Sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent and its preparation method

Abstract

This invention belongs to the field of dyeing and printing auxiliaries technology, specifically relating to a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent and its preparation method. The invention provides a method for preparing a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent, using maleic anhydride, polyetheramine, adipic acid, and hexamethylenediamine as raw materials. Through an amidation polycondensation reaction, a polyether-modified polyamide condensate is obtained. Sodium bisulfite solution is added to the polyether-modified polyamide condensate, and a sulfonation reaction is carried out at 120-140°C for 3-4 hours. After the reaction, water is removed to obtain the sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent. It can improve the hydrophilicity of nylon fiber fabrics.

Description

Technical Field

[0001] This invention belongs to the field of dyeing and printing auxiliaries technology, specifically relating to a sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent and its preparation method. Background Technology

[0002] Nylon (polyamide) fiber was the first synthetic fiber to be industrially produced and is the world's second largest synthetic fiber after polyester. It is lightweight, soft to the touch, and has excellent abrasion resistance. However, the main chain of nylon fibers lacks strongly hydrophilic groups. Although relatively hydrophilic amide groups exist, they are easily crystallized and blocked due to the good planarity of the amide groups and the strong intermolecular forces between polyamide fiber chains. Therefore, nylon fiber fabrics have poor hydrophilicity and moisture absorption, with a moisture absorption rate of only 4.5% under standard conditions. They are also prone to static electricity, affecting wearing comfort. Therefore, improving the hydrophilicity of nylon fiber fabrics has become a research hotspot in the development of comfortable nylon fabrics.

[0003] Applying hydrophilic finishing agents to nylon fiber fabrics is a simple and commonly used improvement method. However, among the many hydrophilic finishing agents, acrylate-based agents cannot simultaneously achieve both hydrophilicity and softness, resulting in limited improvement in hydrophilicity. The molecular weight of polyamine-based hydrophilic finishing agents significantly impacts the finishing effect; low molecular weight agents lead to poor wash resistance, while high molecular weight agents reduce fabric softness, severely affecting hand feel and causing severe yellowing. Polyurethane-based hydrophilic finishing agents have limited applications on nylon fiber fabrics, are expensive, and offer unsatisfactory results. Polyester polyether-based hydrophilic finishing agents are mainly used on polyester fabrics, and their hydrophilicity and wash resistance on nylon are not ideal. Therefore, it is essential to develop a hydrophilic finishing agent with good hydrophilicity and certain wash resistance suitable for nylon fiber fabrics.

[0004] The paper "Synthesis and Application Performance of Polyether-Modified Polyamide Hydrophilic Finishing Agent for Nylon" describes the synthesis of a polyether-modified polyamide (PMP) finishing agent via amidation polycondensation reaction using maleic anhydride, polyetheramine, adipic acid, and hexamethylenediamine as raw materials. This agent is used for hydrophilic finishing of nylon fabrics; the resulting nylon fabric exhibits a wicking effect of 5.2 cm, and after 10 washes, the wicking effect retention rate reaches 94.23%. The prepared finishing agent demonstrates good hydrophilicity and wash resistance. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent and its preparation method.

[0006] To address the aforementioned technical problems, this invention provides a method for preparing a sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent. Using maleic anhydride, polyetheramine, adipic acid, and hexamethylenediamine as raw materials, an amidation condensation reaction is conducted to obtain a polyether-modified polyamide condensate. The method is characterized by: adding a sodium bisulfite solution (aqueous solution) to the polyether-modified polyamide condensate and subjecting it to a sulfonation reaction at 120-140°C (preferably 130°C) for 3-4 hours (preferably 3.5 hours); after the reaction, removing water (cooling down, removing water) to obtain the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent. The molar ratio of maleic anhydride to sodium bisulfite is 1:(1.1±0.05); preferably, the molar ratio of maleic anhydride to sodium bisulfite is 1:1.1.

[0007] That is, the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention introduces double bonds into the polymer and further improves the hydrophilicity of the finishing agent by grafting sulfonic acid groups onto the double bonds.

[0008] As an improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention: the mass concentration of sodium bisulfite solution is 20~40% (preferably 30%).

[0009] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention: dehydration is carried out in a vacuum oven at 70~90°C for 0.5~1h.

