Antistatic dyeing auxiliary agent and preparation method and application thereof

Abstract

The present application relates to the field of textile technology, and in particular to an antistatic dyeing auxiliary agent, a preparation method thereof and an application thereof. The antistatic dyeing auxiliary agent comprises the following raw materials in parts by weight: 20-30 parts of chitosan-modified graphene oxide, 20-60 parts of polyoxyethylene nonionic surfactant and 30-40 parts of ionic compound; the preparation method of the chitosan-modified graphene oxide comprises the following steps: S1, mixing graphene oxide with water to form a graphene oxide solution; mixing chitosan and polyethylene glycol in an acid solution to form a chitosan-polyethylene glycol mixed solution; S2, mixing the chitosan-polyethylene glycol mixed solution with the graphene oxide solution to obtain a mixed solution; filtering, washing and drying the mixed solution; wherein the mass ratio of graphene oxide, chitosan and polyethylene glycol is 1: (3-5): (1-2). The antistatic dyeing auxiliary agent of the present application has excellent antistatic effect and durability on polyester fabrics.

Description

Technical Field

[0001] The present application relates to the technical field of textile auxiliaries, and in particular to an antistatic auxiliaries and a preparation method and application thereof. Background Art

[0002] Polyester is a widely used synthetic fiber. It has excellent properties that natural fibers cannot match, such as durability, good elasticity, high strength, wear resistance, corrosion resistance, insect-free, easy to wash and dry, etc. The market demand is constantly expanding and it is deeply loved by people. However, there are fewer hydrophilic groups in the structure of polyester fibers, poor hygroscopicity, and it is very easy to generate static electricity. This leads to the fact that during use, polyester fabrics will not only absorb dust in the air, but also easily produce electric shocks. Due to static electricity, the fabric will be wound and sticky, which may cause uneven dyeing and even color loss in severe cases. Therefore, factories often use antistatic agents to treat polyester fabrics with antistatic agents during the production process, but it is difficult to obtain a durable antistatic effect.

[0003] At present, quaternary ammonium salt compounds are widely used as cationic antistatic agents. They not only have good antistatic effects, but also have excellent softness. They can be used as antistatic agents for synthetic fibers such as polyester, acrylic, and polypropylene. However, since there are fewer reactive groups on the surface of synthetic fibers, the antistatic agent is only adsorbed on the surface of the fiber, so its durability is poor.

[0004] Therefore, developing a durable antistatic dyeing auxiliary is of great significance to improve the antistatic properties of polyester fabrics. Summary of the invention

[0005] In order to improve the durability of antistatic dyeing auxiliary agents and improve the antistatic properties of polyester fabrics, the present application provides an antistatic dyeing auxiliary agent and a preparation method and application thereof.

[0006] In the first aspect, the present application provides an antistatic dyeing auxiliary agent, which adopts the following technical solution:

[0007] An antistatic dyeing auxiliary agent is made of the following raw materials in parts by weight: 20-30 parts of chitosan-modified graphene oxide, 20-60 parts of polyoxyethylene nonionic surfactant and 30-40 parts of ionic compound;

[0008] The preparation method of chitosan-modified graphene oxide comprises the following steps:

[0009] S1, mixing graphene oxide with water to form a graphene oxide solution; mixing chitosan and polyethylene glycol in an acid solution to form a chitosan-polyethylene glycol mixed solution;

[0010] S2, mixing the chitosan-polyethylene glycol mixed solution with the graphene oxide solution to obtain a mixed solution; filtering, washing and drying the mixed solution; wherein the mass ratio of graphene oxide, chitosan and polyethylene glycol is 1:(3-5):(1-2).

[0011] By adopting the above technical scheme, chitosan can be dissolved in most dilute acids, and after being dissolved in acid, the amino groups in the molecules can combine with protons to make themselves carry positive charges. On the one hand, they repel each other with the same charges as static electricity, which is beneficial to the dispersion of amino groups and improves the uniformity of chitosan dispersion on the fabric; on the other hand, since polyester fabrics carry negative charges, positive and negative charges attract each other, so that graphene oxide can be well attached to the fabric, enhancing the durability of the antistatic dyeing auxiliary agent.

[0012] Secondly, graphene oxide has strong cytotoxicity to cells. It can directly contact the cell membrane of bacteria and decompose it. The antibacterial mechanism of graphene oxide is the combined action of cell membrane and oxidative stress. Graphene can also absorb a certain amount of ultraviolet rays and can be used as an ultraviolet absorber in textile finishing. More importantly, graphene has super high conductivity. When graphene oxide is applied to the surface of the fabric, a conductive layer can be formed on the surface of the fabric, which has a good anti-static effect.

