Special dual-activity modifier for fibers and fabrics thereof and preparation method of special dual-activity modifier

Abstract

The invention relates to the field of textile printing and dyeing auxiliaries, in particular to a special double-activity modifier for fibers and fabrics thereof and a preparation method of the special double-activity modifier, and the special double-activity modifier comprises the following raw materials in parts by weight: 8-10 parts of a modified active agent, 4-5 parts of composite titanium oxide, 0.8-1 part of a printing and dyeing improver and 30-40 parts of water; by preparing the modified active agent and combining the modified active agent with the composite titanium oxide, the double-active modifier is formed, and the problems that the rubbing fastness, the scrubbing fastness, the dye uptake during dyeing and the fixation rate of fibers and fabrics thereof modified by an existing active modifier are insufficient are solved.

Description

Technical Field

[0001] The invention relates to the field of textile printing and dyeing auxiliaries, and in particular to a special dual-active modifier for fibers and fabrics thereof and a preparation method thereof. Background Art

[0002] Cotton fibers and fabrics are mainly dyed with reactive dyes. However, a large amount of electrolytes need to be added to promote dyeing when reactive dyes are used, which will result in a large amount of alkali solution waste. At the same time, the dye uptake rate and the dye fixation rate cannot meet the demand. Therefore, in pursuit of better dyeing effects, the fibers and fabrics need to be modified. Currently, active modifiers are usually used to modify cotton fibers or fabrics to make them carry positive charges or active groups to increase their affinity with reactive dyes, thereby achieving the purpose of salt-free or low-salt dyeing. However, the commonly used cationic active modifiers still have problems with rubbing fastness, washing fastness, and insufficient dye uptake and fixation rates during dyeing, and cannot meet the increasing market requirements. Summary of the invention

[0003] The purpose of the present invention is to provide a special dual-active modifier for fibers and fabrics and a preparation method thereof. By preparing a modified active agent and combining it with composite titanium oxide to form a dual-active modifier, the problems of friction fastness, washing fastness, and insufficient dye uptake and fixation rate of fibers and fabrics modified by existing active modifiers are solved.

