Preparation method and application of performance-adjustable reactive cationic polymer

Abstract

The application relates to a preparation method and application of a performance-adjustable reactive cationic polymer, and belongs to the field of textile printing and dyeing. The preparation method of the performance-adjustable reactive cationic polymer comprises the following process steps: mixing an epoxy reactive monomer with concentrated hydrochloric acid, reacting for a certain time under ice bath, and adjusting the pH of the reaction system to be neutral; adding a cationic monomer into the above reaction system, simultaneously adding a phase transfer catalyst or an organic solvent, adding an initiator drop by drop under a nitrogen atmosphere, stirring to carry out a free radical polymerization reaction, naturally cooling after the reaction is completed, and drying to obtain the reactive cationic polymer. According to the application, salt-free high-color-yield dyeing of reactive dyes can be realized when the amount of the cationic polymer is very low.

Description

Technical Field

[0001] This invention relates to a method for preparing and applying a reactive cationic polymer with adjustable properties, belonging to the field of textile printing and dyeing. Background Technology

[0002] Cotton and linen fibers, with their excellent moisture absorption, softness, comfort, breathability, and biodegradability, are important textile fibers with high market demand. Viscose, Modal, and Lyocell fibers are fibers made from natural plant raw materials (such as wood pulp and cotton linters) through chemical processing. They are regenerated cellulose fibers, possessing the moisture absorption and breathability of natural fibers while having improved dyeing performance, leading to a year-on-year increase in their use in the textile market. Meanwhile, considering the functional requirements of textile fibers such as elasticity and durability, cellulose blended fibers occupy a significant share of the textile market. Both natural fibers like cotton and linen, and regenerated fibers like Modal and Lyocell, have the structure of cellulose fibers and contain reactive hydroxyl groups; therefore, reactive dyes are the main dyes for dyeing cellulose fibers. Traditional reactive dyeing technology suffers from drawbacks such as high salt consumption, low dye fixation rate, and large wastewater volume. The resulting saline dyeing wastewater is difficult to treat and poses a significant environmental hazard. Therefore, achieving salt-free, high-fixation dyeing of cellulose fibers and their blends is a key research focus in the textile printing and dyeing industry.

[0003] Cationic modification of fibers involves introducing cations into the fiber structure through physical or chemical methods, thereby altering the fiber's electronegativity to achieve salt-free dyeing. Chemical modification utilizes the chemical reaction between cationic reagents and hydroxyl groups on the fiber to introduce cations into the fiber structure. When the modifier has a large molecular weight and contains many cationic groups, it exhibits high affinity for the fiber and is easily adsorbed onto the fiber surface. Conversely, when the modifier contains many reactive groups, it improves the reaction efficiency between the reagent and the fiber, reducing reagent hydrolysis. However, excessively high molecular weight and cationic group content may lead to poor reagent penetration, affecting the dyeing permeability. Therefore, it is necessary to investigate the effects of different cationic and reactive group contents on the effectiveness of cationic auxiliaries. Cationic polymers obtained from dimethyl diallyl ammonium chloride and allyl glycidyl ether are promising cationic auxiliaries. The polymerization reaction of these two polymers is carried out in aqueous solution. Allyl glycidyl ether has low solubility in water, resulting in low two-phase reaction efficiency with the cationic monomer. Furthermore, during polymerization, epoxy groups are prone to hydrolysis, making it difficult to control the content of reactive groups in the product. Most of the reported patents use direct aqueous solution polymerization, which fails to effectively suppress the hydrolysis of epoxy groups, resulting in insufficient epoxy group retention in the polymerization product. This affects the reactivity of the subsequent polymer and fiber. Consequently, the reported patents use a large amount of auxiliaries, leading to resource waste. Furthermore, fiber modification and dyeing are carried out at 25–35 °C with a liquor ratio of 1:100. While low temperatures reduce the possibility of epoxy group hydrolysis in the polymer and a large liquor ratio ensures uniform dyeing, the reaction rate is slower at low temperatures, resulting in longer reaction times for modification and dyeing, and lower production efficiency. Summary of the Invention

[0004] The purpose of this invention is to synthesize a reactive cationic polymer that enables salt-free, high-fixation dyeing of cellulose fibers and their blends at low dosages.