[0013] Finally, the present application adds a long-chain polyether structure in a polyoxyethylene nonionic surfactant to undergo a complex reaction with the ionic compound, thereby promoting the stable dispersion of the ionic compound in the antibacterial electro-dyeing auxiliary agent. At the same time, due to the adsorption of cations in the ionic compound by graphene oxide, the uniformity of the distribution of graphene oxide in the antistatic dyeing auxiliary agent can be further improved, thereby improving the antistatic effect of the antistatic dyeing auxiliary agent.

[0014] In summary, the antistatic dyeing auxiliary agent formed by the interaction and coordination between chitosan-modified graphene oxide, polyoxyethylene nonionic surfactant and ionic compound in the present application has a high-efficiency and long-lasting antibacterial effect on polyester fabrics.

[0015] Preferably, the molecular weight of the polyethylene glycol is 15000-25000, and more preferably, the molecular weight of the polyethylene glycol is 20000.

[0016] By adopting the above technical scheme, polyethylene glycol with different molecular weights has different effects on chitosan. When the molecular weight of polyethylene glycol is 15000-25000, the porosity of the chitosan-modified graphene oxide formed is higher and the pore size is appropriate. Especially when the molecular weight of polyethylene glycol is 2000, the effect is better and more conducive to the penetration of graphene oxide.

[0017] Preferably, the specific steps of S1 are: dissolving chitosan with an acid solution to obtain a chitosan solution; uniformly mixing polyethylene glycol with the chitosan solution to obtain a chitosan-polyethylene glycol mixed solution; adding graphene oxide to water and ultrasonically oscillating to obtain a graphene oxide solution.

[0018] By adopting the above technical scheme, graphene oxide is peeled off into single-layer or few-layer graphene dispersed in the solution through ultrasonic treatment, and cations in ionic compounds are adsorbed. In the subsequent hydrothermal reaction process, the cations are successfully embedded in the graphene oxide sheet structure, which has a stable and dense structure, can improve the stability of graphene oxide, and the antistatic effect of polyester fabric is maintained long-term and effectively.

[0019] Preferably, the polyoxyethylene nonionic surfactant is one or more of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and polyethylene glycol; further preferably, the polyoxyethylene nonionic surfactant is polyethylene glycol.

[0020] By adopting the above technical scheme, polyethylene glycol has excellent lubricity, moisturizing and dispersibility, and can be widely used as a binder, antistatic agent and softener in the field of chemical fibers. At the same time, the application adopts polyethylene glycol as a non-ionic surfactant to improve the compatibility with chitosan-modified graphene oxide. The long-chain polyether structure in polyethylene glycol undergoes a complex reaction with the cations in the ionic compound, which promotes the graphene oxide that acts with the cations to be evenly and stably dispersed on the fabric surface, effectively improving the antistatic effect of the antistatic dyeing auxiliary on polyester fabrics.

[0021] Preferably, the ionic compound is a salt formed by a metal and an organic acid or an inorganic acid.

[0022] Preferably, the ionic compound is one or more of lithium acetate, lithium chloride, lithium perchlorate, lithium hexafluorophosphate, lithium acetate, lithium phosphate, potassium thiocyanate, sodium bromide, sodium perchlorate, and zinc chloride.

[0023] Preferably, the ionic compound is zinc chloride.

[0024] By adopting the above technical scheme, zinc oxide is used as a metal oxide with a certain conductivity, and graphene oxide adsorbs zinc ions. In the subsequent hydrothermal reaction process, the zinc ions are converted into nano zinc oxide and successfully embedded in the graphene oxide sheet structure. The structure is stable and dense, which can effectively avoid the loss of zinc oxide during use and improve the durability of the antistatic dyeing auxiliary. At the same time, zinc oxide has a strong sterilization ability, which can improve the antibacterial effect of the antistatic dyeing auxiliary on polyester fabrics.

[0025] In the second aspect, the present application provides a method for preparing an antistatic dyeing auxiliary agent, adopting the following technical scheme: A method for preparing an antistatic dyeing auxiliary agent: weigh the raw materials according to the formula, mix chitosan-modified graphene oxide, polyoxyethylene nonionic surfactant and deionized compound, and carry out a hydrothermal reaction.

