Cellulose fiber cationic modifier and method of making

Abstract

This invention relates to the field of cationic modifiers and discloses a cationic modifier for cellulose fibers and its preparation method, comprising the following steps: mixing methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, a modifier, an initiator, and deionized water, stirring until homogeneous, to obtain a mixture; stirring the mixture to react, cooling to room temperature, adding ethanol, collecting the white precipitate by vacuum filtration, washing and drying the white precipitate to obtain the cationic modifier for cellulose fibers. The cationic modifier for cellulose fibers formed by methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, and the modifier can penetrate into the fiber interior, resulting in a uniform distribution of cationic groups on the fiber surface, thereby improving the dye uptake and fixation rate of subsequent dyes.

Description

Technical Field

[0001] This invention relates to the field of cationic modifiers, specifically to a cationic modifier for cellulose fibers and its preparation method. Background Technology

[0002] Cellulose fibers (cotton, linen, etc.) are widely used due to their moisture absorption, breathability, and comfortable wear. Dyeing cellulose fibers with reactive dyes is a common method to improve the washing fastness of fibers. However, cellulose fibers carry a negative charge during the dyeing process, while most reactive dyes used for dyeing cellulose fibers and fabrics are anionic. The electrostatic repulsion between the two results in low dye uptake and fixation rates of reactive dyes on the surface of cellulose fibers. In existing technologies, inorganic salts are used extensively as dyeing accelerators to solve the problem of low dye uptake and fixation rates. The inorganic salts contained in the dyeing wastewater, after treatment, are discharged, which can easily lead to soil salinization and pollute the ecological environment. Therefore, how to solve the problem of high salt consumption and high pollution in the reactive dyeing process has become a difficult problem that the industry urgently needs to overcome.

[0003] Cationic modification technology enables salt-free dyeing of reactive dyes. After being treated with cationic modifiers, cellulose fibers exhibit positive charge, which promotes the dyeing of reactive dye anions onto the fibers, improving the dyeing rate and reducing the discharge of saline wastewater. Traditional cationic modifiers are mostly linear molecular structures, with reactive and cationic groups arranged linearly along the molecular chain. The spatial configuration is not conducive to multi-point anchoring with multiple hydroxyl groups on the fiber, resulting in insufficient binding strength between the cationic modifier and the fiber, poor wash resistance, and limited adsorption capacity of the cationic modifier, leading to insufficient dyeing uniformity of the fiber. Summary of the Invention

[0004] This invention provides a cationic modifier for cellulose fibers and its preparation method, which solves the problems of insufficient bonding strength between the cationic modifier and the fiber, poor wash resistance, and limited adsorption capacity of the cationic modifier, resulting in insufficient dyeing uniformity of the fiber.

[0005] The technical solution of the present invention:

[0006] A method for preparing a cellulose fiber cationic modifier includes the following steps:

[0007] S1. Mix methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifier, initiator and deionized water, and stir until uniform to obtain a mixture;

[0008] S2. The mixture is stirred and reacted at 60-70℃ for 4-6 hours. After cooling to room temperature, ethanol is added, and the white precipitate is collected by vacuum filtration. The white precipitate is washed and dried to obtain the cellulose fiber cationic modifier.

[0009] The modified additive is obtained by mixing and reacting amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, modified zeolite and silane coupling agent;

[0010] The modified zeolite is obtained by calcining a mixture of zeolite and glucose, followed by amino-polyethylene glycol-carboxyl surface treatment.

[0011] Further, in step S1, the mass ratio of methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator and deionized water is (3-4):(4-5):(2-3):(1-2):(0.02-0.05):(50-60).

[0012] Further, in step S1, the initiator is composed of potassium persulfate and sodium bisulfite mixed in a mass ratio of 1:(0.3-0.4).

[0013] Further, in step S2, the mass ratio of the mixture to ethanol is 1:(1.3-1.4).