[0010] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention, the synthesis method of the polyether-modified polyamide condensate includes the following steps: 1) Under the protection of an inert gas (including N2), polyetheramine is added dropwise to molten maleic anhydride (maleic anhydride), and then the temperature is raised to 60±10℃ for acylation reaction for 2±0.2h to obtain bi-carboxyl-terminated polyetheramide. The molar ratio of maleic anhydride to polyetheramine is (2±0.1):1; 2) The double-terminated carboxyl polyether amide obtained in step 2) is mixed evenly with adipic acid, hexamethylenediamine, catalyst and deionized water. Under the protection of inert gas (including N2), the mixture is heated to 210~250℃ (preferably 230℃) for polycondensation reaction for 1~3h (preferably 2h). Then, under vacuum conditions (-0.08~-0.095 MPa), the mixture is kept at a constant temperature and stirred for 20~40min (to remove the water generated in the reaction). The mixture is then cooled and discharged to obtain the polyether-modified polyamide condensate. The molar ratio of adipic acid: hexamethylenediamine: polyetheramine in step 1) is (0.5~1.5):2:1 (preferably 1:2:1); the amount of deionized water added is 25~35 (preferably 30%) of the total mass of the bi-carboxyl-terminated polyether amide, adipic acid, and hexamethylenediamine; the amount of catalyst added is 1~3 wt% (preferably 2 wt%) of the total mass of the bi-carboxyl-terminated polyether amide, adipic acid, and hexamethylenediamine.

[0011] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention: in step 1), the number average molecular weight of the polyether amine is 600.

[0012] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention, the catalyst is phosphorous acid.

[0013] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention, all the above steps are carried out under stirring conditions, with the stirrer speed being 280~320 rpm.

[0014] As a further improvement to the preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention, the heating rate of the oil bath in the above steps is 1~2℃ / min.

[0015] The reaction structure of the above preparation method is as follows:

[0016]

[0017]

[0018] The present invention also provides a sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent prepared by any of the above methods.

[0019] The structural formula is as follows:

[0020] Where x+z=3.6, y=9, and n>m. The number-average molecular weight ranges from 40,000 to 48,000.

[0021] This invention also provides the application of the above-mentioned sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent in the process of finishing fabrics: Applying sulfonic acid-based polyamide polyether copolymer water-based finishing agents to fabrics can impart good hydrophilicity to the fabrics.

[0022] The fabric is a nylon fiber fabric.

[0023] Specifically: A finishing solution is prepared by dissolving a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent in water. The fabric to be finished is then quickly immersed in the solution, followed by padding, drying, and baking to complete the hydrophilic finishing process. The finishing solution dosage is 20 g / L. The padding rate is 90%. The drying temperature is 80℃, and the drying time is 5 min. The baking temperature is 170℃, and the baking time is 60 s.

[0024] The sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent prepared by this invention contains polyamide segments, polyether segments, and anionic groups (sulfonic acid groups). The polyamide segments co-crystallize with nylon fiber molecules at high temperatures, anchoring them within the nylon fibers to improve the washing resistance of the finishing agent. The polyether segments cover the surface of the nylon fibers, imparting hydrophilicity to the nylon fabric through hydrogen bonding between the polyether and water. The anionic sulfonic acid groups on the finishing agent molecular chain further enhance the hydrophilicity of the finished nylon fabric through ionization with water molecules. This invention has a relatively simple preparation process, low cost, good reproducibility, and good hydrophilicity, showing broad application prospects.

[0025] In order to address the technical deficiencies of existing hydrophilic finishing agents for nylon fiber fabrics, this invention provides a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent with good hydrophilic properties and its preparation method. The polyamide-polyether copolymer hydrophilic finishing agent imparts hydrophilicity to nylon fiber fabrics through hydrogen bonding between polyether and water; by introducing sulfonic acid groups into the polyamide-polyether copolymer molecule, the hydrophilicity of nylon fiber fabrics is further improved through the ionization effect between the sulfonic acid groups and water.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention has hydrophilic polyether segments in its molecule, which gives the finished nylon fiber fabric a certain degree of hydrophilicity; by introducing sulfonic acid groups, the hydrophilicity of the finished nylon fiber fabric is enhanced through water ionization, thereby improving the wearing performance of the nylon fiber fabric. Compared with the original nylon fiber fabric (capillary effect 2.3cm / 5min, wetting time 240s), the capillary effect of the nylon fiber fabric treated with the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent can reach up to 6.4cm / 5min, and the wetting time is 2.2s, which greatly improves the hydrophilicity of the nylon fiber fabric.

