Super-hydrophobic modal fabric and preparation method thereof

Abstract

The invention relates to a super-hydrophobic modal fabric and a preparation method thereof. The fabric can be prepared by the following method: firstly, preparing a reaction solution containing double-bond graphene oxide; secondly, preparing a graphene oxide modified polyacrylic acid coating agent from the reaction liquid containing the double-bond graphene oxide, acrylic acid, styrene, butyl acrylate and the like; then, uniformly mixing the graphene oxide modified polyacrylic acid coating agent with a pore-forming agent solution to prepare a composite coating agent; thirdly, the modal fabric is subjected to coating finishing; finally, ultrasonic washing and drying are conducted, and the super-hydrophobic modal fabric is prepared. The surface of the prepared super-hydrophobic modal fabric contains graphene, the apparent contact angle range of water drops on the modal fabric ranges from 153 degrees to 156 degrees, and the super-hydrophobic modal fabric shows good super-hydrophobicity; after 10 times of water washing, the hydrophobic performance of the modal fabric is still not obviously weakened.

Description

Technical Field

[0001] The invention belongs to the technical field of fabric preparation, and particularly relates to a super-hydrophobic modal fabric and a preparation method thereof. Background Art

[0002] With the accelerated pace of life and the increasing pressure of life in recent years, most people spend less and less time on clothing care, and the simplification of clothing care has become another basic requirement for choosing clothes and fabrics. Therefore, fabrics with super hydrophobicity, self-cleaning and antibacterial properties are becoming more and more popular among consumers.

[0003] Modal fabric is a fabric made of modal fiber. Modal fiber is a cellulose fiber, which is the same as rayon and is a pure man-made fiber. It is made from wood pulp from European shrubs and then through a special spinning process. Modal products are mostly used in the production of underwear because of their good softness and excellent moisture absorption but poor stiffness.

[0004] Modal fiber can also show its weavability in the weaving process of woven fabrics, and can also be interwoven with yarns of other fibers to weave into various fabrics. Modal products have broad development prospects in modern clothing and accessories.

[0005] Literature research shows that modal fabrics have received widespread attention in recent years. For example, Chinese invention patent application No. 202011617298.2 discloses a processing method for modal fiber embroidery fabrics: first pre-treat the modal fabric, then embroider it, then dip and roll it with a health-care shea butter treatment agent at room temperature, and finally dry it at high temperature to obtain the finished embroidery fabric. Shea butter additive is a nano-scale weak cationic additive with excellent anti-drying and antioxidant properties. When used, it can promote the combination of shea butter with fibers of various materials; Chinese invention patent application No. 201910137442.3 discloses a method for preparing anti-mite modal fabric: the present invention prepares anti-mite modal fabric by attaching calcium carbonate anti-mite microcapsules on modal fabric, completely wrapping the organic anti-mite agent with calcium carbonate microcapsules, and then adhering it to the modal fabric through the action of a water-based adhesive. It can effectively reduce the loss of organic anti-mite agents in the modal fabric during the washing process, thereby delaying the action time of the organic anti-mite agent and improving the anti-mite effect of the modal fabric.

[0006] However, the existing modal fabric has good overall hygroscopicity and poor super-hydrophobicity, which affects the use effect of modal fabric in specific fields. Therefore, it is of great significance to improve the preparation process of modal fabric in the prior art to obtain a modal fabric with super-hydrophobicity and low cost. Summary of the invention

[0007] In view of the above-mentioned drawbacks existing in the prior art, the object of the present invention is to provide a super hydrophobic modal fabric and a preparation method thereof.

[0008] The invention aims to provide a super-hydrophobic modal fabric, which has the characteristics of antibacterial, super-hydrophobicity and the like. The fabric can be prepared by the following method: firstly, graphene oxide is grafted with double bonds to prepare a reaction solution containing double-bond graphene oxide; secondly, the reaction solution containing double-bond graphene oxide, acrylic acid, styrene, butyl acrylate and the like are used to prepare a graphene oxide-modified polyacrylic acid coating agent; then, the graphene oxide-modified polyacrylic acid coating agent and a pore-forming agent solution are uniformly mixed to prepare a composite coating agent; thirdly, the modal fabric is subjected to coating finishing; and finally, ultrasonic washing and drying are performed to prepare the super-hydrophobic modal fabric.

[0009] The object of the present invention is achieved through the following technical solutions:

[0010] A method for preparing a super-hydrophobic modal fabric comprises the following steps:

[0011] (1) Preparation of graphene oxide containing double bonds: Under ice bath conditions, graphene oxide and acryloyl chloride are weighed and dissolved in tap water to obtain a reaction solution; the pH of the reaction solution is adjusted to 9 to 11 with a 30% by mass aqueous sodium hydroxide solution, and the reaction is stirred to obtain a reaction solution containing graphene oxide containing double bonds.