[0004] The object of the present invention can be achieved by the following technical scheme: a preparation method of a special dual-active modifier for fiber and its fabric, which comprises the following steps: weighing the following raw materials by weight: 3-4 parts of cationic modifier, 8-10 parts of modified active agent, 4-5 parts of composite titanium oxide, 0.8-1 part of printing and dyeing enhancer and 30-40 parts of water, mixing the modified active agent, composite titanium oxide, printing and dyeing enhancer and water to prepare a special dual-active modifier for fiber and its fabric; The modified active agent is prepared by the following steps: Step A1: 3-aminophenylboronic acid, anhydrous sodium acetate and acetic acid are mixed, stirred at a stirring rate of 120-140 rpm and a temperature of 30° C., cyanuric chloride is added, and the reaction is carried out for 3-4 hours to obtain intermediate 1; N-methyl-2,2-diaminodiethylamine and acetone are mixed, stirred at a stirring rate of 60-80 rpm and a temperature of 120° C., intermediate 1 is added, and the reaction is carried out for 3-4 hours to obtain intermediate 2; The ratio of 3-aminophenylboric acid, anhydrous sodium acetate and cyanuric chloride is 0.02-0.022 mol: 4.5-5 g: 0.04-0.044 mol; the ratio of N-methyl-2,2-diaminodiethylamine and intermediate 1 is 0.01-0.011 mol: 0.02-0.022 mol; During the reaction, the reaction temperature was controlled at 30°C, and the chlorine in cyanuric chloride reacted with the amino group in 3-aminophenylboronic acid to obtain intermediate 1. Then, at 120°C, the unreacted chlorine in the cyanuric chloride structure of intermediate 1 reacted with the amino groups at both ends of N-methyl-2,2-diaminodiethylamine to obtain intermediate 2. Step A2: Mix the intermediate 2, the diamine intermediate, 1,3-dibromopropane, isopropanol and acetone, and react for 12 hours at a stirring rate of 120-140 rpm and a temperature of 60° C., then cool to 50° C., stir and add hydrochloric acid solution and epichlorohydrin, and react for 3-4 hours to obtain a modified active agent; The mass fraction of the hydrochloric acid solution is 20%, and the amount ratio of intermediate 2, diamine intermediate, 1,3-dibromopropane, isopropanol, hydrochloric acid solution and epichlorohydrin is 0.012-0.014 mol: 0.006-0.007 mol: 0.06-0.07 mol: 6-8 mL: 2-3 mL: 0.07-0.08 mol; The diamine intermediate is one of tetramethylpropylenediamine and bis(dimethylamino)ethyl ether; During the reaction, under the action of isopropanol, bromine in 1,3-dibromopropane reacts with intermediate 2 and tertiary amine in diamine intermediate to form a quaternary ammonium structure, which is then connected. Then, under acidic conditions, epichlorohydrin is added to react with the secondary amine or tertiary amine group therein, thereby introducing an epoxy group to obtain a modified active agent. The composite titanium oxide is prepared by the following steps: Step B1: Tetrabutyl titanate, glacial acetic acid, deionized water and anhydrous ethanol are mixed, stirred at a stirring rate of 80-100 rpm, and cerium nitrate hexahydrate is added at room temperature, stirred for 10-15 minutes, and then a nitric acid solution is added to adjust the pH value to 3, and heated to 60°C, and the reaction is continued for 3-4 hours, dried, ground, and calcined at 800°C for 3-4 hours to obtain hybrid titanium oxide; The mass fraction of nitric acid solution is 30%, and the dosage ratio of tetrabutyl titanate, glacial acetic acid and cerium nitrate hexahydrate is 10-12mL: 5-6mL: 0.08-0.09g; During the reaction, cerium-doped hybrid titanium oxide was prepared by sol-gel method using tetrabutyl titanate as titanium source. Step B2: benzaldehyde, 5-nitrosalicylicaldehyde and propionic acid are mixed, stirred at a stirring speed of 120-140 rpm and a temperature of 135°C, pyrrole is