[0027] (2) The polyamide segments in the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent of the present invention are similar to the molecular structure of nylon fibers. They can co-crystallize with the fabric at high temperatures, giving the finishing agent good wash resistance. After 10 household washes, the fabric retains a high wicking effect and the wetting time is still excellent.

[0028] (3) The preparation method of the present invention is relatively simple and the reaction reproducibility is good.

[0029] In summary, the preparation method of the present invention further improves the hydrophilicity of the polyamide polyether copolymer hydrophilic finishing agent by introducing sulfonic acid groups, so that nylon fiber fabrics not only have excellent hydrophilic properties, but also have certain wash resistance; moreover, the preparation method is simple, low in cost, and has good reproducibility.

[0030] The preparation method of this invention involves first obtaining a polyether containing double-bond-terminated carboxyl groups through an acylation reaction, then mixing the polyether containing double-bond-terminated carboxyl groups, adipic acid, and hexamethylenediamine for a polycondensation reaction to prepare a polyamide-polyether block copolymer containing double bonds, and finally adding sodium bisulfite solution for sulfonation to obtain a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent. The preparation process is relatively simple, low in cost, and has good reproducibility, showing great application potential. Attached Figure Description

[0031] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0032] Figure 1 The infrared spectrum of the No. 2 sulfonic acid polyamide polyether copolymer hydrophilic finishing agent prepared in Example 1; Figure 2 The image shows the dynamic water contact angle of the nylon fiber fabric before and after treatment with the No. 2 sulfonic acid polyamide polyether copolymer hydrophilic finishing agent prepared in Example 1. Detailed Implementation

[0033] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0034] In the following embodiments: The stirring speed in steps (1) to (3) is 300-360 rpm. The heating rate of the oil bath in steps (2) to (3) is 2 to 3 °C / min.

[0035] Example 1: Preparation method of sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent (considering the selection of the molar ratio of adipic acid, hexamethylenediamine and polyether containing double-bond terminal carboxyl groups) (1) Under N2 atmosphere, 2 mol of maleic anhydride (maleic anhydride) was completely melted at 60°C, and 1 mol of polyetheramine ED600 was added dropwise under stirring (the addition was completed within 30 min). Then, the reaction was stirred at 60°C for 2 h. After the reaction was completed, 1 mol of double-terminated carboxyl polyether amide ED600 (CT-ED600) was obtained.

[0036] The number average molecular weight of polyetheramine is 600, and ED600 from Huntsman Chemicals' diamine series can be selected.

[0037] (2) At room temperature, adipic acid, 2 mol hexamethylenediamine, 1 mol of double-terminated carboxyl polyether amide ED600 obtained in step (1) and 30 wt% water (deionized water) with different molar amounts (0.5 mol, 1 mol and 1.5 mol respectively) were stirred and mixed. Under N2 atmosphere, the temperature was first raised to 170°C to remove most of the water. Then, 2 wt% phosphorous acid catalyst was added and the temperature was raised to 230°C for 2 h of polycondensation reaction. Then, under vacuum conditions (-0.08 to -0.095 MPa), the reaction was kept at the temperature and stirred for 30 min to remove the water generated in the reaction. The product was cooled and discharged to obtain polyether modified polyamide condensate (PMP). Note: The reactants consist of bicarboxyl-terminated polyether amide ED600, adipic acid, and hexamethylenediamine.

[0038] 2wt% phosphorous acid means that the amount of phosphorous acid added as a catalyst is 2% of the total weight of the reactants.

[0039] 30wt% water means that the amount of deionized water added is 30% of the total weight of the reactants.

[0040] (3) Add a 30% (w / w) sodium bisulfite aqueous solution (2.2 mol / w) to the polyether-modified polyamide condensate (PMP) obtained in step (2) at a molar ratio of maleic anhydride to sodium bisulfite of 1:1.1. Heat to 130°C and react for 3.5 h. After the reaction is complete, dry in a vacuum oven at 80°C for 1 h to remove excess moisture (until no bubbles are generated in the solution). Three sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agents were obtained.

[0041] illustrate: When the amount of adipic acid used is 0.5 mol, the resulting product is named No. 1 finishing agent; When the amount of adipic acid used is 1 mol, the resulting product is named No. 2 finishing agent; When the amount of adipic acid used is 1.5 mol, the resulting product is named No. 3 finishing agent.

