Multifunctional nylon bath anti-wrinkle agent and its synthesis method and application

Abstract

This invention discloses a multifunctional anti-wrinkle agent for nylon dyeing, its synthesis method, and its application, belonging to the field of textile auxiliaries technology. The anti-wrinkle agent is a polyester polyether compound containing polymeric cashew bisphenol. Specifically, it is based on ortho-cashew bisphenol polyoxyethylene ether, which is sequentially polymerized with a polyester linker and a polyether linker. After neutralization and sulfonation, the target product is obtained. By controlling the reactant ratio and reaction process parameters, the product is made into an anionic polymer compound. In the acid dyeing process of nylon, it can be efficiently adsorbed onto the surface of nylon fibers, effectively preventing problems such as scratches, bark wrinkles, and abrasions during the dyeing process of nylon fabrics. It also significantly improves the hydrophilicity and hand feel of nylon fabrics, exhibits high stability under 98℃ dye bath conditions, and has good compatibility with weakly acidic and neutral dyes, without forming lakes, oil spots, or color stains, thus improving the overall quality of nylon fabric dyeing and finishing.

Description

Technical Field

[0001] This invention relates to the field of textile auxiliaries technology, and in particular to a multifunctional anti-wrinkle agent for nylon baths, its synthesis method, and its application. Background Technology

[0002] Nylon fiber fabrics, due to their excellent abrasion resistance, extensibility, and tensile strength, have broad application prospects in the fields of sports and outdoor fabrics, making them the second largest synthetic fiber fabric after polyester. With the domestic production of caprolactam, the monomer raw material for nylon, its output continues to increase. Thanks to its superior performance properties, nylon fabrics have become synonymous with high quality in the apparel industry, with mainstream applications including nylon-cotton Roma fabric, nylon-cotton four-way stretch, superfine denier twill, and nylon-spandex knitted fabrics.

[0003] The conventional dyeing process for nylon fabrics involves an acidic dyeing process at around 98℃. Because nylon has a relatively low glass transition temperature, during overflow dyeing, especially in air-jet dyeing, when the fabric is partially stacked and the temperature exceeds the glass transition temperature, the "shape memory" effect can cause creases such as "chicken claw marks" and the characteristic "bark wrinkles" of nylon-spandex fabrics. Simultaneously, friction between the fabric and the dyeing bath easily produces abrasions, a problem particularly pronounced in low-weight nylon twill fabrics. To address these issues, the industry typically adds in-bath anti-wrinkle agents to the dye bath. Their mechanism of action primarily involves forming a film on the fiber surface to prevent abrasions and reducing static friction during fabric stacking, thus preventing the formation of persistent creases at high temperatures. Currently, commonly used anti-wrinkle agents are mainly high-molecular-weight polyacrylamide and polyterephthalate polyether products, but both have significant drawbacks: polyacrylamide is cationic under acidic dyeing conditions for nylon and easily forms lakes with poorly water-soluble weak acid dyes and neutral dyes, resulting in color stains and spots on the fabric; water-soluble polyterephthalate polyether has poor stability in a 98℃ dye bath and is prone to self-polymerization to form oil spots, affecting the dyeing quality.

[0004] Therefore, developing a multifunctional in-bath anti-wrinkle agent that exhibits high stability and good anti-wrinkle effect in acidic dyeing baths, while also improving the hydrophilicity and hand feel of nylon fabrics, has become an urgent need for the nylon dyeing and finishing industry. Summary of the Invention

[0005] The purpose of this invention is to provide a multifunctional anti-wrinkle agent for nylon baths, its synthesis method, and its application, in order to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides a multifunctional nylon bath anti-wrinkle agent, wherein the anti-wrinkle agent is a polyester polyether compound containing polymeric cashew bisphenol A, with the following structural formula: ; Where a, b, c, and d range from 2 to 100, and m, n, and p are all ≥ 2; R is a cashew alkyl group, with the general structural formula C0.15 H 31-2x x is 1, 2 or 3.

[0007] This invention also provides a method for synthesizing the above-mentioned multifunctional anti-wrinkle agent in nylon bath, characterized by comprising the following steps: (1) Add cashew bisphenol polyether to a four-necked flask equipped with a thermometer, a constant pressure dropper and a reflux condenser, heat to 60~70℃, add solid polyester linker dropwise under nitrogen protection, heat to 115~125℃ and keep warm for 2~4 hours. (2) Cool down to 60°C, add polyether linker, and heat up to 160~180°C under nitrogen protection for 6~8 hours; (3) Cool down to 50~55℃, add deionized water and organic solvent, stir evenly, and then add alkali to adjust the pH to 5.5~6.5; (4) Heat to 95°C, add sulfonating agent, stir evenly, then heat to 110~115°C and keep warm for 3~4 hours, then cool to 35~40°C to obtain the target product.