[0026] By adopting the above technical scheme, the antistatic dyeing auxiliary produced by the hydrothermal method has high purity, good dispersibility, controllable crystal shape, low production cost, and the antistatic dyeing auxiliary powder prepared by the hydrothermal method does not need to be sintered, which can avoid the disadvantages of grain growth and easy mixing of impurities during the sintering process. The overall preparation method of the antistatic dyeing auxiliary is simple and suitable for industrial large-scale production.

[0027] Preferably, the conditions of the hydrothermal reaction are: temperature 140-180° C., pressure 1.2-3.2 MPa, and reaction time 1-2 h.

[0028] In a third aspect, the present application provides an application of an antistatic dyeing auxiliary agent, using the following technical solution:

[0029] Antistatic dyeing auxiliaries are used in the printing and dyeing process of polyester fibers.

[0030] By adopting the above technical scheme, after the antistatic dyeing auxiliary agent of the present application is used for printing and dyeing polyester fibers, the resulting products have good and lasting antistatic effect and excellent water-washing resistance.

[0031] In summary, the present application includes at least one of the following beneficial technical effects:

[0032] 1. The present application utilizes the interaction of chitosan-modified graphene oxide, polyoxyethylene nonionic surfactant and ionic compound, which has good synergistic effect. The antistatic dyeing auxiliary agent formed is used in the printing and dyeing of polyester fibers, so that the formed products have excellent antistatic effect and durability;

[0033] 2. The present application uses polyethylene glycol as a polyoxyethylene nonionic surfactant. Polyethylene glycol itself has a good antistatic effect. At the same time, its long-chain polyether structure is complexed with the cations in the ionic compound, promoting the uniform and stable dispersion of graphene oxide that reacts with the cations; thus, the antistatic effect of the antistatic dyeing auxiliary on the fabric is improved;

[0034] 3. This application uses zinc chloride as the ionic compound. Since zinc chloride itself has a certain conductivity, and in the subsequent hydrothermal reaction process, zinc ions are converted into nano zinc oxide and successfully embedded in the graphene oxide sheet structure. The formed structure is stable and dense, which can effectively avoid the loss of zinc oxide during use and improve the durability of the antistatic dyeing auxiliary agent. DETAILED DESCRIPTION

[0035] The present application is further described in detail below through preparation examples and embodiments.

[0036] Preparation Example

[0037] Preparation Example 1

[0038] This preparation example discloses a method for preparing chitosan-modified graphene oxide, which specifically comprises the following steps:

[0039] S1, dissolve 3g chitosan in 200ml acetic acid solution with a concentration of 2wt%, stir magnetically for 6h, fully dissolve to obtain chitosan solution; weigh 2g polyethylene glycol-20000 and add it to the above chitosan solution, continue stirring for 1h, make it fully dissolved and mixed, and obtain chitosan-polyethylene glycol mixed solution; weigh 1g graphene oxide in 200ml deionized water, 500W power ultrasonic oscillation for 3h, make it fully dissolved, and obtain graphene oxide solution; wherein chitosan CAS: 9012-76-4; polyethylene glycol was purchased from Nantong Zimeng Chemical Co., Ltd.; graphene oxide was purchased from Shanghai Maoguo Nano Co., Ltd.;

[0040] S2, mixing the chitosan-polyethylene glycol mixed solution with the graphene oxide solution to obtain a mixed solution; filtering the mixed solution to obtain a filter cake, washing the obtained filter cake with dimethylformamide, and then vacuum drying to obtain chitosan-modified graphene oxide.

[0041] Preparation Example 2

[0042] This preparation example is basically the same as preparation example 1, except that: in S1, 5 g of chitosan is dissolved in 200 ml of 2 wt% acetic acid solution, and magnetically stirred for 6 h to fully dissolve to obtain a chitosan solution; 1 g of polyethylene glycol-20000 is weighed and added to the above chitosan solution, and stirring is continued for 1 h to fully dissolve and mix to obtain a chitosan-polyethylene glycol mixed solution; 1 g of graphene oxide is weighed and added to 200 ml of deionized water, and ultrasonically oscillated at a power of 500 W for 3 h to fully dissolve it to obtain a graphene oxide solution.

[0043] Example

[0044] Examples 1-7

[0045] As shown in Table 1, the main difference between Examples 1-7 is the different raw material ratios of the antistatic dyeing auxiliary agent.