[0042] The infrared spectrum of finishing agent #2 in Example 1 above is as follows: Figure 1 As shown. From Figure 1 As can be seen from this, 3267cm -1 1656cm -1 and 1548cm -1 The peaks at 1708 cm⁻¹ represent the stretching vibration peak of NH in the amide bond (-CONH-), the stretching absorption peak of C=O, and the bending vibration peak of NH, respectively. -1 The peak at 1121 cm⁻¹ represents the stretching vibration of the C=O group in the carboxyl group. -1 The peak at 2857 cm⁻¹ represents the stretching vibration peak of COC in the polyether segment. -1The peak at 1237 cm⁻¹ represents the symmetric absorption vibration of the -CH₂- group in the polyamide chain. -1 and 1036cm -1 The peaks are characteristic of sulfonic acid groups. In summary, the finishing agent macromolecular chain contains polyamide, polyether, and sulfonic acid groups.

[0043] Experiment 1: The three finishing agents obtained in Example 1 were each diluted with water to prepare a 20 g / L finishing solution. Nylon fiber fabrics were then immersed in the finishing solutions. The nylon fiber fabrics were treated using a one-dip, two-ply method (total wash rate 90%), dried at 80°C for 5 min, and then baked at 170°C for 60 s. The three finished nylon fiber fabrics were designated as #1, #2, and #3, respectively. The untreated original fabric was designated as #0.

[0044] To compare the effect of material input ratio on the hydrophilicity of the finished fabric, the wetting time of the fabric was measured according to AATCC79-2014 "Absorbency of Textiles", and the capillary height of the fabric was tested according to FZ / T01071-2008 "Test Method for Capillary Effect of Textiles". The results are shown in Table 1.

[0045] Table 1. Effect of material input ratio on the hydrophilicity of finished fabrics

[0046] n(adipic acid):n(hexamethylenediamine):n(bi-terminated carboxyl polyether amide) (mol), is equivalent to n(adipic acid):n(hexamethylenediamine):n(polyether amine) (mol).

[0047] Table 1 shows that compared with the original fabric #0, the wicking effect and wetting time of the fabrics treated with the three finishing agents were improved. Changing the amount of adipic acid affects the relative proportion of polyether and polyamide segments in the hydrophilic finishing agent. Too little adipic acid results in fewer polyamide segments, which is not conducive to the adsorption of finishing agent molecules onto the fabric surface, leading to a low content of finishing agent on the fabric and thus poor hydrophilicity. Too much adipic acid results in more polyamide segments, affecting the overall hydrophilicity of the finishing agent. When the molar ratio of adipic acid, hexamethylenediamine, and bi-carboxyl-terminated polyether amide is 1:2:1, the polyether and polyamide segments in the finishing agent are most suitable, and fabric treated with #2 exhibits the best hydrophilicity.

[0048] The dynamic water contact angle of the nylon fiber fabric before and after treatment with finishing agent #2 in Example 1 above is as follows: Figure 2 As shown. The horizontal axis represents the change in the contact angle of a water droplet (the volume of a droplet is 3 microliters) on the fabric over time; the vertical axis represents the original nylon fabric, fabric #2 prepared by the method in Experiment 1, and fabric #2 after 10 washes.

[0049] Therefore, the instantaneous water contact angles of 0# (original fabric) at room temperature at 0s, 1s, and 3s are 111.2°, 104.5°, and 102.6°, respectively. The instantaneous water contact angles of the No. 2 treated fabric at 0s, 1s, and 3s were 77.3°, 38.4°, and 0°, respectively. After washing the No. 2 fabric ten times, the instantaneous water contact angles at room temperature at 0s, 1s, and 3s were 86.9°, 73.6°, and 52.3°, respectively.

[0050] Example 2: Preparation method of sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent (considering the selection of the amount of phosphorous acid catalyst): (1) The same as step (1) in Example 1; (2) 1 mol adipic acid, 2 mol hexamethylenediamine, 1 mol of double-terminated carboxyl polyether amide ED600 obtained in step (1), different amounts (1 wt%, 2 wt%, 3 wt%) of phosphorous acid catalyst and 30 wt% water were stirred and mixed, and the mixture was heated to 230℃ for polycondensation reaction for 2 h. After the reaction was completed, polyether modified polyamide condensate (PMP) was obtained.

[0051] (3) The same as step (3) in Example 1.