[0008] Preferably, the proportions of each raw material by weight are as follows: 18-25 parts cashew bisphenol polyether, 5-7 parts polyester linker, 6-8 parts polyether linker, 10-15 parts organic solvent, 35-40 parts deionized water, 2-3 parts alkali agent, and 3-4 parts sulfonating agent.

[0009] Preferably, in step (1), the cashew bisphenol polyether is ortho-cashew bisphenol polyoxyethylene ether; and the polyester linker is maleic anhydride.

[0010] Preferably, in step (2), the polyether linker is polyetheramine.

[0011] Preferably, in step (3), the organic solvent is ethylene glycol or isopropanol; the alkaline agent is sodium hydroxide or potassium hydroxide.

[0012] Preferably, in step (4), the sulfonating agent is sodium bisulfite or sodium metabisulfite.

[0013] This invention also provides the application of the above-mentioned multifunctional anti-wrinkle agent in nylon bath in acid dyeing of nylon fibers.

[0014] The multifunctional anti-wrinkle agent for nylon baths of this invention uses ortho-cashew bisphenol polyoxyethylene ether as the core raw material. It is prepared through a four-step controllable reaction process: esterification polycondensation, chain extension polymerization, neutralization, and sulfonation, to produce an anionic polyester polyether sulfonate polymer containing polymeric cashew bisphenol. In the first step, the hydroxyl groups of the cashew bisphenol polyether undergo ring-opening esterification with maleic anhydride to form a carboxyl-containing polyester prepolymer. In the second step, the polyester prepolymer undergoes amidation chain extension with polyether amine at high temperature to construct a polymer backbone with both a rigid skeleton and a flexible polyether chain. In the third step, the residual carboxyl groups in the system are neutralized with alkali to adjust the pH to a weakly acidic state suitable for dyeing conditions. In the fourth step, a sulfonating agent is used to add to the unsaturated double bonds in the molecular chain, introducing a strongly hydrophilic sulfonate group and endowing the product with stable anionic properties.

[0015] Therefore, the multifunctional nylon bath anti-wrinkle agent, its synthesis method, and its application provided by this invention have the following beneficial effects: (1) The anti-wrinkle agent synthesized in this invention is an anionic polymer compound that can be efficiently adsorbed onto the surface of positively charged nylon fibers in an acidic dyeing bath, forming a dense protective film on the fiber surface, avoiding direct contact between the fiber and the dyeing vat and causing abrasions, thus effectively solving the problem of abrasion marks in nylon fabric dyeing.

[0016] (2) The long straight-chain alkyl and propylene oxide block polymer contained in the product structure can significantly reduce the static friction between fibers, avoid local stacking of fabric for a long time, and effectively suppress the generation of wrinkles such as chicken claw marks and bark wrinkles when combined with the creases formed by high temperature. The anti-wrinkle effect is significantly better than existing products.

[0017] (3) The product structure contains both ionic structure and hydrophilic segments of ethylene oxide, which gives it extremely high thermal stability. It will not undergo self-polymerization under the acidic dyeing bath conditions of nylon at 98℃, thus avoiding the formation of oil spots. It is also compatible with weak acid dyes and neutral dyes and will not form color lakes, thus completely solving the problems of color stains and color spots caused by existing anti-wrinkle agents.

[0018] (4) While the anti-wrinkle and anti-friction agent of the present invention plays an anti-wrinkle and anti-friction role, its polyether segment can give nylon fabric good hydrophilicity, and the long straight-chain alkyl can optimize the fabric feel, achieving a multi-functional effect of anti-wrinkle, hydrophilicity and improved feel, without the need to add additional hydrophilic agents and softeners, simplifying the dyeing and finishing process and reducing processing costs.

[0019] (5) The synthesis method of the present invention has simple process steps, mild and easy-to-control reaction conditions, and readily available raw materials, making it suitable for large-scale industrial production.

[0020] The technical solution of the present invention will be further described in detail below through embodiments. Detailed Implementation

[0021] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the invention should be considered equivalent substitutions and are included within the scope of protection of the invention. Furthermore, it should be understood that after reading the contents of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims and are all within the scope of protection of the invention.