added, the reaction is carried out for 3 hours, the temperature is cooled to room temperature, and the reaction is continued for 12 hours to obtain intermediate a; intermediate a, sodium hydroxide, methanol and deionized water are mixed, stirred at a stirring speed of 60-80 rpm and a temperature of 60°C, 1,4-butanesulfonic acid lactone is added, and the reaction is carried out for 4-6 hours to obtain intermediate b; The dosage ratio of benzaldehyde, 5-nitrosalicylicylaldehyde, propionic acid and pyrrole is 0.07-0.075 mol: 0.05-0.055 mol: 120-140 mL: 0.12-0.13 mol; the dosage ratio of intermediate a, sodium hydroxide and 1,4-butanesulfonic acid lactone is 0.03-0.032 mol: 7-8 g: 0.6-0.07 mol; During the reaction, benzaldehyde and 5-nitrosalicylic aldehyde are used as monomers to synthesize an intermediate a having a porphyrin structure through the propionic acid method, and then 1,4-butane sultone is ring-opened under alkaline conditions and reacts with the hydroxyl group in the intermediate a to introduce a sulfonic acid group to obtain an intermediate b. Step B3: Mix the intermediate b and the hydrochloric acid solution, stir and add stannous chloride dihydrate and deionized water under nitrogen protection, stirring at a rate of 60-80 rpm and a temperature of 80°C, and react for 30-40 minutes to obtain the intermediate c, mix the hybrid titanium oxide and 1,4-dioxane and ultrasonically disperse for 10-15 minutes, stir and add the intermediate c at a temperature of 80°C and a stirring rate of 120-140 rpm, and react for 2-3 hours to obtain the composite titanium oxide; The mass fraction of the hydrochloric acid solution is 35%, the dosage ratio of the intermediate b, the hydrochloric acid solution and the stannous chloride is 0.02-0.024 mol: 100-110 mL: 0.04-0.05 mol; the dosage ratio of the hybrid titanium oxide and the intermediate c is 2-2.3 g: 0.008-0.01 mol; During the reaction, under the action of stannous chloride, the nitro group in intermediate b is hydrogenated and reduced to amino group to obtain intermediate c. Since intermediate c contains sulfonic acid group, it combines with the surface hydroxyl group of hybrid titanium oxide to obtain composite titanium oxide. Beneficial effects of the invention: The invention discloses a special dual-active modifier for fibers and fabrics and a preparation method thereof. The dual-active modifier is formed by preparing a modified active agent and combining it with composite titanium oxide, thereby solving the problems of insufficient friction fastness, washing fastness, dyeing rate and fixation rate of fibers and fabrics modified by existing active modifiers. During the use of the dual-active modifier, since the modified active agent contains a large number of epoxy groups and cyanuric chloride structures, it can effectively covalently and non-covalently bind to cellulose in the fibers and fabrics, so that the modified active agent containing a cationic quaternary ammonium structure and a phenylboronic acid group It is firmly fixed on the fiber and its fabric, thus showing excellent friction fastness and washing fastness. Because phenylboric acid is combined with the composite titanium oxide containing amino groups, the composite titanium oxide is also fixed on the fiber and its fabric. At the same time, since the modified active agent itself can undergo a certain degree of self-crosslinking behavior, a micro-crosslinking network with the composite titanium oxide as a node is formed. Since the composite titanium oxide itself is based on hybrid titanium oxide and has a porphyrin structure containing a sulfonic acid group grafted on the surface, it is combined with the modified active agent containing a quaternary ammonium structure and can be effectively combined with active dyes, thus showing excellent color uptake and fixation rates. DETAILED DESCRIPTION