[0005] A method for preparing a reactive cationic polymer with tunable properties includes the following process steps:

[0006] Epoxy reactive monomers were mixed with concentrated hydrochloric acid and reacted in an ice bath for a certain time, adjusting the pH of the reaction system to neutral. Cationic monomers were then added to the reaction system, along with a phase transfer catalyst or organic solvent. An initiator was added dropwise under a nitrogen atmosphere, and the mixture was stirred to carry out a free radical polymerization reaction. After the reaction was completed, the mixture was allowed to cool naturally and dried to obtain a reactive cationic polymer. The epoxy reactive monomer is one of allyl glycidyl ether, 4-vinylbenzyl glycidyl ether, and glycidyl methacrylate. The cationic monomer is dimethyl diallyl ammonium chloride, allyl trimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, (3-acrylamidopropyl)trimethyl ammonium chloride, methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride. N,N -Dimethylallylamine, N One of the methyldiallylamines.

[0007] In the above technical solution, epoxy reactive monomers are mixed with concentrated hydrochloric acid, and the epoxy groups undergo a ring-opening reaction to be converted into chlorohydrin groups.

[0008] Furthermore, the molar ratio of the epoxy reactive monomer to HCl in concentrated hydrochloric acid is 1.25:1 to 1:1.5.

[0009] Furthermore, the concentration of the concentrated hydrochloric acid is 36% to 37%.

[0010] Furthermore, the epoxy reactive monomers are mixed with concentrated hydrochloric acid and reacted in an ice bath for 10 to 60 minutes.

[0011] Furthermore, the pH of the reaction system was adjusted to neutral using NaOH solution, with a concentration of 2 mol / L to 8 mol / L.

[0012] Furthermore, the molar ratio of the epoxy reactive monomer to the cationic monomer is 1:10 to 4:1.

[0013] Furthermore, the total concentration of the epoxy reactive monomer and the cationic monomer is controlled within the range of 20 wt% to 60 wt%.

[0014] In the method of this invention, the reaction system in which the polymerization reaction occurs is a pure water system or a solution system composed of water and an organic solvent. When a pure water system is used, a phase transfer catalyst is added to the reaction solution, and the total concentration of all monomers in the polymerization reaction (the epoxy reactive monomers and cationic monomers) is controlled within the range of 20 wt% to 60 wt% by adjusting the amount of water. When a solution system composed of water and an organic solvent is used, the total concentration of all monomers in the polymerization reaction is controlled within the range of 20 wt% to 60 wt% by adding an organic solvent, and the amount of organic solvent in the polymerization reaction system is ensured to be 10% to 50% of the water mass.

[0015] Furthermore, the phase transfer catalyst is one or a combination of two or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, polyethylene glycol, and 18-crown ether-6.

[0016] Furthermore, the amount of the phase transfer catalyst is 0.5% to 4% of the total mass of the cationic monomer and the epoxy reactive monomer.

[0017] Further, the organic solvent is ethanol, isopropanol, acetone, etc. N,N One of the dimethylformamides.

[0018] Furthermore, the initiator is one of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisobutyramidine hydrochloride, azobisisobutyramidine imidazoline hydrochloride, and potassium persulfate-sodium bisulfite.

[0019] Furthermore, the initiator is added to the polymerization reaction system in the form of an initiator aqueous solution, and the amount of water in the reaction system can be controlled by controlling the concentration of the initiator aqueous solution, thus ensuring that the monomer concentration in the polymerization reaction system is within an appropriate range.

[0020] Furthermore, the amount of initiator used is 0.5% to 10% of the total mass of the monomer, and the dropping rate is 0.1 mL / min to 10 mL / min.

[0021] Furthermore, the free radical polymerization reaction temperature is 35 ℃~80 ℃, and the reaction time is 4 h~24 h.

[0022] Furthermore, after the free radical polymerization reaction is completed, the product is allowed to cool naturally, then poured into acetone to precipitate the product. After filtration, the product is dried under vacuum at 30 °C.

[0023] Another object of the present invention is to provide a method for cationizing cellulose fibers using the above-described reactive cationic polymer with tunable properties.