[0022] In this document, the term "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The term "embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment, nor does it specifically limit its independence or connection with other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0023] Unless otherwise defined, the technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the use of related terms herein is merely for the purpose of describing particular embodiments and is not intended to limit this application.

[0024] Unless otherwise specified, the reagents, instruments, and equipment used in this invention are all commonly used by those skilled in the art, and the testing standards all use national or international standards commonly used in the field, without further explanation.

[0025] It should be noted that the anti-wrinkle agent obtained by the present invention is a high molecular polymer, and in its structural formula, a, b, c, and d represent the average number of repeating units of the corresponding polyether segments, and m, n, and p represent the average degree of polymerization of the corresponding polyester or polyether segments.

[0026] Due to the polydispersity of the polymer products, i.e., the number of repeating units in each polymer chain is not exactly the same, but is distributed within a certain range, the specific values ​​given in the following examples are based on the raw material feed ratio, reaction conversion rate and theoretically calculated number-average degree of polymerization (rounded down), and are only used to illustrate the feasibility of the present invention, and do not constitute a limitation on the scope of protection of the claims.

[0027] Example 1 This embodiment provides a multifunctional nylon bath anti-wrinkle agent and its preparation method. The mass proportions of each raw material of the anti-wrinkle agent are as follows, by weight: 25 parts of ortho-cashew bisphenol polyoxyethylene ether, 5 parts of maleic anhydride, 6 parts of polyetheramine, 3 parts of sodium bisulfite, 2 parts of potassium hydroxide, 10 parts of ethylene glycol, and 40 parts of deionized water.

[0028] Its synthesis method includes the following steps: (1) Add 25 parts of ortho-cashew bisphenol polyoxyethylene ether to a four-necked flask equipped with a thermometer, a constant pressure dropper and a reflux condenser. After stirring thoroughly, heat to 65°C, replace the air in the flask with nitrogen and keep the flask under nitrogen protection throughout the process. Slowly add 5 parts of solid maleic anhydride through the constant pressure dropper. After the addition is completed, heat to 120°C and keep the reaction at this temperature for 3 hours.

[0029] (2) After the reaction is complete, the temperature is lowered to 60°C, 6 parts of polyetheramine are added, the air is replaced with nitrogen again, and after thorough stirring, the temperature is raised to 170°C and kept at this temperature for 7 hours.

[0030] (3) After the reaction is complete, cool down to 52°C, add 40 parts of deionized water and 10 parts of ethylene glycol, stir at 300 r / min for 20 min, add 2 parts of potassium hydroxide, and adjust the pH of the system to 6.0.

[0031] (4) Turn on the reflux condenser, heat to 95°C, add 3 parts of sodium bisulfite and stir evenly, continue to heat to 112°C, keep the reaction at this temperature for 3.5 h, and cool to 38°C after the reaction to obtain the target anti-wrinkle agent, denoted as CT-20. The number of repeating units is: a=8, b=6, c=10, d=12; the degree of polymerization of the polyamide segment is m=5, the degree of polymerization of the polyether segment is n=6, p=4; R is pentadecadienyl, and the structural formula is -C 15 H 27 It should be noted that, due to the polydispersity of the molecular weight of the polymer products, the above m, n, and p are statistical averages. The degree of polymerization of each chain segment in the actual product is distributed within a certain range, but the overall performance is stable. Those skilled in the art can obtain polymer compounds with the same function by means of the synthesis method of the present invention.

[0032] Example 2 This embodiment provides a multifunctional nylon bath anti-wrinkle agent and its preparation method. The mass proportions of each raw material of the anti-wrinkle agent are as follows, by weight: The mixture consists of 18 parts of ortho-cashew bisphenol polyoxyethylene ether, 7 parts of maleic anhydride, 8 parts of polyetheramine, 4 parts of sodium metabisulfite, 3 parts of sodium hydroxide, 15 parts of isopropanol, and 35 parts of deionized water.

[0033] Its synthesis method includes the following steps: (1) Add 18 parts of ortho-cashew bisphenol polyoxyethylene ether to a four-necked flask equipped with a thermometer, a constant pressure dropper and a reflux condenser. After stirring thoroughly, heat to 60°C, replace air with nitrogen and provide nitrogen protection throughout the process. Add 7 parts of solid maleic anhydride. After the addition is complete, heat to 115°C and keep the reaction at this temperature for 4 hours.