[0052] When the amount of phosphorous acid catalyst is 1 wt%, the resulting product is named No. 4 finishing agent; When the amount of phosphorous acid catalyst is 2wt%, the result is the No. 2 finishing agent in Example 1; When the amount of phosphorous acid catalyst is 3wt%, the resulting product is named No. 5 finishing agent.

[0053] Experiment 2: The finishing agent obtained in Example 2 was tested in accordance with the method described in Experiment 1 to compare the effect of different catalyst dosages on the hydrophilicity of the finished fabric. The results are shown in Table 2.

[0054] Table 2. Effect of different catalyst dosages on the hydrophilic properties of finished fabrics

[0055] Table 2 shows that the hydrophilicity of all three treated fabrics was improved to varying degrees compared to the original fabric #0. Increasing the amount of catalyst helps the reaction proceed in the forward direction and accelerates the reaction rate; however, when the amount of catalyst exceeds 2 wt%, excessive catalyst leads to an increase in by-products in the reaction system, reducing the yield of the target product. Considering all factors, the finishing agent works best when the amount of catalyst is 2 wt%.

[0056] Example 3: Preparation method of sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent (considering the selection of polycondensation reaction temperature): (1) The same as step (1) in Example 1; (2) Mix 1 mol adipic acid, 2 mol hexamethylenediamine, 1 mol of double-terminated carboxyl polyether amide ED600 obtained in step (1), 2 wt% catalyst phosphorous acid and 30 wt% water, and heat to different temperatures (210℃, 230℃, 250℃) for 2 h for polycondensation reaction. After the reaction is completed, polyether modified polyamide condensate (PMP) is obtained.

[0057] (3) The same as step (3) in Example 1.

[0058] When the polycondensation reaction temperature is 210℃, the resulting product is named No. 6 finishing agent; When the polycondensation reaction temperature is 230°C, the resulting product is the No. 2 finishing agent in Example 1; When the polycondensation reaction temperature is 250℃, the resulting product is named No. 7 finishing agent.

[0059] Experiment 3: The finishing agent obtained in Example 3 was tested in accordance with the method described in Experiment 1 to compare the effect of different polycondensation reaction temperatures on the hydrophilicity of the finished fabric. The results are shown in Table 3.

[0060] Table 3. Effect of polycondensation reaction temperature on the hydrophilic properties of finished fabrics

[0061] Table 3 shows that compared with the original fabric #0, the wicking effect and wetting time of the fabrics treated with the three finishing agents were improved. Increasing the reaction temperature increased the wicking effect height and shortened the wetting time; when the reaction temperature reached 230℃, the wicking effect height of the treated fabric was the highest and the wetting time was the shortest. Further increasing the temperature significantly reduced the wicking effect height and prolonged the wetting time. This is because increasing the temperature helps accelerate the polycondensation reaction rate and promotes product formation. However, excessively high temperatures can lead to polyether pyrolysis, affecting the hydrophilicity of the fabric. Considering all factors, a polycondensation reaction temperature of 230℃ is recommended for optimal hydrophilicity.

[0062] Example 4: Preparation method of sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent (considering the selection of polycondensation reaction time) (1) The same as step (1) in Example 1; (2) After stirring and mixing 1 mol adipic acid, 2 mol hexamethylenediamine, 1 mol of double-terminated carboxyl polyether amide ED600 obtained in step (1), 2 wt% catalyst phosphorous acid and 30 wt% water, the mixture was heated to 230℃ for polycondensation reaction for different times (reaction times were 1h, 2h and 3h respectively). After the reaction was completed, polyether modified polyamide condensate (PMP) was obtained.

[0063] (3) The same as step (3) in Example 1; When the polycondensation reaction time is 1 hour, the resulting product is named No. 8 finishing agent.

[0064] When the polycondensation reaction time is 2 hours, the resulting product is the No. 2 finishing agent in Example 1.

[0065] When the polycondensation reaction time is 3 h℃, the resulting product is named No. 9 finishing agent.

[0066] Experiment 4: The finishing agent obtained in Example 4 was tested in accordance with the method described in Experiment 1 to compare the effect of different polycondensation reaction times on the hydrophilicity of the finished fabric. The results are shown in Table 4.