[0024] A method for cationizing cellulose fibers, characterized in that the cellulose fibers are placed in a modified solution of a prepared reactive cationic polymer for a period of time to obtain cationized cellulose fibers.

[0025] Furthermore, the concentration of the reactive cationic polymer in the modified solution is 0.3 g / L to 8 g / L.

[0026] Furthermore, the cellulose fiber is one of cotton fiber, linen fiber, viscose fiber, modal fiber, or lyocell fiber.

[0027] Furthermore, the modified solution also includes additives, which are one or a combination of two or more of sodium hydroxide, potassium hydroxide, and sodium carbonate, and the concentration of the additives is 0.5 g / L to 8 g / L.

[0028] Furthermore, the bath ratio of the cellulose fibers to the modified solution is 1:6 to 1:20.

[0029] Furthermore, the specific treatment method is as follows: first, treat at 10 ℃~30 ℃ for 10~40 min, then raise the temperature to 50 ℃~100 ℃ at a heating rate of 0.5 ℃~3 ℃ and treat for 10~60 min, with a bath ratio of 1:6~1:20.

[0030] Another object of the present invention is to provide a method for salt-free dyeing of cationized cellulose fibers.

[0031] A salt-free reactive dyeing method involves placing the prepared cationic cellulose fibers in a dye bath, first treating them at 10℃~30℃ for 5~60 min, then raising the temperature to 60℃~90℃ at a rate of 0.5℃~3℃ and treating them for 10~100 min. The bath ratio is 1:4~1:20, the dye concentration in the dye bath is 1%~6%, and sodium carbonate is added to the dye bath at a concentration of 0 g / L~20 g / L.

[0032] The beneficial effects of this invention are as follows: This invention provides a method for synthesizing a reactive cationic polymer with adjustable performance, and uses the polymer for cationic modification of cellulose fibers, achieving salt-free, high-fixation dyeing of reactive dyes with very low amounts of cationic polymer. Firstly, before the free radical polymerization reaction, concentrated hydrochloric acid and epoxy-based reactive monomers are reacted to convert epoxy groups to chlorohydrin groups, increasing the water solubility of the monomers and allowing the entire polymerization system to proceed in a more homogeneous aqueous solution, which is beneficial for promoting the copolymerization reaction and simultaneously protecting the epoxy groups. Secondly, cationic polymers with different reactive group contents and different cationic contents are prepared. Finally, the prepared reactive cationic polymer is used for fiber pretreatment. After treatment, the fibers achieve effective dye adsorption and high-efficiency fixation without the addition of inorganic salts. Attached Figure Description

[0033] Figure 1 The salt-free dyed fabric samples obtained in Examples 2, 7, and 8 are examples of dyed fabrics.

[0034] Figure 2 The infrared spectra of the original fiber and the cationic modified fiber obtained in Example 11 are shown. Detailed Implementation

[0035] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the invention, but do not limit the invention in any way.

[0036] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are commercially available unless otherwise specified.

[0037] In the following examples, the concentration of concentrated hydrochloric acid used is 36% to 37%. The molar ratio of epoxy reactive monomer to concentrated hydrochloric acid mentioned in the examples refers to the molar ratio of epoxy reactive monomer to solute in concentrated hydrochloric acid.

[0038] In the following examples, "total monomer mass" refers to the sum of the mass of cationic monomers and the mass of epoxy reactive monomers.

[0039] Comparative Example 1 (1) Preparation of cationic polymers Dimethyl diallyl ammonium chloride and allyl glycidyl ether were added to a three-necked flask at a mass ratio of 7.5:1. Potassium persulfate, accounting for 1% of the total mass of the monomers, was added at once as an initiator. The mixture was stirred at 80 °C for 6 h. The mixture was then removed, allowed to cool naturally to room temperature, and acetone was added to precipitate the product. The product was then dried under vacuum at 50 °C.

[0040] (2) Fiber pretreatment The synthesized cationic polymer was prepared into a cationic polymer aqueous solution with a concentration of 0.7 g / L using deionized water, and sodium hydroxide solution was added to adjust its pH value to 13. Cotton fabric was then immersed in the solution at a bath ratio of 1:100, maintained at 25 ℃, and slowly stirred for 6 h. The fabric was then removed and washed with water until neutral.