[0014] Furthermore, the modified additive is specifically prepared by the following steps:

[0015] A1. Add zeolite and glucose to deionized water, stir, filter, dry to remove moisture, place in a tube furnace, add potassium hydroxide solution, purge with nitrogen gas, carbonize, cool to room temperature, remove, wash, and dry to obtain zeolite loaded with porous carbon.

[0016] A2. Add amino-polyethylene glycol-carboxyl zeolite loaded with porous carbon to deionized water, stir evenly, add hydrochloric acid to adjust pH, stir until the reaction is complete, filter, wash and dry to obtain modified zeolite.

[0017] A3. Add lignin to deionized water, stir well, add sodium hydroxide solution to adjust the pH of the solution, heat up, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir the reaction, cool to room temperature, then put it into a dialysis bag for dialyzing, and freeze-dry to obtain amphoteric alkali lignin.

[0018] A4. Add amphoteric alkali lignin and carboxymethyl-β-cyclodextrin to N,N-dimethylformamide, stir until homogeneous, add p-toluenesulfonic acid, stir and react at 100-110℃ for 3-4h, cool to room temperature, precipitate in ethanol, wash the precipitate, dry, and obtain the complex.

[0019] The complex, modified zeolite, and silane coupling agent were added to deionized water and ethanol, stirred until homogeneous, and hydrochloric acid was added to adjust the pH. The mixture was stirred and reacted, then filtered, washed, and dried to obtain the modified additive.

[0020] Furthermore, in the above A1 reaction process, zeolite has high adsorption performance and can adsorb glucose on the zeolite surface. After high-temperature carbonization, glucose decomposes to form a dense carbon layer. Potassium hydroxide solution, as an activator, can form pores on the surface of the dense carbon layer, thereby achieving the synthesis of a porous carbon layer on the zeolite surface and obtaining zeolite with a porous carbon layer.

[0021] Furthermore, the carbonization process can remove impurities such as moisture and organic matter from the zeolite pores, clear the pores of the zeolite, and improve the adsorption capacity and specific surface area of ​​the zeolite.

[0022] Furthermore, during the A2 reaction described above, the carboxyl groups contained in the amino-polyethylene glycol-carboxyl group can chemically bond with the hydroxyl groups on the surface of the zeolite supported on the porous carbon layer, thereby grafting the amino-polyethylene glycol-carboxyl group onto the surface of the zeolite supported on the porous carbon layer to obtain modified zeolite.

[0023] Furthermore, in the A3 reaction process described above, the chlorine element in 3-chloro-2-hydroxypropyltrimethylammonium chloride can react with the hydroxyl groups on the lignin molecular chain, grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride onto the lignin molecular chain, so that the lignin carries quaternary ammonium cationic groups, and the carboxyl and hydroxyl groups it contains are anionic groups, forming amphoteric alkali lignin.

[0024] Furthermore, during the A4 reaction process described above, the carboxyl and hydroxyl groups contained in amphoteric lignin can react with the carboxyl groups of carboxymethyl-β-cyclodextrin, causing carboxymethyl-β-cyclodextrin to be grafted onto the amphoteric lignin molecular chain to form a complex.

[0025] Furthermore, the amino groups on the surface of the modified zeolite are electrostatically bonded to the unreacted carboxyl and hydroxyl groups of the amphoteric lignin in the complex, so that the complex is coated on the surface of the zeolite. The silanol groups generated by the hydrolysis of the silane coupling agent continue to consume the remaining carboxyl and hydroxyl groups of the amphoteric lignin, thus obtaining the modified additive.

[0026] Further, in step A1, the mass ratio of the zeolite, glucose, deionized water and potassium hydroxide solution is (2-3):(1-1.5):(20-30):(4-4.5).

[0027] Further, in step A2, the mass ratio of the amino-polyethylene glycol-carboxyl group, the zeolite supported on porous carbon, and the deionized water is (1-1.2):(2-2.5):(70-90).

[0028] Further, in step A3, the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is (2.5-3):(80-100):(4-5).

