter after the reaction, wash with ethanol, and dry to obtain a modified gemini quaternary ammonium salt.

[0011] (3) Under nitrogen conditions, acrylamide and modified gemini quaternary ammonium salt are added to deionized water, stirred and dispersed, heated to 60-80° C., ammonium persulfate is added thereto, and stirred to react for 5-10 hours to obtain a fabric fixing agent.

[0012] Furthermore, in the step (1), the mass ratio of triethanolamine, potassium hydroxide and epichlorohydrin is 1:0.5-0.8:1.8-3.

[0013] Furthermore, in the step (2), the mass ratio of the intermediate 1 to 1,4-dichloro-2-butene is 5-6.5:1.

[0014] Furthermore, in the step (3), the mass ratio of acrylamide to modified gemini quaternary ammonium salt is 1:1-5.

[0015] Furthermore, in the step (4), the mass fraction of ammonium persulfate is 0.5-2%.

[0016] Furthermore, at a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 5-7, the reactive dye-dyed fabric is added to the fabric fixing agent, and double dipping and double rolling are performed, wherein the rolling rate is 75-90%, and the fabric is pre-baked at 45° C. for 5 minutes and baked at 120° C. for 3 minutes to obtain the fixed reactive dye.

[0017] (III) Beneficial technical effects

[0018] The invention uses triethanolamine, epichlorohydrin, 1,4-dichloro-2-butene and the like as raw materials, and prepares a modified gemini quaternary ammonium salt through substitution reaction and quaternization reaction. Under the initiation of ammonium persulfate, acrylamide and the alkenyl contained in the modified gemini quaternary ammonium salt are copolymerized to prepare a fabric color fixing agent.

[0019] The present invention applies the prepared fabric color fixing agent to reactive dyes, wherein the quaternary ammonium salt contained therein is a cationic group, which can be ionically bonded with the anionic group in the structure of the anionic dye, so that the dye and the color fixing agent form an insoluble color lake that is deposited on the fabric fiber, reducing the water solubility, thereby improving the color fastness of the dye; wherein it contains a large number of epoxy groups, which can covalently crosslink with the fiber and the active groups in the reactive dye, such as hydroxyl, amino, etc., to improve the color fastness of the dye. In addition, the amino group contained in the fabric color fixing agent prepared by the present invention using acrylamide as a raw material can also form hydrogen bonds with the fiber and the hydroxyl and amino groups contained in the reactive dye. The fabric color fixing agent prepared by the present invention is a high molecular polymer, which can fix the colorant on the fiber surface while crosslinking with the fiber, making it difficult to fall off, further improving the color fastness of the dye.

[0020] The fabric color fixing agent prepared by the invention has the characteristics of novel structure and simple preparation method. The fabric color fixing agent prepared by the invention is applied to dyed fabrics to improve the color fastness of dyes and has a better color fixing effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a preparation route for modified gemini quaternary ammonium salts. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0023] The preparation method of reactive dye dyed fabric is as follows: pure cotton fabric is added into 3% reactive scarlet R-3G, dyed for 15 minutes, then 40g / L sodium chloride is added thereto for dyeing for 15 minutes, the temperature is increased to 70°C at a heating rate of 2°C, 10g / L sodium carbonate is added thereto for color fixation for 30 minutes, wherein the bath ratio is 1:40, after the completion, the fabric is washed with water, soaped, washed with water, and dried to obtain the reactive dye dyed fabric.

[0024] Example 1

[0025] (1) 10 g of triethanolamine and 5 g of potassium hydroxide were added to a dimethyl sulfoxide solvent, stirred and dispersed, and then 20 g of epichlorohydrin was added thereto. The mixture was reacted at 190° C. for 24 h. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and distilled under reduced pressure to obtain an intermediate 1.

[0026] (2) 45 g of the intermediate 1 and 8 g of 1,4-dichloro-2-butene were added to an acetonitrile solvent, stirred and dispersed, and reacted at 60° C. for 24 h. After the reaction was completed, the mixture was filtered, washed with ethanol, and dried to obtain a modified gemini quaternary ammonium salt.

[0027] (3) Under nitrogen conditions, 15 g of acrylamide and 15 g of modified gemini quaternary ammonium salt were added to deionized water, stirred and dispersed, and the temperature was raised to 75° C., and 1.5% by mass of ammonium persulfate was added thereto, and the reaction was stirred for 6 h to obtain a fabric fixing agent.