[0005] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0006] Example 1 A method for preparing a special dual-active modifier for fibers and fabrics thereof, comprising the following steps: weighing the following raw materials by weight: 8 parts of a modified active agent, 4 parts of composite titanium oxide, 0.8 parts of a commercially available RG-G52A printing and dyeing enhancer, and 30 parts of water, mixing the modified active agent, composite titanium oxide, printing and dyeing enhancer, and water to prepare a special dual-active modifier for fibers and fabrics thereof; The modified active agent is prepared by the following steps: Step A1: 3-aminophenylboric acid, anhydrous sodium acetate and acetic acid were mixed, and cyanuric chloride was added under stirring at a rate of 120 rpm and a temperature of 30°C, and the mixture was reacted for 3 hours to obtain intermediate 1; N-methyl-2,2-diaminodiethylamine and acetone were mixed, and intermediate 1 was added under stirring at a rate of 60 rpm and a temperature of 120°C, and the mixture was reacted for 3 hours to obtain intermediate 2; The ratio of 3-aminophenylboric acid, anhydrous sodium acetate and cyanuric chloride is 0.02 mol: 4.5 g: 0.04 mol; the ratio of N-methyl-2,2-diaminodiethylamine and intermediate 1 is 0.01 mol: 0.02 mol; Step A2: Intermediate 2, tetramethylpropylenediamine, 1,3-dibromopropane, isopropanol and acetone were mixed, and the mixture was reacted for 12 hours at a stirring rate of 120 rpm and a temperature of 60° C., and then the mixture was cooled to 50° C., and hydrochloric acid solution and epichlorohydrin were added while stirring, and the mixture was reacted for 3 hours to obtain a modified active agent; The mass fraction of hydrochloric acid solution is 20%, and the amount ratio of intermediate 2, tetramethylpropylenediamine, 1,3-dibromopropane, isopropanol, hydrochloric acid solution and epichlorohydrin is 0.012mol: 0.06mol: 0.06mol: 6mL: 2mL: 0.07mol; The composite titanium oxide is prepared by the following steps: Step B1: Tetrabutyl titanate, glacial acetic acid, deionized water and anhydrous ethanol are mixed, stirred at a stirring rate of 80 rpm, and cerium nitrate hexahydrate is added at room temperature, stirred for 10 minutes, and then a nitric acid solution is added to adjust the pH value to 3, and heated to 60°C, and the reaction is continued for 3 hours, dried, ground, and calcined at 800°C for 3 hours to obtain hybrid titanium oxide; The mass fraction of nitric acid solution is 30%, and the dosage ratio of tetrabutyl titanate, glacial acetic acid and cerium nitrate hexahydrate is 10mL:5mL:0.08g; Step B2: benzaldehyde, 5-nitrosalicylicaldehyde and propionic acid were mixed, stirred at a stirring speed of 120 rpm and a temperature of 135°C, pyrrole was added, and the mixture was reacted for 3 hours, cooled to room temperature, and the mixture was reacted for 12 hours to obtain intermediate a; intermediate a, sodium hydroxide, methanol and deionized water were mixed, stirred at a stirring speed of 60 rpm and a temperature of 60°C, 1,4-butanesulfonate was added, and the mixture was reacted for 4 hours to obtain intermediate b; The ratio of benzaldehyde, 5-nitrosalicylicaldehyde, propionic acid and pyrrole is 0.07 mol: 0.05 mol: 120 mL: 0.12 mol; the ratio of intermediate a, sodium hydroxide and 1,4-butanesulfonate is 0.03 mol: 7 g: 0.6 mol; Step B3: Mix the intermediate b and the hydrochloric acid solution, stir and add stannous chloride dihydrate and deionized water under nitrogen protection, stirring at a rate of 60 rpm and a temperature of 80°C, and react for 30 minutes to obtain the intermediate c, mix the hybrid titanium oxide and 1,4-dioxane and ultrasonically disperse for 10 minutes, stir and add the intermediate c at a temperature of 80°C and a stirring rate of 120 rpm, and react for 2 hours to obtain the composite titanium oxide; The mass fraction of the hydrochloric acid solution is 35%, the amount ratio of the intermediate b, the hydrochloric acid solution and the stannous chloride is 0.02 mol:100 mL:0.04 mol; the amount ratio of the hybrid titanium oxide and the intermediate c is 2 g:0.008 mol.