[0029] Further, in step A4, the mass ratio of the amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide and p-toluenesulfonic acid is (1-1.2):(0.6-0.8):(30-40):(0.02-0.04).

[0030] Further, in step A4, the mass ratio of the complex, modified zeolite, silane coupling agent, deionized water and ethanol is (1-1.3):(2-2.5):(0.5-0.7):(30-40):(90-100).

[0031] The present invention has the following beneficial effects:

[0032] (1) In the technical solution of the present invention, a porous carbon layer is synthesized on the surface of zeolite. On the one hand, the porous carbon layer synthesized by zeolite has high adsorption performance, which can adsorb and fix the metal elements in zeolite, and prevent the metal elements from leaking to the fiber surface and affecting the dyeing of the fiber. Moreover, the composite porous structure formed by the combination of zeolite and porous carbon layer can increase the adsorption capacity of zeolite, adsorb the anionic dyes adsorbed by the cationic modifier into the pores of zeolite and porous carbon layer, thereby increasing the adsorption performance of cationic modifier on anionic dyes and improving the dyeing uniformity of the fiber. On the other hand, the disordered internal structure of zeolite and porous carbon layer can prevent the anionic dyes from falling off and precipitating, so that the cationic modifier has high wash resistance. In addition, zeolite has a small size effect, which can be uniformly adsorbed on the fiber surface and penetrate into the fiber interior along with the cationic modifier, so that the cationic groups on the fiber surface are evenly distributed, improving the dyeing rate and fixation rate of subsequent dyes, and improving the uniformity of fiber dyeing.

[0033] (2) In the technical solution of the present invention, amino-polyethylene glycol-carboxyl grafts are applied to the surface of the zeolite loaded with porous carbon layer, which imparts more polar functional groups to the zeolite loaded with porous carbon layer. This is beneficial for coating the zeolite surface with amphoteric alkali lignin and carboxymethyl-β-cyclodextrin, thereby improving the dispersibility of zeolite in cationic modifiers and its adsorption performance on anionic dyes.

[0034] (3) In the technical solution of the present invention, amphoteric alkali lignin and carboxymethyl-β-cyclodextrin are coated on the surface of modified zeolite. On the one hand, the amino groups contained in amphoteric alkali lignin can adsorb anionic dyes, further improving the adsorption performance of cationic modifiers for anionic dyes. In addition, lignin has good compatibility with cellulose fibers, which can also improve the dispersibility of modified zeolite in cationic modifiers, thereby increasing the binding force of cationic modifiers on the fiber surface and improving the dyeing rate of fibers. On the other hand, the carboxyl groups contained in carboxymethyl-β-cyclodextrin and the amino groups contained in amino-polyethylene glycol-carboxyl groups on the surface of modified zeolite can consume the anionic groups in amphoteric alkali lignin, avoiding the repulsive effect of lignin on anionic dyes. In addition, the internal cavity of carboxymethyl-β-cyclodextrin has hydrophobic properties, which can form inclusion complexes with anionic dyes through hydrophobic interactions, further improving the adsorption performance of cationic modifiers for dyes and improving the fixation rate.

[0035] (4) In the technical solution of the present invention, amino-polyethylene glycol-carboxyl and amphoteric alkali lignin have high molecular weights and can form a network structure of organic molecular layer on the surface of modified zeolite through long chain entanglement or cross-linking, thereby generating a steric hindrance effect, making it difficult for anionic dyes adsorbed in modified zeolite to migrate and precipitate, thus improving the fixation rate and dyeing rate.