[0012] Preferably, the reaction time is 60 to 90 minutes.

[0013] Preferably, the usage ratio of the graphene oxide, acryloyl chloride and tap water is: 1 g: (1-2) g: (100-200) mL.

[0014] (2) Preparation of coating agent: The reaction solution prepared in step (1), sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10), acrylic acid, styrene, butyl acrylate and ammonium persulfate are weighed and dissolved in deionized water, and the mixture is stirred evenly. The temperature is controlled at 75-85° C. and stirred for 1-2 hours. Then, the remaining 2 / 3 of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator are dissolved in deionized water and then added dropwise to the stirred mixed solution. The addition time is controlled at 2-3 hours. After the addition is completed, the mixture is kept warm for 2-3 hours. The emulsion is left for one month. If no stratification or precipitation occurs, the graphene oxide modified polyacrylic acid coating agent is obtained.

[0015] Preferably, the dosage ratio of the sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10), acrylic acid, styrene, butyl acrylate, the reaction solution prepared in step (1) and ammonium persulfate is: 1g: (1-2)g: (0.1-0.2)mol: (0.1-0.2)mol: (0.1-0.2)mol: (2-4)mL: (0.5-1)g.

[0016] (3) Preparation of pore-forming agent solution: dissolve the pore-forming agent in tap water to prepare a pore-forming agent solution.

[0017] Preferably, the pore-forming agent is fatty alcohol polyoxyethylene ether (AEO-9).

[0018] Preferably, the usage ratio of the pore-forming agent (g) to tap water (mL) is 1:100-200.

[0019] (4) Blending: The graphene oxide modified polyacrylic acid coating agent obtained in step (2) and the pore-forming agent solution obtained in step (3) are uniformly mixed by a high-speed dispersing homogenizer to obtain a composite coating agent.

[0020] Preferably, the amount ratio of the graphene oxide modified polyacrylic acid coating agent prepared in step (2) to the pore-forming agent solution prepared in step (3) is 1 mL: (0.1-0.3) mL.

[0021] Preferably, the rotation speed of the high-speed dispersing homogenizer is 15000-20000 r / min; and the mixing time is 5-15 min.

[0022] (5) Coating finishing: Stretch the fabric tightly on the stretcher, and evenly apply the composite coating agent on the fabric with a scraper. The dry weight of the coating is 5-15g / m 2 , dry at 90℃ for 1 to 3 minutes and bake at 110 to 120℃ for 2 to 3 minutes.

[0023] Preferably, the fabric is modal fabric.

[0024] (6) Washing: The fabric treated in step (5) is washed 5 to 7 times under ultrasonic conditions, and then dried to obtain a super-hydrophobic modal fabric.

[0025] Preferably, the usage ratio of the fabric to water is 1 g: (100-200) mL.

[0026] Preferably, the frequency of the ultrasonic wave is 5-7Mz, and the sound intensity is 40-60W / cm 2 .

[0027] The present invention has the following notable features:

[0028] (1) Graphene has strong hydrophobic properties, but it is difficult to apply it to fabrics. The present invention uses graphene oxide as the raw material of the coating agent; the purpose of applying graphene oxide to modal fabrics is achieved; the inventor of the present application unexpectedly discovered that modal fabrics coated with graphene oxide on the surface have good hydrophobicity.

[0029] (2) Fatty alcohol polyoxyethylene ether (AEO-9) is easily soluble in water. It is first used as a raw material for compounding a coating agent and then removed by washing. The inventors of the present application unexpectedly discovered that a rough micro-nano structure is formed on the surface of the modal fabric after washing. The micro-nano structure is beneficial to enhancing the hydrophobicity of the modal fabric.

[0030] (3) The surface of the super-hydrophobic modal fabric prepared by the present invention contains graphene, and the apparent contact angle of water droplets on the modal fabric ranges from 153° to 156°, showing good super-hydrophobicity; after 10 times of washing, the hydrophobicity of the modal fabric is still not significantly weakened.

[0031] (4) After 10 times of washing, the super-hydrophobicity of the super-hydrophobic modal fabric prepared by the present invention is not significantly weakened, which indicates that graphene can be firmly attached to the surface of the modal fabric.

[0032] (5) The super-hydrophobic modal fabric prepared by the present invention has a wide range of raw material sources, a simple preparation process, and has a good market promotion prospect. DETAILED DESCRIPTION

[0033] The following examples and comparative examples illustrate the present invention in detail.