[0007] Example 2 A method for preparing a special dual-active modifier for fibers and fabrics thereof, comprising the following steps: weighing the following raw materials in parts by weight: 10 parts of a modified active agent, 4 parts of composite titanium oxide, 1 part of a commercially available RG-G52A printing and dyeing enhancer, and 40 parts of water, mixing the modified active agent, composite titanium oxide, printing and dyeing enhancer, and water to prepare a special dual-active modifier for fibers and fabrics thereof; The modified active agent is prepared by the following steps: Step A1: 3-aminophenylboronic acid, anhydrous sodium acetate and acetic acid were mixed, stirred at a stirring rate of 140 rpm and a temperature of 30°C, cyanuric chloride was added, and the mixture was reacted for 4 hours to obtain intermediate 1; N-methyl-2,2-diaminodiethylamine and acetone were mixed, stirred at a stirring rate of 80 rpm and a temperature of 120°C, intermediate 1 was added, and the mixture was reacted for 4 hours to obtain intermediate 2; The ratio of 3-aminophenylboric acid, anhydrous sodium acetate and cyanuric chloride is 0.022 mol: 5 g: 0.044 mol; the ratio of N-methyl-2,2-diaminodiethylamine and intermediate 1 is 0.011 mol: 0.022 mol; Step A2: Intermediate 2, bis(dimethylaminoethyl)ether, 1,3-dibromopropane, isopropanol and acetone were mixed, and the mixture was reacted for 12 hours at a stirring rate of 140 rpm and a temperature of 60°C, and then the mixture was cooled to 50°C, stirred and hydrochloric acid solution and epichlorohydrin were added, and the mixture was reacted for 4 hours to obtain a modified active agent; The mass fraction of hydrochloric acid solution is 20%, and the amount ratio of intermediate 2, bis(dimethylaminoethyl)ether, 1,3-dibromopropane, isopropanol, hydrochloric acid solution and epichlorohydrin is 0.014mol: 0.06mol: 0.06mol: 6mL: 2mL: 0.08mol; The composite titanium oxide is prepared by the following steps: Step B1: Tetrabutyl titanate, glacial acetic acid, deionized water and anhydrous ethanol are mixed, stirred at a stirring rate of 100 rpm, and cerium nitrate hexahydrate is added at room temperature, stirred for 15 minutes, and then a nitric acid solution is added to adjust the pH value to 3, and heated to 60°C, and the reaction is continued for 3 hours, dried, ground, and calcined at 800°C for 3-4 hours to obtain hybrid titanium oxide; The mass fraction of nitric acid solution is 30%, and the dosage ratio of tetrabutyl titanate, glacial acetic acid and cerium nitrate hexahydrate is 10mL:6mL:0.08g; Step B2: benzaldehyde, 5-nitrosalicylicaldehyde and propionic acid were mixed, stirred at a stirring speed of 140 rpm and a temperature of 135°C, pyrrole was added, and the mixture was reacted for 3 hours, cooled to room temperature, and the mixture was reacted for 12 hours to obtain intermediate a; intermediate a, sodium hydroxide, methanol and deionized water were mixed, stirred at a stirring speed of 60 rpm and a temperature of 60°C, 1,4-butanesulfonate was added, and the mixture was reacted for 6 hours to obtain intermediate b; The ratio of benzaldehyde, 5-nitrosalicylicylaldehyde, propionic acid and pyrrole is 0.07-0.075 mol: 0.05 mol: 140 mL: 0.12 mol; the ratio of intermediate a, sodium hydroxide and 1,4-butanesulfonic acid lactone is 0.032 mol: 8 g: 0.6 mol; Step B3: Mix the intermediate b and the hydrochloric acid solution, stir and add stannous chloride dihydrate and deionized water under nitrogen protection, stirring at a rate of 80 rpm and a temperature of 80°C, and react for 30 minutes to obtain the intermediate c, mix the hybrid titanium oxide and 1,4-dioxane and ultrasonically disperse for 15 minutes, stir and add the intermediate c at a temperature of 80°C and a stirring rate of 120 rpm, and react for 3 hours to obtain the composite titanium oxide; The mass fraction of the hydrochloric acid solution is 35%, the amount ratio of the intermediate b, the hydrochloric acid solution and the stannous chloride is 0.02 mol:110 mL:0.04 mol; the amount ratio of the hybrid titanium oxide and the intermediate c is 2 g:0.01 mol.