[0036] (5) In the technical solution of the present invention, the cellulose fiber cationic modifier formed by methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate and modifying agent can penetrate into the fiber interior, so that the cationic groups on the fiber surface are evenly distributed, thereby improving the dyeing rate and fixation rate of subsequent dyes. Moreover, the cationic modifier has a high adsorption capacity, which prevents the positive charge sites on the fiber from being occupied by anionic dyes and thus preventing the adsorption of more dyes, thereby affecting the color yield of the cellulose fiber. In addition, the double bond contained in the silane coupling agent in the modifying agent can participate in the reaction of the cationic modifier, so that the cationic modifier is evenly dispersed in the cationic modifier, thereby improving the adsorption performance of the cationic modifier for dyes. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0039] The lignin content is 99%, and it was purchased from Wuhan Kemic Biomedical Technology Co., Ltd.

[0040] The zeolite particle size is 5μm.

[0041] The silane coupling agent is KH570 (γ-methacryloyloxypropyltrimethoxysilane);

[0042] Amino-polyethylene glycol-carboxyl group, product number S25038, was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0043] The carboxymethyl-β-cyclodextrin, catalog number 779873-100G, was purchased from Merck.

[0044] Example 1

[0045] A method for preparing a cellulose fiber cationic modifier includes the following steps:

[0046] S1. Mix methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifier, initiator, and deionized water, and stir until homogeneous to obtain a mixture; wherein, the mass ratio of methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifier, initiator, and deionized water is 3:4:2:1:0.02:50; the initiator is composed of potassium persulfate and sodium bisulfite mixed in a mass ratio of 1:0.3.

[0047] S2. The mixture was stirred and reacted at 60℃ for 4 hours. After cooling to room temperature, ethanol was added, and the white precipitate was collected by vacuum filtration. The white precipitate was washed 5 times with acetone and dried in a vacuum oven at 50℃ for 24 hours to obtain the cellulose fiber cationic modifier. The mass ratio of the mixture to ethanol was 1:1.3.

[0048] The modified additive is prepared by the following steps:

[0049] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 2:1:20:4.

[0050] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in a 70℃ oven for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1:2:70.

[0051] A3. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.5:80:4;

[0052] A4. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 100°C for 3 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1:0.6:30:0.02.

[0053] The complex, modified zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred and reacted at 70°C for 1 h. After filtration, the mixture was washed three times with deionized water and dried in an oven at 70°C for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, KH570, deionized water, and ethanol was 1:2:0.5:30:90.

[0054] Example 2

[0055] A method for preparing a cellulose fiber cationic modifier includes the following steps:

[0056] S1. Mix methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator, and deionized water, and stir until homogeneous to obtain a mixture; wherein, the mass ratio of methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator, and deionized water is 3.5:4.5:2.5:1.5:0.03:55; the initiator is composed of potassium persulfate and sodium bisulfite mixed in a mass ratio of 1:0.35;

[0057] S2. The mixture was stirred and reacted at 65℃ for 5 hours. After cooling to room temperature, ethanol was added, and the white precipitate was collected by vacuum filtration. The white precipitate was washed 5 times with acetone and dried in a vacuum oven at 50℃ for 24 hours to obtain the cellulose fiber cationic modifier. The mass ratio of the mixture to ethanol was 1:1.35.

[0058] The modified additive is prepared by the following steps:

[0059] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 2.5:1.3:25:4.3.

[0060] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1.1:2.3:80;

[0061] A3. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.8:90:4.5;

[0062] A4. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 105℃ for 3.5 h. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60℃ for 10 min to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.1:0.7:35:0.03.

[0063] The complex, modified zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred at 70°C for 1 h, filtered, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, KH570, deionized water, and ethanol was 1.2:2.3:0.6:35:95.

[0064] Example 3

[0065] A method for preparing a cellulose fiber cationic modifier includes the following steps:

[0066] S1. Mix methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator, and deionized water, and stir until homogeneous to obtain a mixture; wherein, the mass ratio of methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator, and deionized water is 4:5:3:2:0.05:60; the initiator is composed of potassium persulfate and sodium bisulfite mixed in a mass ratio of 1:0.4.