[0041] (3) Salt-free dyeing with reactive dyes Reactive blue KN-R (color intensity 3%) was used at a liquor ratio of 1:30. The dye was immersed at 25 ℃ for 0.5 h, then slowly heated to 35 ℃, and 15 g / L sodium carbonate was added for fixation for 4 h. The dye was then washed with water and soaped with a 1 g / L soap flake aqueous solution at 95 ℃ for 10 min. After washing with water, the dye was air-dried. The dye fixation rate was 85.2%.

[0042] Example 1 (1) Preparation of cationic polymers A certain amount of allyl glycidyl ether and concentrated hydrochloric acid were added to a three-necked flask at a molar ratio of 1:1.3. After reacting in an ice bath for 1 h, 3-chloro-2-hydroxypropyl allyl ether was obtained. The mixture was then adjusted to neutral with NaOH (8 mol / L). Dimethyl diallyl ammonium chloride and benzyl triethyl ammonium chloride were then added to the three-necked flask. The amount of both dimethyl diallyl ammonium chloride and allyl glycidyl ether was 0.1 mol, with a molar ratio of 1:1. The amount of benzyl triethyl ammonium chloride was 2% of the total monomer mass. After heating to 65 °C, azobisisobutyramidine hydrochloride, an initiator, was added to the three-necked flask at a molar ratio of 2% of the total monomer mass. 12 g of water was used to dissolve the initiator, with a concentration of 45.97 g / L. The mixture was stirred at a constant temperature for 20 h. After the reaction was completed, the mixture was allowed to cool naturally. The reaction product was poured into acetone to precipitate the product. After filtration, the product was dried under vacuum at 30 °C. The product was prepared into a solution of a certain concentration for later use. The polymer had a cationic content of 1.635 mmol / g, a reactive group content of 4.884 mmol / g, and a weight-average molecular weight of 2733 g / mol.

[0043] (2) Fiber pretreatment Weigh 2 g of cotton fiber and a certain amount of polymer to prepare a concentration of 2.6 g / L. The modification bath ratio is 10:1, the amount of sodium hydroxide is 2 g / L, and the mixture is treated at 30 ℃ for 30 min. Then, the temperature is increased to 70 ℃ at a rate of 2 ℃ / min, and the treatment is continued for 40 min to obtain cationic fiber.

[0044] (3) Salt-free dyeing with reactive dyes A dye bath for Reactive Red M-3BE (2% chroma) was prepared with a dyeing liquor ratio of 20:1. The cationic modified fibers were placed in the dye bath and reacted at 30 °C for 30 min. The temperature was then increased to 60 °C at a rate of 2 °C / min, and the reaction continued for another 40 min. The fibers were then soaped with a 2 g / L soap flake aqueous solution at 95 °C for 10 min, rinsed with water, and air-dried. The dye fixation rate was 92.4%.

[0045] Example 2 (1) Preparation of cationic polymers Same as Example 1.

[0046] (2) Fiber pretreatment Weigh 2 g of cotton fiber and a certain amount of polymer to prepare a concentration of 1.6 g / L. The modification bath ratio is 9:1, the amount of sodium hydroxide is 2 g / L, and the mixture is treated at 30 ℃ for 30 min. Then, the temperature is increased to 70 ℃ at a rate of 2 ℃ / min, and the treatment is continued for 40 min to obtain cationic fiber.

[0047] (3) Salt-free dyeing with reactive dyes The dye used was Reactive Yellow M-3RE (1% chroma), the dyeing bath ratio was 20:1, and the procedure was the same as in Example 1. The final dye fixation rate was 91.2%.