[0008] Example 3 A method for preparing a special dual-active modifier for fibers and fabrics thereof, comprising the following steps: weighing the following raw materials in parts by weight: 10 parts of a modified active agent, 5 parts of composite titanium oxide, 1 part of a commercially available RG-G52A printing and dyeing enhancer, and 40 parts of water, mixing the modified active agent, composite titanium oxide, printing and dyeing enhancer, and water to prepare a special dual-active modifier for fibers and fabrics thereof; The modified active agent is prepared by the following steps: Step A1: 3-aminophenylboronic acid, anhydrous sodium acetate and acetic acid were mixed, stirred at a stirring rate of 140 rpm and a temperature of 30°C, cyanuric chloride was added, and the mixture was reacted for 4 hours to obtain intermediate 1; N-methyl-2,2-diaminodiethylamine and acetone were mixed, stirred at a stirring rate of 80 rpm and a temperature of 120°C, intermediate 1 was added, and the mixture was reacted for 4 hours to obtain intermediate 2; The ratio of 3-aminophenylboric acid, anhydrous sodium acetate and cyanuric chloride is 0.022 mol: 4.5-5 g: 0.044 mol; the ratio of N-methyl-2,2-diaminodiethylamine and intermediate 1 is 0.011 mol: 0.022 mol; Step A2: Intermediate 2, bis(dimethylaminoethyl)ether, 1,3-dibromopropane, isopropanol and acetone were mixed, and the mixture was reacted for 12 hours at a stirring rate of 140 rpm and a temperature of 60°C, and then the mixture was cooled to 50°C, stirred and hydrochloric acid solution and epichlorohydrin were added, and the mixture was reacted for 4 hours to obtain a modified active agent; The mass fraction of the hydrochloric acid solution is 20%, and the amount ratio of intermediate 2, bis(dimethylaminoethyl)ether, 1,3-dibromopropane, isopropanol, hydrochloric acid solution and epichlorohydrin is 0.014mol: 0.07mol: 0.07mol: 8mL: 3mL: 0.08mol; The composite titanium oxide is prepared by the following steps: Step B1: Tetrabutyl titanate, glacial acetic acid, deionized water and anhydrous ethanol are mixed, stirred at a stirring rate of 100 rpm, and cerium nitrate hexahydrate is added at room temperature, stirred for 15 minutes, and then a nitric acid solution is added to adjust the pH value to 3, and heated to 60°C, and the reaction is continued for 4 hours, dried, ground, and calcined at 800°C for 4 hours to obtain hybrid titanium oxide; The mass fraction of nitric acid solution is 30%, and the dosage ratio of tetrabutyl titanate, glacial acetic acid and cerium nitrate hexahydrate is 12mL:6mL:0.09g; Step B2: benzaldehyde, 5-nitrosalicylicaldehyde and propionic acid were mixed, stirred at a stirring speed of 140 rpm and a temperature of 135°C, pyrrole was added, and the mixture was reacted for 3 hours, cooled to room temperature, and the mixture was reacted for 12 hours to obtain intermediate a; intermediate a, sodium hydroxide, methanol and deionized water were mixed, stirred at a stirring speed of 80 rpm and a temperature of 60°C, 1,4-butanesulfonate was added, and the mixture was reacted for 6 hours to obtain intermediate b; The ratio of benzaldehyde, 5-nitrosalicylicylaldehyde, propionic acid and pyrrole is 0.075 mol: 0.055 mol: 120-140 mL: 0.13 mol; the ratio of intermediate a, sodium hydroxide and 1,4-butanesulfonic acid lactone is 0.032 mol: 8 g: 0.07 mol; Step B3: Mix the intermediate b and the hydrochloric acid solution, stir and add stannous chloride dihydrate and deionized water under nitrogen protection, stirring at a rate of 80 rpm and a temperature of 80°C, and react for 40 minutes to obtain the intermediate c, mix the hybrid titanium oxide and 1,4-dioxane and ultrasonically disperse for 15 minutes, stir and add the intermediate c at a temperature of 80°C and a stirring rate of 140 rpm, and react for 3 hours to obtain the composite titanium oxide; The mass fraction of the hydrochloric acid solution is 35%, the amount ratio of the intermediate b, the hydrochloric acid solution and the stannous chloride is 0.024 mol:110 mL:0.05 mol; the amount ratio of the hybrid titanium oxide and the intermediate c is 2.3 g:0.01 mol.