[0034] (2) After the reaction is complete, the temperature is lowered to 60°C, 8 parts of polyetheramine are added, the air is replaced with nitrogen, and the temperature is raised to 160°C and kept at this temperature for 8 hours.

[0035] (3) After the reaction is complete, cool down to 50°C, add 35 parts of deionized water and 15 parts of isopropanol, stir at a rate of 400 r / min for 15 min, add 3 parts of sodium hydroxide, and adjust the pH of the system to 5.5.

[0036] (4) Turn on the reflux condenser, heat to 95°C, add 4 parts of sodium metabisulfite and stir evenly, continue to heat to 110°C, keep the reaction at this temperature for 4 hours, and cool to 35°C after the reaction is complete to obtain the target anti-wrinkle agent, denoted as CT-30. The theoretical number-average degree of polymerization of each repeating unit is: a=6, b=8, c=8, d=6; the average degree of polymerization of the polyester segment is m=6, the average degree of polymerization of the polyether segment is n=5, p=5; R is pentadecadienyl, with the structural formula -C 15 H 27 It should be noted that, due to the polydispersity of the molecular weight of the polymer products, the above m, n, and p are statistical averages. The degree of polymerization of each chain segment in the actual product is distributed within a certain range, but the overall performance is stable. Those skilled in the art can obtain polymer compounds with the same function by means of the synthesis method of the present invention.

[0037] Using the anti-wrinkle agent product synthesized in the above embodiments as the test object, the product was tested at 98°C on a nylon knitted fabric. Added to the 45-minute acid staining process at a dosage of 2%, the effect was evaluated in terms of hand feel, hydrophilicity, and antistatic properties through a blank control experiment. The specific results are as follows: 1. Evaluation of the fabric's soft and smooth feel The evaluation was conducted using a multi-person feel rating method, focusing only on the smoothness.

[0038] Second: Improvement effect on hydrophilicity Its hydrophilicity was tested using the water droplet diffusion method.

[0039] Three: Improvement effect against static electricity Its antistatic effect was characterized by surface resistance and half-life.

[0040] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A multifunctional nylon bath anti-wrinkle agent, characterized in that, The anti-wrinkle agent is a polyester polyether compound containing polymeric cashew bisphenol A, with the following structural formula: ； Where a, b, c, and d range from 2 to 100, and m, n, and p are all ≥ 2; R is a cashew alkyl group, with the general structural formula C0. 15 H 31-2x x is 1, 2 or 3.

2. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent as described in claim 1, characterized in that, Includes the following steps: (1) Add cashew bisphenol polyether to a four-necked flask equipped with a thermometer, a constant pressure dropper and a reflux condenser, heat to 60~70℃, add solid polyester linker dropwise under nitrogen protection, heat to 115~125℃ and keep warm for 2~4 hours. (2) Cool down to 60°C, add polyether linker, and heat up to 160~180°C under nitrogen protection for 6~8 hours; (3) Cool down to 50~55℃, add deionized water and organic solvent, stir evenly, and then add alkali to adjust the pH to 5.5~6.5; (4) Heat to 95°C, add sulfonating agent, stir evenly, then heat to 110~115°C and keep warm for 3~4 hours, then cool to 35~40°C to obtain the target product.

3. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent according to claim 2, characterized in that: The proportions of each raw material by weight are as follows: 18-25 parts cashew bisphenol polyether, 5-7 parts polyester linker, 6-8 parts polyether linker, 10-15 parts organic solvent, 35-40 parts deionized water, 2-3 parts alkali agent, and 3-4 parts sulfonating agent.

4. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent according to claim 2, characterized in that: In step (1), the cashew bisphenol polyether is ortho-cashew bisphenol polyoxyethylene ether; the polyester linker is maleic anhydride.

5. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent according to claim 2, characterized in that: In step (2), the polyether linker is polyetheramine.

6. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent according to claim 2, characterized in that: In step (3), the organic solvent is ethylene glycol or isopropanol; the alkaline agent is sodium hydroxide or potassium hydroxide.

7. The method for synthesizing a multifunctional nylon bath anti-wrinkle agent according to claim 2, characterized in that: In step (4), the sulfonating agent is sodium bisulfite or sodium metabisulfite.

8. The application of the multifunctional nylon bath anti-wrinkle agent as described in claim 1, characterized in that: The anti-wrinkle agent used is for acid dyeing of nylon fibers.

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