[0048] Example 3 (1) Preparation of cationic polymers A certain amount of allyl glycidyl ether and concentrated hydrochloric acid were added to a three-necked flask at a molar ratio of 1:1.2. After reacting in an ice bath for 1 h, 3-chloro-2-hydroxypropyl allyl ether was obtained. The mixture was then adjusted to neutral with NaOH (8 mol / L). Allyl trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, and benzyl triethylammonium chloride were then added to the three-necked flask. The amounts of (3-acrylamidopropyl)trimethylammonium chloride, allyl trimethylammonium chloride, and allyl glycidyl ether were 0.04 mol, 0.04 mol, and 0.1 mol, respectively, at a molar ratio of 1:1:2.5. The amount of benzyl triethylammonium chloride was 1% of the total monomer mass. After heating to 65 °C, azobisisobutyramidine hydrochloride, an initiator, was added to the three-necked flask at a molar ratio of 2% of the total monomer mass. 12 g of water was used to dissolve the initiator, resulting in a concentration of 41.92%. The reaction mixture was stirred at a constant temperature for 24 h at a concentration of g / L. After the reaction was completed, the mixture was allowed to cool naturally, and the product was poured into acetone to precipitate. After filtration, the product was dried under vacuum at 30 °C. The product was then prepared into a solution of a specific concentration for later use. The cationic content of the polymer was 2.492 mmol / g.

[0049] (2) Fiber pretreatment The polymer dosage was 4.0 g / L, the sodium hydroxide dosage was 2.5 g / L, the modification bath ratio was 8:1, and the treatment was carried out at 30 °C for 30 min. Then the temperature was increased to 70 °C at a rate of 2 °C / min, and the treatment was continued for 40 min to obtain cationic fibers.

[0050] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (2% chroma), and the dyeing bath ratio was 20:1. The procedure was the same as in Example 1. The final dye fixation rate was 96.8%.

[0051] Example 4 (1) Preparation of cationic polymers The difference between the preparation of the cationic polymer and Example 1 is that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1.2, the initiator used was 1% of the total monomer mass, and the amount of water used to dissolve the initiator was 6 g with a concentration of 45.97 g / L. All other operations were the same. The polymer had a cationic content of 2.818 mmol / g, a reactive group content of 3.612 mmol / g, and a weight-average molecular weight of 2962 g / mol.

[0052] (2) Fiber pretreatment The polymer dosage was 1.8 g / L, the sodium hydroxide dosage was 1.8 g / L, and the operation was the same as in Example 2.

[0053] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (color intensity 2%), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the dye fixation rate was 90.4%.

[0054] Example 5 (1) Preparation of cationic polymers Same as Example 4.

[0055] (2) Fiber pretreatment The polymer dosage was 2.2 g / L, the sodium hydroxide dosage was 2.2 g / L, and the operation was the same as in Example 2.

[0056] (3) Salt-free staining The dye used for dyeing was Reactive Blue KN-R (3% chroma), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the dye fixation rate was 92.3%.

[0057] Example 6 (1) Preparation of cationic polymers The preparation of the cationic polymer differed from that in Example 1 in that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1.2, the reaction temperature was different, and the type of initiator was also different. The reaction temperature was 45 °C, and the initiator was potassium persulfate-sodium bisulfite, used at 2% of the total monomer mass. Potassium persulfate and sodium bisulfite were added to the reaction system separately, with 12 g of water used for dissolution, at concentrations of 45.97 g / L and 27.58 g / L, respectively. All other operations were the same. The polymer had a cationic content of 2.994 mmol / g and a reactive group content of 3.424 mmol / g.

[0058] (2) Fiber pretreatment The polymer dosage was 1.8 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 3.

[0059] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (color intensity 2%), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the dye fixation rate was 98.9%.

[0060] Example 7 (1) Preparation of cationic polymers The preparation of the cationic polymer differed from that in Example 1 in that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1.2, the monomer ratio and the amount of benzyl triethyl ammonium chloride were different. The amounts of dimethyl diallyl ammonium chloride and allyl glycidyl ether were 0.2 mol and 0.1 mol, respectively, with a molar ratio of 2:1. The amount of benzyl triethyl ammonium chloride was 1.3% of the total monomer mass. Other operations were the same. The cationic content of the polymer was 4.444 mmol / g, and the reactive group content was 1.868 mmol / g.

[0061] (2) Fiber pretreatment The polymer dosage was 1.5 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 2.

[0062] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (color intensity 2%), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 96.1%.