[0028] (4) At a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 5, and the reactive dye-dyed fabric is added to the fabric fixing agent for double immersion and double padding, wherein the padding ratio is 75%, and the fabric is pre-baked at 45° C. for 5 min and baked at 120° C. for 3 min to obtain the reactive dye after fixation.

[0029] Example 2

[0030] (1) 10 g of triethanolamine and 8 g of potassium hydroxide were added to a dimethyl sulfoxide solvent, stirred and dispersed, and then 18 g of epichlorohydrin was added thereto. The mixture was reacted at 190° C. for 12 h. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and distilled under reduced pressure to obtain an intermediate 1.

[0031] (2) 50 g of the intermediate 1 and 8 g of 1,4-dichloro-2-butene were added to an acetonitrile solvent, stirred and dispersed, and reacted at 60° C. for 12 h. After the reaction was completed, the mixture was filtered, washed with ethanol, and dried to obtain a modified gemini quaternary ammonium salt.

[0032] (3) Under nitrogen conditions, 15 g of acrylamide and 30 g of modified gemini quaternary ammonium salt were added to deionized water, stirred and dispersed, and the temperature was raised to 70° C., and 1% by mass of ammonium persulfate was added thereto, and the reaction was stirred for 8 h to obtain a fabric fixing agent.

[0033] (4) At a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 6, and the reactive dye-dyed fabric is added to the fabric fixing agent for double dipping and double padding, wherein the padding ratio is 80%, and the fabric is pre-baked at 45° C. for 5 min and baked at 120° C. for 3 min to obtain the reactive dye after fixation.

[0034] Example 3

[0035] (1) 10 g of triethanolamine and 7 g of potassium hydroxide were added to a dimethyl sulfoxide solvent, stirred and dispersed, and then 20 g of epichlorohydrin was added thereto. The mixture was reacted at 185° C. for 20 h. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and distilled under reduced pressure to obtain an intermediate 1.

[0036] (2) 50 g of the intermediate 1 and 8 g of 1,4-dichloro-2-butene were added to an acetonitrile solvent, stirred and dispersed, and reacted at 55° C. for 24 h. After the reaction was completed, the mixture was filtered, washed with ethanol, and dried to obtain a modified gemini quaternary ammonium salt.

[0037] (3) Under nitrogen conditions, 15 g of acrylamide and 45 g of modified gemini quaternary ammonium salt were added to deionized water, stirred and dispersed, and the temperature was raised to 80° C., and 0.5% by mass of ammonium persulfate was added thereto, and the mixture was stirred and reacted for 6 h to obtain a fabric fixing agent.

[0038] (4) At a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 7, and the reactive dye-dyed fabric is added to the fabric fixing agent for double dipping and double padding, wherein the padding ratio is 80%, and the fabric is pre-baked at 45° C. for 5 min and baked at 120° C. for 3 min to obtain the reactive dye after fixation.

[0039] Example 4

[0040] (1) 10 g of triethanolamine and 6 g of potassium hydroxide were added to a dimethyl sulfoxide solvent, stirred and dispersed, and then 30 g of epichlorohydrin was added thereto. The mixture was reacted at 180° C. for 20 h. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and distilled under reduced pressure to obtain an intermediate 1.

[0041] (2) 40 g of the intermediate 1 and 8 g of 1,4-dichloro-2-butene were added to an acetonitrile solvent, stirred and dispersed, and reacted at 60° C. for 12 h. After the reaction was completed, the mixture was filtered, washed with ethanol, and dried to obtain a modified gemini quaternary ammonium salt.

[0042] (3) Under nitrogen conditions, 15 g of acrylamide and 60 g of modified gemini quaternary ammonium salt were added to deionized water, stirred and dispersed, and the temperature was raised to 65° C., and 2% by mass of ammonium persulfate was added thereto, and the reaction was stirred for 10 h to obtain a fabric fixing agent.

[0043] (4) At a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 7, and the reactive dye-dyed fabric is added to the fabric fixing agent for double dipping and double padding, wherein the padding ratio is 90%, and the fabric is pre-baked at 45° C. for 5 min and baked at 120° C. for 3 min to obtain the reactive dye after fixation.

[0044] Example 5

[0045] (1) 10 g of triethanolamine and 7 g of potassium hydroxide were added to a dimethyl sulfoxide solvent, stirred and dispersed, and then 25 g of epichlorohydrin was added thereto. The mixture was reacted at 190° C. for 24 h. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and distilled under reduced pressure to obtain an intermediate 1.