[0067] S2. The mixture was stirred and reacted at 70℃ for 6 hours. After cooling to room temperature, ethanol was added, and the white precipitate was collected by vacuum filtration. The white precipitate was washed 5 times with acetone and dried in a vacuum oven at 50℃ for 24 hours to obtain the cellulose fiber cationic modifier. The mass ratio of the mixture to ethanol was 1:1.4.

[0068] The modified additive is prepared by the following steps:

[0069] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 3:1.5:30:4.5.

[0070] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1.2:2.5:90;

[0071] A3. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 3:100:5;

[0072] A4. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.2:0.8:40:0.04.

[0073] The complex, modified zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred at 70°C for 1 h, filtered, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, KH570, deionized water, and ethanol was 1.3:2.5:0.7:40:100.

[0074] Comparative Example 1

[0075] The only difference between this comparative example and Example 3 is the preparation of the modifying agent, as detailed below:

[0076] The modified additive is prepared by the following steps:

[0077] A1. Add amino-polyethylene glycol-carboxyl and zeolite to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in a 70℃ oven for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl, zeolite and deionized water is 1.2:2.5:90;

[0078] A2. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 3:100:5;

[0079] A3. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.2:0.8:40:0.04.

[0080] The complex, modified zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred at 70°C for 1 h, filtered, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, KH570, deionized water, and ethanol was 1.3:2.5:0.7:40:100.

[0081] Comparative Example 2

[0082] The only difference between this comparative example and Example 3 is the preparation of the modifying agent, as detailed below:

[0083] The modified additive is prepared by the following steps:

[0084] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 3:1.5:30:4.5.

[0085] A2. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 3:100:5;

[0086] A3. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.2:0.8:40:0.04.

[0087] The composite, carbon-supported zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred at 70°C for 1 h, filtered, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain the modified additive. The mass ratio of the composite, carbon-supported zeolite, KH570, deionized water, and ethanol was 1.3:2.5:0.7:40:100.

[0088] Comparative Example 3

[0089] The only difference between this comparative example and Example 3 is the preparation of the modifying agent, as detailed below:

[0090] The modified additive is prepared by the following steps:

[0091] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 3:1.5:30:4.5.

[0092] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1.2:2.5:90;

[0093] A3. Lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.2:0.8:40:0.04.

[0094] The complex, modified zeolite, and KH570 were added to deionized water and ethanol, stirred until homogeneous, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred at 70°C for 1 h, filtered, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, KH570, deionized water, and ethanol was 1.3:2.5:0.7:40:100.

[0095] Comparative Example 4

[0096] The only difference between this comparative example and Example 3 is the preparation of the modifying agent, as detailed below:

[0097] The modified additive is prepared by the following steps:

[0098] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 3:1.5:30:4.5.

[0099] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1.2:2.5:90;

[0100] A3. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 3:100:5;

[0101] A4. Add amphoteric alkali lignin, modified zeolite, and KH570 to deionized water and ethanol, stir well, add 1 mol / L hydrochloric acid to adjust the pH to 4.5, stir and react at 70℃ for 1 h, filter, wash three times with deionized water, and dry in a 70℃ oven for 10 min to obtain the modified additive; the mass ratio of amphoteric alkali lignin, modified zeolite, KH570, deionized water, and ethanol is 1.3:2.5:0.7:40:100.

[0102] Comparative Example 5

[0103] The only difference between this comparative example and Example 3 is the preparation of the modifying agent, as detailed below:

[0104] The modified additive is prepared by the following steps:

[0105] A1. Zeolite and glucose were added to deionized water and stirred at 40°C for 30 min. After filtration, the mixture was dried in an oven at 100°C for 10 min to remove moisture. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain zeolite loaded with porous carbon. The mass ratio of zeolite, glucose, deionized water, and potassium hydroxide solution was 3:1.5:30:4.5.