[0067] Table 4. Effect of polycondensation reaction time on the hydrophilic properties of finished fabrics

[0068] Table 4 shows that the hydrophilicity of all three treated fabrics was improved to varying degrees compared to the original fabric #0. Extending the reaction time increased the wicking height and shortened the wetting time. At a reaction time of 2 hours, the treated fabric exhibited the highest wicking height and the shortest wetting time. Further extending the reaction time significantly reduced the wicking height and increased the wetting time. This is because extending the reaction time increases the degree of polycondensation, making the reaction more complete. However, when the reaction time exceeds 2 hours, the sustained high temperature environment leads to the thermal degradation of the polyether, affecting the finishing effect of the finishing agent. Considering all factors, a polycondensation reaction time of 2 hours provides the best hydrophilicity.

[0069] Comparative Experiment 1: The No. 2 finishing agent obtained in Example 1, commercially available polyamide-polyether hydrophilic finishing agent, polyether-modified silicone oil hydrophilic finishing agent, and polyether-modified polyamide condensate (PMP) were tested according to the method described in Experiment 1. The treated fabrics were washed according to GB / T8629-2017 "Home Washing and Drying Procedures for Textile Testing". After each wash, the fabrics were dried in an oven at 60°C for 10 minutes. 0 washes represent nylon fabrics treated with the finishing agent, and 10 washes represent nylon fabrics after 10 washes.

[0070] The results are shown in Table 5.

[0071] Table 5. Comparison of the properties of nylon fiber fabrics treated with different hydrophilic finishing agents

[0072] As can be seen from Table 5, compared with commercially available polyamide-polyether hydrophilic finishing agents and commercially available polyether-modified silicone oil hydrophilic finishing agents, the sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent of the present invention has better hydrophilicity and wash resistance.

[0073] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a sulfonic acid-based polyamide-polyether copolymer hydrophilic finishing agent, comprising using maleic anhydride, polyetheramine, adipic acid, and hexamethylenediamine as raw materials, and obtaining a polyether-modified polyamide condensate through an amidation polycondensation reaction, characterized in that: A sodium bisulfite solution was added to the polyether-modified polyamide condensate and sulfonated at 120-140°C for 3-4 hours. After the reaction, water was removed to obtain a sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent. The molar ratio of maleic anhydride to sodium bisulfite is 1:(1.1±0.05).

2. The preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to claim 1, characterized in that: The mass concentration of sodium bisulfite solution is 20-40%.

3. The preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to claim 2, characterized in that: The dehydration process involves using a vacuum oven at 70-90°C for 0.5-1 hours.

4. The method for preparing the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to any one of claims 1 to 3, characterized in that... The synthesis method of polyether-modified polyamide condensate is as follows: 1) Under inert gas protection, polyetheramine was added dropwise to molten maleic anhydride, and then the temperature was raised to 60±10℃ for acylation reaction for 2±0.2h to obtain bi-carboxyl-terminated polyetheramide; The molar ratio of maleic anhydride to polyetheramine is (2±0.1):1; 2) The double-ended carboxyl polyether amide obtained in step 2) is mixed with adipic acid, hexamethylenediamine, catalyst and deionized water. Under inert gas protection, the mixture is heated to 210~250℃ for polycondensation reaction for 1~3h. Then, under vacuum conditions, the mixture is stirred and kept at the temperature for 20~40min. After cooling, the mixture is discharged to obtain the polyether-modified polyamide condensate. The molar ratio of adipic acid: hexamethylenediamine: polyetheramine in step 1) is (0.5~1.5):2:1; the amount of deionized water added is 25~35% of the total mass of the bi-carboxyl-terminated polyether amide, adipic acid, and hexamethylenediamine; the amount of catalyst added is 1~3 wt% of the total mass of the bi-carboxyl-terminated polyether amide, adipic acid, and hexamethylenediamine.

5. The preparation method of the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to claim 4, characterized in that, In step 1), the number average molecular weight of the polyetheramine is 600.

6. The method for preparing the sulfonate-based polyamide polyether copolymer hydrophilic finishing agent according to claim 5, characterized in that, The catalyst is phosphorous acid.

7. The method for preparing the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to claim 6, characterized in that, All the above steps are carried out under stirring conditions, with the stirrer speed being 280~320 rpm.

8. The method for preparing the sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent according to claim 7, characterized in that, The heating rate of the oil bath in the above steps is 1~2℃ / min.

9. A sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent prepared by any one of claims 1 to 8.

10. The application of sulfonic acid-based polyamide polyether copolymer hydrophilic finishing agent in the finishing process of fabrics, characterized in that: Sulfonic acid-based polyamide polyether copolymer water finishing agent is applied to the fabric to give it good hydrophilic properties.

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