[0046] (2) 52 g of the intermediate 1 and 8 g of 1,4-dichloro-2-butene were added to an acetonitrile solvent, stirred and dispersed, and reacted at 65° C. for 24 h. After the reaction was completed, the mixture was filtered, washed with ethanol, and dried to obtain a modified gemini quaternary ammonium salt.

[0047] (3) Under nitrogen conditions, 15 g of acrylamide and 75 g of modified gemini quaternary ammonium salt were added to deionized water, stirred and dispersed, and the temperature was raised to 60° C., 1% by mass of ammonium persulfate was added thereto, and the reaction was stirred for 5 h to obtain a fabric fixing agent.

[0048] (4) At a bath ratio of 1:30, the pH of the fabric fixing solution is controlled to be 6, and the reactive dye-dyed fabric is added to the fabric fixing agent for double dipping and double padding, wherein the padding ratio is 90%, and the fabric is pre-baked at 45° C. for 5 min and baked at 120° C. for 3 min to obtain the reactive dye after fixation.

[0049] Comparative Example 1

[0050] The difference between this comparative example and Example 1 is that in step (4), a modified gemini quaternary ammonium salt is used instead of the fabric fixing agent.

[0051] Comparative Example 2

[0052] The difference between this comparative example and Example 1 is that in step (4), acrylamide is used instead of the fabric fixing agent.

[0053] Refer to GB / T3920-2008 and use a friction color fastness tester to test the color fastness of materials to dry and wet friction. According to GB / T250-2008, rate the color change.

[0054] Refer to GB / T3921-2008 and use a wash fastness tester to test the color fastness of materials to soap washing. According to GB / T250-2008, rate the color change.

[0055] Table 1: Color fastness test of various embodiments and comparative examples

[0056]

[0057]

[0058] As can be seen from the table, in Examples 1-5, as the amount of fabric color fixing agent used increases, the color fastness of the dyed fabric is continuously improved. The color fastness results in the examples are better than those in the comparative examples, because all of the examples 1-5 contain modified gemini quaternary ammonium salt structures and acrylamide structures, while the comparative example 1 contains only modified gemini quaternary ammonium salts, and the comparative example 2 contains only acrylamide. Therefore, its color fastness is poorer than that of the examples.

[0059] 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.

Claims

1. A fabric fixing agent for reactive dyeing, characterized in that: The preparation method of the fabric fixing agent is: (1) Add triethanolamine and potassium hydroxide to dimethyl sulfoxide solvent, stir and disperse, then add epichlorohydrin, react at 180-190°C for 12-24 hours. After the reaction is completed, filter, wash with dichloromethane, and distill under reduced pressure to obtain intermediate 1; (2) adding the intermediate 1, 1,4-dichloro-2-butene to acetonitrile solvent, stirring and dispersing, reacting at 55-65°C for 12-24 hours, filtering after the reaction, washing with ethanol, and drying to obtain a modified gemini quaternary ammonium salt; (3) Under nitrogen conditions, acrylamide and modified gemini quaternary ammonium salt are added to deionized water, stirred and dispersed, and the temperature is raised to 60-80°C. Ammonium persulfate is added thereto, and the reaction is stirred for 5-10 hours to obtain a fabric fixing agent.

2. The fabric fixing agent for reactive dyeing according to claim 1, characterized in that: In the step (1), the mass ratio of triethanolamine, potassium hydroxide and epichlorohydrin is 1:0.5-0.8:1.8-3.

3. The fabric fixing agent for reactive dyeing according to claim 1, characterized in that: In the step (2), the mass ratio of the intermediate 1 to 1,4-dichloro-2-butene is 5-6.5:

1.

4. The fabric fixing agent for reactive dyeing according to claim 1, characterized in that: In the step (3), the mass ratio of acrylamide to modified gemini quaternary ammonium salt is 1:1-5.

5. The fabric fixing agent for reactive dyeing according to claim 1, characterized in that: In the step (3), the mass fraction of ammonium persulfate is 0.5-2%.

6. Use of the fabric fixing agent for reactive dyeing according to any one of claims 1 to 5 in reactive dyeing: at a bath ratio of 1:30, the pH of the fabric fixing agent is controlled to be 5-7, a fabric dyed with reactive dye is added to the fabric fixing agent, and double dipping and double padding is performed, wherein: The rolling rate is 75-90%, and the fabric is pre-dried at 45°C for 5 minutes and baked at 120°C for 3 minutes to obtain a fabric dyed with reactive dyes after fixation.

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