[0106] A2. Add amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water, stir evenly, add 1 mol / L hydrochloric acid to adjust the pH to 3.5, stir and react at 70℃ for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10 min to obtain modified zeolite; the mass ratio of amino-polyethylene glycol-carboxyl zeolite with porous carbon supported to deionized water is 1.2:2.5:90;

[0107] A3. Add lignin to deionized water, stir well, add 20% sodium hydroxide solution to adjust the pH of the solution to 12, heat to 85℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir and react for 4 hours, cool to room temperature, then dialyze in a dialysis bag (Mw=1000Da) for 7 days, freeze dry at -20℃ for 1 hour to obtain amphoteric alkali lignin; the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is 3:100:5;

[0108] A4. Amphoteric alkali lignin and carboxymethyl-β-cyclodextrin were added to N,N-dimethylformamide and stirred until homogeneous. P-toluenesulfonic acid was added, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the mixture was placed in ethanol for precipitation. The precipitate was washed three times with ethanol and dried in an oven at 60°C for 10 minutes to obtain the complex. The mass ratio of amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide, and p-toluenesulfonic acid was 1.2:0.8:40:0.04.

[0109] The complex and modified zeolite were added to deionized water and ethanol, stirred evenly, and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. The mixture was stirred and reacted at 70℃ for 1 h. After filtration, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10 min to obtain the modified additive. The mass ratio of the complex, modified zeolite, deionized water and ethanol was 2:2.5:40:100.

[0110] The performance of the cellulose fiber cationic modifiers prepared in Examples 1-3 and Comparative Examples 1-5 was then tested.

[0111] Cellulose fibers were impregnated in a cationic modifier solution at a liquor ratio of 30:1 and treated in a constant temperature water bath at 90℃ for 1 hour. Then, the fibers were immersed and rubbed twice (80% immersion rate) using a padding machine. After the fabric was removed, it was first dried in an oven at 85℃, then baked at 140℃ for 3 minutes, then washed 5 times with water, and dried at 80℃ for 8 minutes to obtain cellulose fibers modified by the cationic modifier.

[0112] Dyeing of cellulose fibers modified with cationic modifiers:

[0113] The dye used was Reactive Red X-3B, with an amount of 2% (owf). The dyeing temperature was 60℃, the liquor ratio was 30:1, and the dyeing time was 1 hour. The dyed fibers were then removed, washed 5 times with water, and dried in an oven at 70℃ for 8 minutes to obtain the dyed cellulose fibers.

[0114] According to GB / T6688-2008, the K / S value of dyed polyester is used to represent the apparent color depth (color gain) of polyester, reflecting the amount of dye fixed on cellulose fibers and the dyeing effect; according to GB / T3921-2008 "Textiles - Tests for color fastness to soaping", the color fastness to soaping of dyed cellulose fibers is determined using a wash fastness tester.

[0115] According to GB / T3920-2008 "Textiles - Tests for color fastness to rubbing", the dry and wet rubbing fastness of dyed cellulose fibers is tested. It is used to indicate that the dye on the surface of cellulose fibers treated with cationic modifiers is firmly bonded and is not prone to fading or staining under dry and wet rubbing conditions.

[0116] As shown in Table 1 below.

[0117] Table 1. Performance testing of cellulose fiber cationic modifiers prepared in Examples 1-3 and Comparative Examples 1-5

[0118] As can be seen from the data in Table 1, the cellulose fiber cationic modifiers prepared in Examples 1-3 can penetrate into the fiber interior, making the cationic groups on the fiber surface uniformly distributed, improving the dyeing rate and fixation rate of subsequent dyes, and the cationic modifiers have a high adsorption capacity.