[0009] Comparative Example 1 Compared with Example 3, this comparative example is different in that 3-aminophenylboronic acid in the preparation process of the modified active agent in Example 3 is replaced by aniline, and the other steps are the same.

[0010] Comparative Example 2 Compared with Example 3, this comparative example replaces the hybrid titanium oxide in the preparation process of the composite titanium oxide in Example 3 with commercially available Xinzhongda XD-TA10 titanium oxide, and the other steps are the same.

[0011] Comparative Example 3 Compared with Example 3, this comparative example is different in that the composite titanium oxide in the preparation process of the dual-active modifier for fibers and fabrics thereof in Example 3 is replaced by the hybrid titanium oxide in Example 3, and the other steps are the same.

[0012] Take the special double-active modifier for fiber and its fabric obtained in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3, mix the special double-active modifier for fiber and its fabric, sodium hydroxide and water, wherein the concentration of the special double-active modifier for fiber and its fabric is 60g / L, the concentration of sodium hydroxide is 2g / L, and the fiber and its fabric are finished by two-immersion and two-rolling process, the temperature of the two immersions is 30°C, the immersion time is 1h, the bath ratio is 1:40, the rolling rate is 100%, and then at 80°C The fibers and fabrics were pre-baked at 110°C for 2 minutes and baked at 110°C for 4 minutes. The finished fibers and fabrics were then dyed, soaped, washed and dried to obtain dyed fibers and fabrics. The dye concentration was 2%, the sodium carbonate concentration was 20 g / L, the acetic acid concentration was 1 g / L, the bath ratio was 1:40, and during the soaping process, the soap solution was 2 g / L, the bath ratio was 1:30, and the temperature was 90°C. The dye used was Reactive Red 3BS. The dye uptake was determined by the residual liquid method, and the K / S value was determined by a colorimeter. The color fastness to soaping was tested with reference to GB / T 3921-2008, and the color fastness to rubbing was tested with reference to GB / T 3920-2008. The test results are shown in Table 1.

[0013] It can be seen from the test results in the table shown that when Example 1, Example 2 and Example 3 are compared with Comparative Example 1, Comparative Example 2 and Comparative Example 3, Comparative Example 1 replaces the 3-aminophenylboric acid in the preparation process of the modified active agent in Example 3 with aniline. Due to the lack of phenylboric acid groups, it cannot combine with the composite titanium oxide, resulting in a decrease in its performance. Comparative Example 2 replaces the hybrid titanium oxide in the preparation process of the composite titanium oxide in Example 3 with the commercially available Xinzhongda XD-TA10 titanium oxide. Due to the lack of a doping step, its dye adsorption performance is reduced. Comparative Example 3 replaces the composite titanium oxide in the preparation process of the dual-active modifier for fibers and fabrics in Example 3 with the hybrid titanium oxide in Example 3, resulting in a significant decrease in its performance.

[0014] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0015] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a special dual-active modifier for fibers and fabrics thereof, characterized in that: The method comprises the following steps: weighing the following raw materials by weight: 8-10 parts of a modified active agent, 4-5 parts of composite titanium oxide, 0.8-1 part of a printing and dyeing enhancer and 30-40 parts of water, mixing the modified active agent, the composite titanium oxide, the printing and dyeing enhancer and the water to prepare a special dual-active modifier for fibers and fabrics thereof.

2. The method for preparing a dual-active modifier for fibers and fabrics thereof according to claim 1, characterized in that: The modified active agent is prepared by the following steps: Step A1: 3-aminophenylboronic acid, anhydrous sodium acetate and acetic acid are mixed, stirred at a stirring rate of 120-140 rpm and a temperature of 30° C., cyanuric chloride is added, and the reaction is carried out for 3-4 hours to obtain intermediate 1; N-methyl-2,2-diaminodiethylamine and acetone are mixed, stirred at a stirring rate of 60-80 rpm and a temperature of 120° C., intermediate 1 is added, and the reaction is carried out for 3-4 hours to obtain intermediate 2; Step A2: Mix intermediate 2, diamine intermediate, 1,3-dibromopropane, isopropanol and acetone, react for 12 hours at a stirring rate of 120-140 rpm and a temperature of 60°C, then cool to 50°C, stir and add hydrochloric acid solution and epichlorohydrin, react for 3-4 hours to obtain a modified active agent.

3. The method for preparing a dual-active modifier for fibers and fabrics thereof according to claim 2, characterized in that: In step A1, the ratio of 3-aminophenylboric acid, anhydrous sodium acetate and cyanuric chloride is 0.02-0.022 mol: 4.5-5 g: 0.04-0.044 mol; the ratio of N-methyl-2,2-diaminodiethylamine and intermediate 1 is 0.01-0.011 mol: 0.02-0.022 mol.