[0063] Example 8 (1) Preparation of cationic polymers Same as Example 7.

[0064] (2) Fiber pretreatment The polymer dosage was 1.6 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 2.

[0065] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Blue KN-R (3% chroma), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 97.3%.

[0066] Example 9 (1) Preparation of cationic polymers The preparation of the cationic polymer differed from that in Example 1 in that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1; all other operations were the same. The polymer had a cationic content of 3.386 mmol / g, a reactive group content of 3.005 mmol / g, and a weight-average molecular weight of 26144 g / mol.

[0067] (2) Fiber pretreatment The polymer dosage was 1.4 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 3.

[0068] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (2% chroma), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 87.4%.

[0069] Example 10 (1) Preparation of cationic polymers The preparation of the cationic polymer differed from that in Example 1 in that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1.2, and the amount of benzyltriethylammonium chloride was 4% of the total monomer mass; all other operations were the same. The polymer had a cationic content of 4.742 mmol / g and a reactive group content of 1.548 mmol / g.

[0070] (2) Fiber pretreatment The polymer dosage was 1 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 2.

[0071] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (color intensity 2%), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 95.0%.

[0072] Example 11 (1) Preparation of cationic polymers Same as Example 10.

[0073] (2) Fiber pretreatment The polymer dosage was 1.25 g / L, the sodium hydroxide dosage was 2.5 g / L, and the operation was the same as in Example 1.

[0074] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Blue KN-R (3% chroma), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 94.7%.

[0075] Example 12 (1) Preparation of cationic polymers A certain amount of allyl glycidyl ether and concentrated hydrochloric acid were added to a three-necked flask at a molar ratio of 1:1.2. After reacting in an ice bath for 30 min, 3-chloro-2-hydroxypropyl allyl ether was obtained. The mixture was then adjusted to neutral with NaOH (8 mol / L). Vinylbenzyltrimethylammonium chloride and benzyltriethylammonium chloride were then added to the three-necked flask. The amount of vinylbenzyltrimethylammonium chloride and allyl glycidyl ether was 0.05 mol each, with a molar ratio of 1:1. The amount of benzyltriethylammonium chloride was 2% of the total monomer mass. After heating to 60 °C, azobisisobutyramidine hydrochloride, an initiator, was added to the three-necked flask at a molar ratio of 2% of the total monomer mass. 12 g of water was used to dissolve the initiator, with a concentration of 27.15 g / L. The mixture was then stirred at 65 °C for 20 h. After the reaction was completed, the mixture was allowed to cool naturally. The reaction product was poured into acetone to precipitate the product. After filtration, the product was dried under vacuum at 30 °C. The product is prepared into a solution of a certain concentration for later use.

[0076] (2) Fiber pretreatment The polymer dosage was 1.5 g / L, the sodium hydroxide dosage was 2.2 g / L, and the operation was the same as in Example 3.

[0077] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (2% chroma), the dyeing bath ratio was 20:1, the operation was the same as in Example 1, and the final dye fixation rate was 86.6%.

[0078] Example 13 (1) Preparation of cationic polymers The difference between the preparation of the cationic polymer and Example 1 is that the molar ratio of allyl glycidyl ether to concentrated hydrochloric acid was 1:1.2, the initiator used was 3% of the total monomer mass, and the amount of water used to dissolve the initiator was 18 g with a concentration of 45.97 g / L. All other operations were the same. The cationic content of the polymer was 4.744 mmol / g, and the reactive group content was 4.527 mmol / g.

[0079] (2) Fiber pretreatment The polymer dosage was 1 g / L, the sodium hydroxide dosage was 2 g / L, and the operation was the same as in Example 1.

[0080] (3) Salt-free dyeing with reactive dyes The dye used for dyeing was Reactive Red M-3BE (color intensity 2%), the dyeing bath ratio was 20:1, the amount of sodium carbonate used was 10 g / L, the operation was the same as in Example 1, and the final dye fixation rate was 87.0%.

[0081] Table 1. Comparison of water consumption, time, and auxiliary agent dosage for treating 1 kg of fabric in the comparative example and the example.