[0119] In Comparative Example 1, the zeolite loaded with porous carbon was replaced with a zeolite-based modifying agent used to prepare a cationic modifier for cellulose fibers. After modification, the dyeing performance of the cellulose fibers decreased, demonstrating that the porous carbon layer synthesized on the zeolite surface has high adsorption capacity. This layer can adsorb and fix metal elements in the zeolite, preventing metal elements from leaking to the fiber surface and affecting fiber dyeing. Furthermore, the composite porous structure formed by the combination of zeolite and porous carbon layer can increase the adsorption capacity of zeolite, allowing the anionic dyes adsorbed by the cationic modifier to be adsorbed into the pores of the zeolite and porous carbon layer. This further increases the adsorption performance of the cationic modifier for anionic dyes, improving the dyeing uniformity of the fibers. In addition, the disordered internal structure of the zeolite and porous carbon layer can hinder the shedding and precipitation of anionic dyes, giving the cationic modifier high wash resistance. Moreover, zeolite has a small size effect, which allows it to be uniformly adsorbed on the fiber surface and penetrate into the fiber interior along with the cationic modifier, resulting in a uniform distribution of cationic groups on the fiber surface. This improves the dyeing rate and fixation rate of subsequent dyes, while also improving the fiber's even dyeing properties.

[0120] In Comparative Example 2, the modified zeolite was replaced with zeolite loaded with porous carbon to prepare a cationic modifier for cellulose fibers. After modification, the dyeing performance of the cellulose fibers decreased, demonstrating that the grafting of amino-polyethylene glycol-carboxyl groups onto the surface of the zeolite loaded with porous carbon layers endows the zeolite with more polar functional groups. This is beneficial for coating the zeolite surface with amphoteric alkali lignin and carboxymethyl-β-cyclodextrin, improving the dispersibility of the zeolite in the cationic modifier and its adsorption performance for anionic dyes. Furthermore, the amino-polyethylene glycol-carboxyl groups and amphoteric alkali lignin have high molecular weights and can form a network structure of organic molecular layers on the surface of the modified zeolite through long chain entanglement or cross-linking, generating a steric hindrance effect. This makes it difficult for anionic dyes adsorbed in the modified zeolite to migrate and precipitate, thereby improving the fixation rate and dyeing rate.

[0121] In Comparative Example 3, the modification agent prepared by replacing amphoteric alkali lignin with lignin was used to prepare a cationic modifier for cellulose fibers. After modification, the dyeing rate of cellulose fibers decreased, which proved that the amino groups contained in amphoteric alkali lignin can adsorb anionic dyes. Furthermore, lignin has good compatibility with cellulose fibers and can also improve the dispersibility of modified zeolite in the cationic modifier, thereby increasing the binding force of the cationic modifier on the fiber surface and improving the dyeing rate of the fibers.

[0122] In Comparative Example 4, the complex was replaced with a modified auxiliary agent prepared from amphoteric alkali lignin to prepare a cationic modifier for cellulose fibers. After modification, the staining of cellulose fibers decreased, demonstrating that the carboxyl groups in carboxymethyl-β-cyclodextrin and the amino groups in the amino-polyethylene glycol-carboxyl groups on the modified zeolite surface can consume the anionic groups in amphoteric alkali lignin, avoiding the repulsion of anionic dyes by lignin. Furthermore, the internal cavity of carboxymethyl-β-cyclodextrin has hydrophobic properties, which can form inclusion complexes with anionic dyes through hydrophobic interactions, further improving the adsorption performance of the cationic modifier for dyes and increasing the fixation rate.

[0123] In Comparative Example 5, KH570 was replaced by a modified auxiliary agent prepared from the complex to prepare a cation modifier for cellulose fibers. After modification, the dyeing performance of the cellulose fibers decreased, proving that the double bonds contained in the silane coupling agent in the modified auxiliary agent can participate in the reaction of the cation modifier, so that the cation modifier is uniformly dispersed in the cation modifier and the adsorption performance of the cation modifier for dyes is improved.

[0124] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0125] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a cellulose fiber cationic modifier, characterized in that, Includes the following steps: S1. Mix methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifier, initiator and deionized water, and stir until uniform to obtain a mixture; S2. The mixture is stirred and reacted at 60-70℃ for 4-6 hours. After cooling to room temperature, ethanol is added, and the white precipitate is collected by vacuum filtration. The white precipitate is washed and dried to obtain the cellulose fiber cationic modifier. The modified additive is obtained by mixing and reacting amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, modified zeolite and silane coupling agent; The modified zeolite is obtained by calcining a mixture of zeolite and glucose, followed by amino-polyethylene glycol-carboxyl surface treatment.