4. The method for preparing a dual-active modifier for fibers and fabrics thereof according to claim 2, characterized in that: In step A2: the mass fraction of the hydrochloric acid solution is 20%, and the amount ratio of intermediate 2, diamine intermediate, 1,3-dibromopropane, isopropanol, hydrochloric acid solution and epichlorohydrin is 0.012-0.014 mol: 0.06-0.07 mol: 0.06-0.07 mol: 6-8 mL: 2-3 mL: 0.07-0.08 mol.

5. The method for preparing a special dual-active modifier for fiber and fabric thereof according to claim 2, characterized in that: In step A2: the diamine intermediate is one of tetramethylpropylenediamine and bis(dimethylaminoethyl)ether.

6. The method for preparing a special dual-active modifier for fiber and fabric thereof according to claim 1, characterized in that: The composite titanium oxide is prepared by the following steps: Step B1: Tetrabutyl titanate, glacial acetic acid, deionized water and anhydrous ethanol are mixed, stirred at a stirring rate of 80-100 rpm, and cerium nitrate hexahydrate is added at room temperature, stirred for 10-15 minutes, and then a nitric acid solution is added to adjust the pH value to 3, and heated to 60°C, and the reaction is continued for 3-4 hours, dried, ground, and calcined at 800°C for 3-4 hours to obtain hybrid titanium oxide; Step B2: benzaldehyde, 5-nitrosalicylicaldehyde and propionic acid are mixed, stirred at a stirring speed of 120-140 rpm and a temperature of 135°C, pyrrole is added, the reaction is carried out for 3 hours, the temperature is cooled to room temperature, and the reaction is continued for 12 hours to obtain intermediate a; intermediate a, sodium hydroxide, methanol and deionized water are mixed, stirred at a stirring speed of 60-80 rpm and a temperature of 60°C, 1,4-butanesulfonic acid lactone is added, and the reaction is carried out for 4-6 hours to obtain intermediate b; Step B3: Mix the intermediate b and the hydrochloric acid solution, stir and add stannous chloride dihydrate and deionized water under nitrogen protection, stirring at a rate of 60-80 rpm and a temperature of 80°C, and react for 30-40 minutes to obtain the intermediate c. Mix the hybrid titanium oxide and 1,4-dioxane and ultrasonically disperse them for 10-15 minutes. Stir and add the intermediate c at a temperature of 80°C and a stirring rate of 120-140 rpm, and react for 2-3 hours to obtain the composite titanium oxide.

7. The method for preparing a special dual-active modifier for fiber and fabric thereof according to claim 6, characterized in that: In step B1, the mass fraction of the nitric acid solution is 30%, and the dosage ratio of tetrabutyl titanate, glacial acetic acid and cerium nitrate hexahydrate is 10-12 mL: 5-6 mL: 0.08-0.09 g.

8. The method for preparing a special dual-active modifier for fiber and fabric thereof according to claim 6, characterized in that: In step B2, the ratio of benzaldehyde, 5-nitrosalicylicylaldehyde, propionic acid and pyrrole is 0.07-0.075 mol: 0.05-0.055 mol: 120-140 mL: 0.12-0.13 mol; the ratio of intermediate a, sodium hydroxide and 1,4-butanesulfonate is 0.03-0.032 mol: 7-8 g: 0.6-0.07 mol.

9. The method for preparing a dual-active modifier for fibers and fabrics thereof according to claim 6, characterized in that: In step B3: the mass fraction of the hydrochloric acid solution is 35%, the amount ratio of the intermediate b, the hydrochloric acid solution and the stannous chloride is 0.02-0.024 mol: 100-110 mL: 0.04-0.05 mol; the amount ratio of the hybrid titanium oxide and the intermediate c is 2-2.3 g: 0.008-0.01 mol.

10. A dual-active modifier for fibers and fabrics thereof, characterized in that: Prepared according to any one of claims 1 to 9.

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