[0082] This invention first reacts concentrated hydrochloric acid with epoxy-based reactive monomers before polymerization to convert epoxy groups into chlorohydrin forms, and prepares polymers with different cationic and reactive group contents, ultimately reducing the required amount of cationic polymer. Table 1 compares the water consumption, time, and additive dosage required to treat 1 kg of fabric in the comparative examples and embodiments provided by this invention.

Claims

1. A method for preparing a reactive cationic polymer with tunable properties, comprising the following process steps: Epoxy reactive monomers were mixed with concentrated hydrochloric acid and reacted in an ice bath for a certain time, adjusting the pH of the reaction system to neutral. Cationic monomers were then added to the reaction system, along with a phase transfer catalyst or organic solvent. An initiator was added dropwise under a nitrogen atmosphere, and the mixture was stirred to carry out a free radical polymerization reaction. After the reaction was completed, the mixture was allowed to cool naturally and dried to obtain a reactive cationic polymer. The epoxy reactive monomer is one of allyl glycidyl ether, 4-vinylbenzyl glycidyl ether, and glycidyl methacrylate. The cationic monomer is dimethyl diallyl ammonium chloride, allyl trimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, (3-acrylamidopropyl)trimethyl ammonium chloride, methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride. N,N -Dimethylallylamine, N One of the 1, methyldiallylamine.

2. The method according to claim 1, characterized in that, The molar ratio of the epoxy reactive monomer to HCl in concentrated hydrochloric acid is 1.25:1 to 1:1.5; the molar ratio of the epoxy reactive monomer to the cationic monomer is 1:10 to 4:1; and the total concentration of the epoxy reactive monomer and the cationic monomer is controlled within the range of 20 wt% to 60 wt%.

3. The method according to claim 1, characterized in that, The initiator is one of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisobutyramidine hydrochloride, azobisisobutyramidine imidazoline hydrochloride, and potassium persulfate-sodium bisulfite. The amount of initiator is 0.5% to 10% of the total mass of the cationic monomer and the epoxy reactive monomer, and the dropping rate is 0.1 mL / min to 10 mL / min.

4. The method according to claim 1, characterized in that, The phase transfer catalyst is one or a combination of two or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, polyethylene glycol, and 18-crown ether-6, and is used in an amount of 0.5% to 4% of the total mass of the cationic monomer and the epoxy reactive monomer. The organic solvent is ethanol, isopropanol, acetone, N,N One of the dimethylformamides, wherein the amount of organic solvent in the reaction system is 10% to 50% of the mass of water.

5. The method according to claim 1, characterized in that, The free radical polymerization reaction temperature is 35 ℃~80 ℃, and the reaction time is 4 h~24 h.

6. A method for cationizing cellulose fibers, characterized in that, Cellulose fibers are placed in a modified solution containing a reactive cationic polymer prepared by any one of claims 1 to 5 for a period of time to obtain cationic cellulose fibers.

7. The method according to claim 6, characterized in that, The cellulose fiber is one of cotton fiber, linen fiber, viscose fiber, modal fiber, or lyocell fiber.

8. The method according to claim 6, characterized in that, The modified solution also includes additives, which are one or a combination of two or more of sodium hydroxide, potassium hydroxide, and sodium carbonate, and the concentration of the additives is 0.5 g / L to 8 g / L.

9. The method according to claim 6, characterized in that, The specific treatment method is as follows: first, treat at 10 ℃~30 ℃ for 10~40 min, then raise the temperature to 50 ℃~100 ℃ at a heating rate of 0.5 ℃~3 ℃ and treat for 10~60 min, with a bath ratio of 1:6~1:

20.

10. A salt-free dyeing method for reactive dyes, characterized in that, The cationic cellulose fibers obtained by the method according to any one of claims 6 to 9 are placed in a dye bath and treated at 10 ℃ to 30 ℃ for 5 to 60 min. Then, the temperature is raised to 60 ℃ to 90 ℃ at a heating rate of 0.5 ℃ to 3 ℃ and treated for 10 to 100 min. The bath ratio is 1:4 to 1:

20. The color of the dye in the dye bath is 1% to 6%. Sodium carbonate is added to the dye bath, and the amount of sodium carbonate is 0 g / L to 20 g / L.

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