[0046] The following is explained by taking Example 1 as an example, wherein the specific formula of the antistatic dyeing auxiliary agent in the example is: 20 g of chitosan-modified graphene oxide, 20 g of polyethylene glycol and 10 g of zinc chloride, wherein the chitosan-modified graphene oxide is obtained by the preparation example, and zinc chloride is purchased from Changzhou Aked New Material Technology Co., Ltd.

[0047] This embodiment also discloses a method for preparing an antistatic dyeing auxiliary agent, and the specific process is: chitosan-modified graphene oxide, polyethylene glycol and zinc chloride are weighed and mixed according to the formula, and the antistatic dyeing auxiliary agent is obtained by hydrothermal reaction at a temperature of 140° C. and a pressure of 3.2 MPa for 1 hour.

[0048] This embodiment also discloses an application of an antistatic dyeing auxiliary agent, which is used in the polyester fiber printing and dyeing process.

[0049] Embodiment 2-7

[0050] The difference between this embodiment and embodiment 1 is that the raw material ratios used in the antistatic dyeing auxiliary agent are different, as shown in Table 1.

[0051] Table 1 Ratio of raw materials of antistatic dyeing auxiliary in Examples 1-7

[0052]

[0053] Example 8

[0054] The difference between this embodiment and embodiment 6 is that the chitosan-modified graphene oxide is obtained from preparation example 2.

[0055] Example 9

[0056] The difference between this embodiment and embodiment 6 is that in the preparation method of the antistatic dyeing auxiliary agent: chitosan-modified graphene oxide, polyethylene glycol and zinc chloride are weighed and mixed according to the formula, and the antistatic dyeing auxiliary agent is obtained by hydrothermal reaction at a temperature of 180° C. and a pressure of 1.2 MPa for 2 hours.

[0057] Comparative Example

[0058] Comparative Example 1

[0059] This comparative example is different from Example 6 in that an equal amount of polyethylene glycol is replaced by zinc chloride.

[0060] Comparative Example 2

[0061] This comparative example is different from Example 6 in that an equal amount of zinc chloride is replaced by polyethylene glycol.

[0062] Comparative Example 3

[0063] This comparative example is different from Example 6 in that the chitosan-modified graphene oxide is replaced by polyethylene glycol in equal amounts.

[0064] Comparative Example 4

[0065] The difference between this comparative example and Example 6 is that a quaternary ammonium salt compound is used as a cationic antistatic dyeing auxiliary agent, and the quaternary ammonium salt compound is purchased from Yixing Bafangyuan Chemical Co., Ltd.

[0066] Performance Testing

[0067] 5 g of the antistatic dyeing auxiliary agent of Examples 1-9 and Comparative Examples 1-4 and 20 g of the dye were dissolved in 1 kg of water to form a dyeing bath, forming 13 groups of dyeing baths, 50 pieces of polyester fabrics to be dyed were placed in each group of dyeing baths, the temperature was raised to 130° C., kept warm for 5 minutes, then cooled to room temperature, and the fabrics were rinsed in clean water and dried to obtain dyed fabrics.

[0068] 1. Antistatic performance and durability: The test was conducted in accordance with the standard GB / T12703-2008 "Test of electrostatic performance of textiles - Half-life of static voltage", with a temperature of 20°C and a relative humidity of 35%. The average value of 50 polyester fabrics printed and dyed after the test was used as the antistatic performance measurement standard; at the same time, the average value of the polyester fabrics after washing 30 times and then tested was used as the antistatic durability test standard; the test results are recorded in Table 2.

[0069] 2. Dyeing uniformity: observe the uniformity of the dyed fabric. If there are uneven colors in the fabric, the dyeing uniformity is recorded as unqualified. If there are no uneven colors in the fabric, the dyeing uniformity probability is qualified. 50 qualified pieces are recorded as excellent, 30-49 qualified pieces are recorded as good, and <30 qualified pieces are recorded as poor. The test results are recorded in Table 2.

[0070] 3. Dyeing fastness: refer to the test standard of GB / T6151-2016 to test the color fastness of the dyed fabric. If the color fastness of 50 pieces is ≥ level 4, the color fastness is recorded as excellent; if the color fastness of 30-49 pieces is ≥ level 4, the color fastness is recorded as good; if the color fastness of <30 pieces is ≥ level 4, the color fastness is recorded as poor. The test results are recorded in Table 2.

