Highly durable and washable nylon fiber hydrophilic agent, and preparation method and application thereof

Abstract

The application discloses a kind of efficient durable washable nylon fiber hydrophilic agent and its preparation method and application, including steps: polyether amine prepolymer preparation: polyethylene glycol diglycidyl ether, dibasic amine, antioxidant is added to reactor, temperature is raised to 80-100 ℃ backflow reaction 1-3h;Preparation of nylon fiber hydrophilic agent containing polyamide structure: to the reaction product of step (1), dibasic acid is added, temperature is raised to 160-180 ℃ distillation until acid value is constant, temperature is reduced to 100 ℃;Emulsification of nylon fiber hydrophilic agent: to the product of step (2), emulsifying agent is added, stirring is uniform, 80-90 ℃ dropwise water is added to adjust solid content to 10-50%, temperature is reduced, and pH adjusting agent is added to adjust pH to 3-5.The nylon fiber hydrophilic agent of the application has excellent hydrophilicity, can be crystallized with nylon fiber molecule, improve the hydrophilicity of nylon fiber and have durable washability.

Description

Technical Field

[0001] This invention relates to a highly efficient, durable, and washable hydrophilic agent for nylon fibers, its preparation method, and its application, belonging to the field of textile printing and dyeing technology. Background Technology

[0002] Nylon fiber fabrics are soft, abrasion-resistant, dyeable, lightweight, and elastic, making them widely used in various textiles. However, nylon fibers are hydrophobic, resulting in poor wearing comfort, especially when sweating, leading to difficulty in wicking away sweat and a stuffy, uncomfortable feeling. Therefore, hydrophilic treatment of nylon fibers is particularly important. There are generally four methods for hydrophilic treatment of nylon fibers: ① copolymerization or blending with hydrophilic components; ② imparting hydrophilicity to nylon fibers through graft polymerization; ③ imparting hydrophilicity by altering the surface physical structure of nylon fibers; ④ imparting hydrophilicity to nylon fibers through finishing copolymerization. The first three methods require sophisticated equipment and are expensive. They also present challenges such as the need to remove unreacted hydrophilic monomers and the potential alteration of the original properties of the nylon fibers. Finishing copolymerization, which imparts hydrophilicity to nylon fibers, may result in poor wash resistance, color change, and a stiffer hand feel.

[0003] Currently, the main components of hydrophilic agents for nylon fibers on the market are polyurethane-based hydrophilic finishing agents. After treatment with these hydrophilic agents, the fabric begins to have good hydrophilicity, but it is difficult to impart lasting hydrophilicity to the fabric. At the same time, the fabric generally becomes stiffer after treatment with these hydrophilic agents, affecting wearing comfort. Existing literature, "Synthesis and Application Research of Novel Polyamide Fiber Hydrophilic Finishing Agent PPAG" (Dyeing and Finishing Auxiliaries, 2012(6), 14-17, 21), reports a technical scheme for synthesizing a hydrophilic finishing agent for nylon fabrics using polyethylene glycol, maleic anhydride, adipic acid, and hexamethylenediamine. After treatment with this finishing agent, the fabric has a certain degree of hydrophilicity, but the wash resistance of the hydrophilicity is not ideal. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention provides a highly efficient and durable wash-resistant hydrophilic agent for nylon fibers, its preparation method, and its application, which improves the hydrophilicity of nylon fibers and provides durable wash resistance.

[0005] To achieve the above objectives, the present invention employs a method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers, comprising the following steps:

[0006] (1) Preparation of polyetheramine prepolymer: polyethylene glycol diglycidyl ether, diamine and antioxidant are added to a reactor and the mixture is heated to 80-100℃ and refluxed for 1-3 hours; the molar ratio of polyethylene glycol diglycidyl ether to diamine is 0.5:1 to 5:1 and the amount of antioxidant is 0.1-1% of the total mass of raw materials;

[0007] (2) Preparation of hydrophilic agent for nylon fiber containing polyamide structure: Add dicarboxylic acid to the reaction product of step (1), heat to 160-180℃ and distill until the acid value remains unchanged, then cool to 100℃; the molar ratio of the dicarboxylic acid to the diamine in step (1) is 0.5:1 to 2:1.

[0008] (3) Emulsification of nylon fiber hydrophilic agent: Add emulsifier to the product of step (2), stir evenly, add water dropwise at 80-90℃ to adjust the solid content to 10-50%, cool down, add pH adjuster to adjust pH to 3-5; the amount of emulsifier is 1-10% of the total mass of raw materials;

[0009] The total mass of the raw materials is the sum of the masses of polyethylene glycol diglycidyl ether, diamine, antioxidant, dicarboxylic acid and emulsifier.