2. The method for preparing a cellulose fiber cationic modifier according to claim 1, characterized in that, The modified additive is prepared by the following steps: A1. Add zeolite and glucose to deionized water, stir, filter, dry to remove moisture, place in a tube furnace, add potassium hydroxide solution, purge with nitrogen gas, carbonize, cool to room temperature, remove, wash, and dry to obtain zeolite loaded with porous carbon. A2. Add amino-polyethylene glycol-carboxyl zeolite loaded with porous carbon to deionized water, stir evenly, add hydrochloric acid to adjust pH, stir until the reaction is complete, filter, wash and dry to obtain modified zeolite. A3. Add lignin to deionized water, stir well, add sodium hydroxide solution to adjust the pH of the solution, heat up, add 3-chloro-2-hydroxypropyltrimethylammonium chloride, stir the reaction, cool to room temperature, then put it into a dialysis bag for dialyzing, and freeze-dry to obtain amphoteric alkali lignin. A4. Add amphoteric alkali lignin and carboxymethyl-β-cyclodextrin to N,N-dimethylformamide, stir until homogeneous, add p-toluenesulfonic acid, stir and react at 100-110℃ for 3-4h, cool to room temperature, precipitate in ethanol, wash the precipitate, dry, and obtain the complex. The complex, modified zeolite, and silane coupling agent were added to deionized water and ethanol, stirred until homogeneous, and hydrochloric acid was added to adjust the pH. The mixture was stirred and reacted, then filtered, washed, and dried to obtain the modified additive.

3. The method for preparing a cellulose fiber cationic modifier according to claim 2, characterized in that, In step A1, the mass ratio of zeolite, glucose, deionized water and potassium hydroxide solution is (2-3):(1-1.5):(20-30):(4-4.5).

4. The method for preparing a cellulose fiber cationic modifier according to claim 2, characterized in that, In step A2, the mass ratio of amino-polyethylene glycol-carboxyl group, zeolite supported on porous carbon, and deionized water is (1-1.2):(2-2.5):(70-90).

5. The method for preparing a cellulose fiber cationic modifier according to claim 2, characterized in that, In step A3, the mass ratio of lignin, deionized water and 3-chloro-2-hydroxypropyltrimethylammonium chloride is (2.5-3):(80-100):(4-5).

6. The method for preparing a cellulose fiber cationic modifier according to claim 2, characterized in that, In step A4, the mass ratio of the amphoteric alkali lignin, carboxymethyl-β-cyclodextrin, N,N-dimethylformamide and p-toluenesulfonic acid is (1-1.2):(0.6-0.8):(30-40):(0.02-0.04). In step A4, the mass ratio of the composite, modified zeolite, silane coupling agent, deionized water and ethanol is (1-1.3):(2-2.5):(0.5-0.7):(30-40):(90-100).

7. The method for preparing a cellulose fiber cationic modifier according to claim 1, characterized in that, In step S1, the mass ratio of methacryloyloxyethyltrimethylammonium chloride, acrylamide, glycidyl methacrylate, modifying agent, initiator and deionized water is (3-4):(4-5):(2-3):(1-2):(0.02-0.05):(50-60).

8. The method for preparing a cellulose fiber cationic modifier according to claim 1, characterized in that, In step S1, the initiator is composed of potassium persulfate and sodium bisulfite mixed in a mass ratio of 1:(0.3-0.4).

9. The method for preparing a cellulose fiber cationic modifier according to claim 1, characterized in that, In step S2, the mass ratio of the mixture to ethanol is 1:(1.3-1.4).

10. A cellulose fiber cationic modifier prepared by the method of preparing the cellulose fiber cationic modifier according to any one of claims 1-9.

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