[0071] Table 2 Performance test data of Examples 1-9 and Comparative Examples 1-4

[0072]

[0073]

[0074] Referring to Table 2, in combination with Examples 1-9 and Comparative Examples 1-3, it can be seen that the antistatic dyeing auxiliary prepared in the present application has excellent antistatic and durability for polyester fabrics, and the obtained fabrics are uniformly dyed and have excellent color fastness. The graphene oxide is modified by chitosan, which is soluble in most dilute acids, and the amino groups in the molecules after being dissolved in acid can combine with protons to make themselves positively charged, which on the one hand repel the same charges of static electricity and improve the antistatic effect; on the other hand, since the polyester fabric has a negative charge, the positive and negative charges attract each other, so that the modified graphene oxide can be well attached to the fabric, and the antistatic effect of the graphene oxide itself is exerted. In addition, the polyethylene glycol and zinc chloride in the present application both have good antistatic properties, and zinc ions are adsorbed by graphene oxide on the one hand, and in the subsequent hydrothermal reaction process, they are converted into nano zinc oxide and successfully embedded in the graphene oxide sheet structure, forming a stable and dense structure, which can effectively avoid the loss of zinc oxide during use, and improve the durability of the antistatic dyeing auxiliary agent; on the other hand, the long-chain polyether structure in the polyethylene glycol will react with the zinc ions to cause the graphene oxide acting on the zinc ions to be evenly dispersed in the uniformity of the antistatic dyeing auxiliary agent, and improve the effect of the antistatic dyeing auxiliary agent. Through the above mechanism analysis, chitosan-modified graphene oxide, polyethylene glycol and zinc chloride interact with each other, have an efficient synergistic effect, and are indispensable, so the test data of Example 6 is better than the test data of Comparative Examples 1-3.

[0075] Referring to Table 2, in combination with Example 6 and Comparative Example 4, it can be seen that the use of quaternary ammonium salt compounds as cationic antistatic dyeing auxiliary agents to dye polyester fabrics is not as good as the antistatic properties and durability of the antistatic dyeing auxiliary prepared in the present application after dyeing polyester fabrics, and it also affects the dyeing uniformity and color fastness of the fabric.

[0076] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. An antistatic dyeing auxiliary agent, characterized in that: The method is prepared from the following raw materials in parts by weight: 20-30 parts of chitosan-modified graphene oxide, 20-60 parts of polyoxyethylene nonionic surfactant and 30-40 parts of ionic compound; The preparation method of chitosan-modified graphene oxide comprises the following steps: S1, mixing graphene oxide with water to form a graphene oxide solution; mixing chitosan and polyethylene glycol in an acid solution to form a chitosan-polyethylene glycol mixed solution; S2, mixing a chitosan-polyethylene glycol mixed solution with a graphene oxide solution to obtain a mixed solution; filtering, washing and drying the mixed solution; wherein the mass ratio of graphene oxide, chitosan and polyethylene glycol is 1: (3-5): (1-2); the molecular weight of the polyethylene glycol is 15000-25000; The polyoxyethylene nonionic surfactant is one or more of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and polyethylene glycol; The ionic compound is one or more of lithium acetate, lithium chloride, lithium perchlorate, lithium hexafluorophosphate, lithium phosphate, potassium thiocyanate, sodium bromide, sodium perchlorate, and zinc chloride; The preparation method of the antistatic dyeing auxiliary agent comprises the following steps: weighing raw materials according to a formula, mixing chitosan-modified graphene oxide, a polyoxyethylene nonionic surfactant and an ionic compound, and performing a hydrothermal reaction.

2. An antistatic dyeing auxiliary agent according to claim 1, characterized in that: The specific steps of S1 are: dissolving chitosan with an acid solution to obtain a chitosan solution; mixing polyethylene glycol with the chitosan solution to obtain a chitosan-polyethylene glycol mixed solution; adding graphene oxide to water and ultrasonically oscillating to obtain a graphene oxide solution.

3. An antistatic dyeing auxiliary agent according to claim 1, characterized in that: The ionic compound is zinc chloride.

4. The method for preparing an antistatic dyeing auxiliary agent according to any one of claims 1 to 3, characterized in that: The raw materials are weighed according to the formula, the chitosan-modified graphene oxide, the polyoxyethylene nonionic surfactant and the ionic compound are mixed, and a hydrothermal reaction is carried out.

5. The method for preparing an antistatic dyeing auxiliary agent according to claim 4, characterized in that: The conditions of the hydrothermal reaction are: temperature 140-180° C., pressure 1.2-3.2 MPa, and reaction time 1-2 h.

6. The antistatic dyeing auxiliary agent according to any one of claims 1 to 3 is used in the printing and dyeing process of polyester fibers.

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