[0010] As an improved solution, the structural formula of the polyethylene glycol diglycidyl ether is as follows: Where n is from 0 to 200. Preferably, the molecular weight is 500-6000, more preferably 500-2000.

[0011] As an improved option, the diamine is at least one selected from ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, and isophoronediamine.

[0012] As an improvement, the antioxidant is at least one of sodium hypophosphite, hypophosphite, and phosphorous acid.

[0013] As an improved option, the dicarboxylic acid is at least one of succinic acid, glutaric acid, adipic acid, octanoic acid, and azelaic acid.

[0014] As an improvement, the emulsifier is a nonionic surfactant or a cationic surfactant. The emulsifier is isomeric tridecyl alcohol polyoxyethylene ether.

[0015] As an improved solution, the pH adjuster is at least one of acetic acid, hydrochloric acid, formic acid, potassium hydroxide, and sodium hydroxide.

[0016] In addition, the present invention also provides a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers prepared by the aforementioned preparation method.

[0017] Finally, the present invention also provides an application of the aforementioned high-efficiency, durable, and washable nylon fiber hydrophilic agent, wherein the nylon fiber hydrophilic agent is diluted with water to a solid content of 0.1-10%, and applied to nylon fibers and their blended fabrics by methods such as coating, impregnation, padding, spraying, pad dyeing, and roller coating.

[0018] The principle of this invention is as follows: By reacting polyethylene glycol diglycidyl ether with a diamine through a ring-opening reaction, the hydrophilic polyether is directly attached to the diamine to form a polyether amine prepolymer containing all EO, thereby giving the synthesized nylon fiber hydrophilic agent excellent hydrophilicity. The high-efficiency, durable, and wash-resistant nylon fiber hydrophilic agent of this invention contains a polyamide structure, which has a similar affinity structure to nylon fibers. During the setting process, it will crystallize with nylon fiber molecules, thus endowing nylon fibers with hydrophilic, durable, and wash-resistant properties.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] 1) The high-efficiency, durable, and washable hydrophilic agent for nylon fibers of the present invention uses a two-step reaction, which can improve the uniform distribution of molecules and greatly reduce the formation of polyamide by-product.

[0021] 2) The high-efficiency, durable, and washable hydrophilic agent for nylon fibers of the present invention has good compatibility and can be used in combination with a variety of auxiliaries without affecting the effect of other auxiliaries.

[0022] 3) The reaction of the high-efficiency, durable, and washable nylon fiber hydrophilic agent of the present invention does not involve the addition of any solvents, does not generate additional VOCs, and is environmentally friendly.

[0023] 4) The high-efficiency, durable, and wash-resistant hydrophilic agent for nylon fibers of the present invention is applicable to the refining and dyeing processes of pretreatment, as well as the finishing processes. Detailed Implementation

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0025] Example 1

[0026] A method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers includes the following steps:

[0027] (1) Assemble a dry 1L four-necked round-bottom flask with a thermocouple, mechanical stirrer, nitrogen inlet, condenser and gas outlet; add 100g polyethylene glycol diglycidyl ether (molecular weight 500) and 1.2g sodium hypophosphite into the flask, purge with nitrogen, heat to 50°C, slowly add 23.2g of 1,6-hexanediamine that has been melted within 15 minutes, slowly heat to 90°C, pay attention to cooling down during the heating process to prevent the temperature from rising rapidly, reflux at 90°C and keep warm for 2 hours;

[0028] (2) Add 29.2g of adipic acid, distill by rotation, slowly heat to 170℃, keep at 170℃ until the acid value of the product remains unchanged, and obtain a slightly yellow viscous liquid. Cool down to 100℃.

[0029] (3) Add 12.2g TO40 (BASF), stir evenly, add 371.6g water dropwise at 90℃ for 0.5h, after the water is added, stir evenly at 85℃ for 1h until the material is completely dissolved, cool down to 40℃, add 4g acetic acid to adjust the pH to 4, and obtain a nylon fiber hydrophilic agent with a solid content of 30%.

[0030] Example 2

[0031] A method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers includes the following steps:

[0032] (1) Assemble a dry 1L four-necked round-bottom flask with a thermocouple, mechanical stirrer, nitrogen inlet, condenser and gas outlet; add 175g polyethylene glycol diglycidyl ether (molecular weight 500) and 1.2g sodium hypophosphite into the flask, purge with nitrogen, heat to 50°C, slowly add 23.2g of 1,6-hexanediamine that has been melted within 15 minutes, slowly heat to 90°C, pay attention to cooling down during the heating process to prevent the temperature from rising rapidly, reflux at 90°C and keep warm for 2 hours;

[0033] (2) Add 29.2g of adipic acid, distill by rotation, slowly heat to 170℃, keep at 170℃ until the acid value of the product remains unchanged, and obtain a slightly yellow viscous liquid. Cool down to 100℃.

[0034] (3) Add 18g TO40, stir evenly, add 565.6g water dropwise at 90℃ for 0.5h, after the water is added, stir evenly at 80℃ for 1h until the material is completely dissolved, cool down to 40℃, add 4g acetic acid to adjust the pH to 4, and obtain a nylon fiber hydrophilic agent with a solid content of 30%.

[0035] Example 3

[0036] A method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers includes the following steps:

[0037] (1) Assemble a dry 1L four-necked round-bottom flask with a thermocouple, mechanical stirrer, nitrogen inlet, condenser and gas outlet; add 200g polyethylene glycol diglycidyl ether (molecular weight 2000) and 0.6g sodium hypophosphite into the flask, purge with nitrogen, heat to 50°C, slowly add 11.6g of 1,6-hexanediamine that has been melted within 15 minutes, slowly heat to 90°C, pay attention to cooling down during the heating process to prevent the temperature from rising rapidly, reflux at 90°C and keep warm for 2 hours;

[0038] (2) Add 14.6g of adipic acid, distill, slowly heat to 170℃, keep at 170℃ until the acid value of the product remains unchanged, and obtain a slightly yellow viscous liquid. Cool down to 100℃.

[0039] (3) Add 16.2g TO40, stir evenly, add 562.3g water dropwise at 90℃ for 0.5h, after the water is added, stir evenly at 83℃ for 1h until the material is completely dissolved, cool down to 40℃, add 1.5g acetic acid to adjust the pH to 4, and obtain a nylon fiber hydrophilic agent with a solid content of 30%.

[0040] Comparative Example 1

[0041] Assemble a dry 1L four-necked round-bottom flask with a thermocouple, mechanical stirrer, nitrogen inlet, condenser, and gas outlet. Add 200g of Huntsman polyetheramine ED2003 (molecular weight 2000) and 1.1g of sodium hypophosphite to the flask, purge with nitrogen, heat to 90°C, add 14.6g of adipic acid, slowly heat to 170°C, and hold at 170°C until the acid value of the product remains unchanged, resulting in a slightly yellow viscous liquid. Cool to 90°C.

[0042] Add 499.6g of water dropwise at 90℃ over 0.5h. After the water is added, stir at 83℃ for 1h until the material is completely dissolved. Cool down to 40℃ and add the solution to obtain a nylon fiber hydrophilic agent with a solid content of 30%.

[0043] Fabric treatment:

[0044] The nylon fiber hydrophilic agent of the present invention can be used in combination with other surface treatment agents. Water can be added to dilute the solid content of the nylon fiber hydrophilic agent to 0.1-10%, making it suitable for nylon fibers and their blended fabrics. Application methods include coating, impregnation, padding, spraying, pad dyeing, roller coating, or a combination of these methods.

[0045] Specific method: The nylon fiber fabric is pad-dyed by setting the concentration of solid components to 0.1-10% as the pad-dyeing bath. Next, excess liquid is removed with a sizing roller. Drying is usually carried out at a temperature of 80-190°C for 1 minute to 1 hour, preferably at 170°C for about 2-3 minutes to set the drying temperature, thereby obtaining the treated fabric. The treated fabric is then placed at room temperature to rehydrate and the hydrophilicity effect is rated.

[0046] Washability test method:

[0047] The treated fabric is placed in a washing machine and washed with 40°C detergent for 25 minutes (5 minutes * HL, 5 times consecutively), followed by 3 minutes of spin drying, 2 minutes of rinsing, 3 minutes of spin drying, 2 minutes of rinsing, 3 minutes of spin drying, tumble drying, and then oven drying. The hydrophilicity effect is rated. This program is repeated twice, and the hydrophilicity effect is tested after 10 washes.

[0048] Following the above method, the hydrophilic agent for nylon fibers prepared in each embodiment of the present invention was used to prepare an aqueous solution of 10 g / L, and the nylon fabric was treated. The hydrophilicity test results are shown in Table 1.

[0049] Table 1. Hydrophilicity and durable wash resistance of the nylon fiber hydrophilic agents in each embodiment.

[0050] Dosage - 10g / L 10g / L 10g / L 10g / L Wash resistance (L-0) >2min <1 second <1 second <1 second 12 seconds Wash resistance (L-5) >2min 1 second <1 second 1 second 58 seconds Wash resistance (L-10) >2min 1 second 1 second 2 seconds >2min

[0051] As can be seen from the analysis of Table 1, the hydrophilic agent for nylon fibers of the present invention has better hydrophilicity and durable wash resistance than the hydrophilic agent for nylon fibers synthesized by conventional polyetheramine.

[0052] Preparation of multi-component copolymer silicone oil PN: A dry 1L four-necked round-bottom flask was assembled with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet; 200g of terminal epoxy silicone oil (molecular weight 10000), 18g of Huntsman polyetheramine ED600 (molecular weight 600), and 218g of isopropanol were added to the flask, the temperature was slowly raised to 80℃, and kept at 80℃ for 5h. The temperature was then lowered to room temperature to obtain a transparent liquid with a content of 50%.

[0053] Preparation of multi-component copolymer silicone oil emulsion EPN: Add 100g of the multi-component copolymer silicone oil PN obtained above to a beaker. In another beaker, add 1g of acetic acid and 65.7g of water and mix well. While stirring rapidly, slowly add acid water to the beaker containing the multi-component copolymer silicone oil PN until emulsification is uniform, and obtain a 30% bluish milky white liquid.

[0054] The nylon fiber hydrophilic agent of the present invention was mixed with the multi-component copolymer silicone oil emulsion EPN according to the dosages described in Table 2, and then a working solution of 20 g / L was prepared. The nylon fabric was then treated, and the results of the hand feel and hydrophilicity test are shown in Table 2.

[0055] Table 2. Performance of nylon fabrics post-treated with the hydrophilic agent compounded with silicone oil emulsion of the present invention.

[0056]

[0057] As can be seen from Table 2, the nylon fiber hydrophilic agent of the present invention, when combined with silicone oil emulsion, has little impact on the feel and still has excellent hydrophilicity and washability.

[0058] In summary, this invention introduces hydrophilic polyether blocks into polyamide molecules, thereby giving the synthesized nylon fiber hydrophilic agent excellent hydrophilicity. At the same time, the hydrophilic agent molecule has a polyamide structure, which has a similar affinity structure to nylon fibers, and can crystallize with nylon fiber molecules, thereby improving the hydrophilicity of nylon fibers and giving them durable wash resistance.

[0059] Furthermore, those skilled in the art will understand that although some embodiments described herein include certain features found in other embodiments but not others, combinations of features from different embodiments are also within the scope of protection of this invention and form different embodiments. For example, in the embodiments described above, those skilled in the art can use them in combination based on known technical solutions and the technical problems to be solved by this application.

Claims

1. A method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers, characterized in that, Includes the following steps: (1) Preparation of polyetheramine prepolymer: polyethylene glycol diglycidyl ether, diamine, and antioxidant are added to a reactor and refluxed at 80-100℃ for 1-3 hours; the molar ratio of polyethylene glycol diglycidyl ether to diamine is 0.5:1 to 5:1, and the amount of antioxidant is 0.1-1% of the total mass of raw materials; (2) Preparation of hydrophilic agent for nylon fiber containing polyamide structure: Add dicarboxylic acid to the reaction product of step (1), heat to 160-180℃ and distill until the acid value remains unchanged, then cool to 100℃; the molar ratio of the dicarboxylic acid to the diamine in step (1) is 0.5:1 to 2:1; (3) Emulsification of nylon fiber hydrophilic agent: Add emulsifier to the product of step (2), stir evenly, add water dropwise at 80-90℃ to adjust the solid content to 10-50%, cool down, add pH adjuster to adjust pH to 3-5; the amount of emulsifier is 1-10% of the total mass of raw materials; The total mass of the raw materials is the sum of the masses of polyethylene glycol diglycidyl ether, diamine, antioxidant, dicarboxylic acid and emulsifier. The structural formula of the polyethylene glycol diglycidyl ether is as follows: , where n is 0 to 200, and the molecular weight is 500-6000; The diamine is at least one selected from ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, and isophoronediamine. The antioxidant is at least one of sodium hypophosphite, hypophosphite, and phosphorous acid. The dicarboxylic acid is at least one of succinic acid, glutaric acid, adipic acid, octanoic acid, and azelaic acid.

2. The method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers according to claim 1, characterized in that, The emulsifier is a nonionic surfactant or a cationic surfactant.

3. The method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers according to claim 1, characterized in that, The emulsifier used is tridecyl alcohol polyoxyethylene ether.

4. The method for preparing a highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers according to claim 1, characterized in that, The pH adjuster is at least one of acetic acid, hydrochloric acid, formic acid, potassium hydroxide, and sodium hydroxide.

5. A highly efficient, durable, and wash-resistant hydrophilic agent for nylon fibers prepared by the preparation method according to any one of claims 1-4.

6. The application of the highly efficient, durable, and wash-resistant nylon fiber hydrophilic agent according to any one of claims 1-5, characterized in that, The nylon fiber hydrophilic agent is diluted with water to a solid content of 0.1-10%, and then applied to nylon fibers and their blended fabrics by methods such as coating, impregnation, padding, spraying, pad dyeing, and roller coating.

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