[0034] Example 1

[0035] In this embodiment, a method for preparing a super hydrophobic modal fabric is provided, and the preparation method comprises the following steps:

[0036] (1) Preparation of graphene oxide containing double bonds: Under ice bath conditions, 1 g of graphene oxide and 1.5 g of acryloyl chloride were weighed and dissolved in 150 mL of tap water to prepare a reaction solution; the pH of the reaction solution was adjusted to 10 with a 30% by mass aqueous sodium hydroxide solution, and the reaction was stirred for 75 minutes to prepare a reaction solution containing graphene oxide containing double bonds.

[0037] (2) Preparation of coating agent: 3 mL of the reaction solution prepared in step (1), 1 g of sodium dodecylbenzene sulfonate, 1.5 g of octylphenol polyoxyethylene ether (OP-10), 0.15 mol of acrylic acid, 0.15 mol of styrene, 0.15 mol of butyl acrylate and 0.75 g of ammonium persulfate were taken, and all of the sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10) and 1 / 3 of the total amount of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate were introduced into the mixture. The initiator is dissolved in 200 mL of deionized water, stirred evenly, and the temperature is controlled at 80° C. for 1.5 h. Then, the remaining 2 / 3 of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator are dissolved in 200 mL of deionized water and then added dropwise to the mixed solution just stirred. The dropping time is controlled to be 2.5 h. After the dropping is completed, the mixture is kept warm for 2.5 h. The emulsion is left for one month. If no stratification or precipitation occurs, the graphene oxide modified polyacrylic acid coating agent can be obtained.

[0038] (3) Preparation of pore-forming agent solution: Dissolve 1 g of pore-forming agent fatty alcohol polyoxyethylene ether (AEO-9) in 150 mL of tap water to prepare a pore-forming agent solution.

[0039] (4) Blending: 100 mL of the graphene oxide modified polyacrylic acid coating agent prepared in step (2) and 20 mL of the pore-forming agent solution prepared in step (3) were uniformly mixed by a high-speed disperser homogenizer at a speed of 175,000 r / min for a mixing time of 10 min to obtain a composite coating agent.

[0040] (5) Coating finishing: Stretch the modal fabric tightly on the stretcher, and evenly apply the composite coating agent on the fabric with a scraper. The dry weight of the coating is 10g / m 2 , dried at 90℃ for 2 minutes and baked at 115℃ for 2.5 minutes.

[0041] (6) Washing: The fabric treated in step (5) was washed 6 times under ultrasonic conditions, with the ratio of fabric to water being 1 g:150 mL, the frequency of the ultrasonic wave being 6 MHz, and the sound intensity being 50 W / cm 2 , and then dried to obtain super hydrophobic modal fabric.

[0042] Example 2

[0043] In this embodiment, a method for preparing a super hydrophobic modal fabric is provided, and the preparation method comprises the following steps:

[0044] (1) Preparation of graphene oxide containing double bonds: Under ice bath conditions, 1 g of graphene oxide and 1.0 g of acryloyl chloride were weighed and dissolved in 100 mL of tap water to obtain a reaction solution; the pH of the reaction solution was adjusted to 9 with a 30% by mass aqueous sodium hydroxide solution, and the reaction was stirred for 60 minutes to obtain a reaction solution containing graphene oxide containing double bonds.

[0045] (2) Preparation of coating agent: 2 mL of the reaction solution prepared in step (1), 1 g of sodium dodecylbenzene sulfonate, 1.0 g of octylphenol polyoxyethylene ether (OP-10), 0.1 mol of acrylic acid, 0.1 mol of styrene, 0.1 mol of butyl acrylate and 0.5 g of ammonium persulfate were taken, and all of the sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10) and 1 / 3 of the total amount of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator were mixed. Dissolve in 200 mL of deionized water, stir evenly, control the temperature to 75°C, and stir for 1.0 h; then, dissolve the remaining 2 / 3 of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator in 200 mL of deionized water and add dropwise to the mixed solution just stirred, the dropping time is controlled to 2.0 h, and after the dropping is completed, keep warm for 2.0 h; the emulsion is left for one month, and no stratification or precipitation occurs, so that the graphene oxide modified polyacrylic acid coating agent can be obtained.

[0046] (3) Preparation of pore-forming agent solution: Dissolve 1 g of pore-forming agent fatty alcohol polyoxyethylene ether (AEO-9) in 100 mL of tap water to prepare a pore-forming agent solution.

[0047] (4) Blending: 100 mL of the graphene oxide modified polyacrylic acid coating agent prepared in step (2) and 10 mL of the pore-forming agent solution prepared in step (3) are uniformly mixed by a high-speed disperser homogenizer at a speed of 150,000 r / min for a mixing time of 5 min to obtain a composite coating agent.

[0048] (5) Coating finishing: Stretch the modal fabric tightly on the stretcher, and evenly apply the composite coating agent on the fabric with a scraper. The dry weight of the coating is 5g / m 2 , dried at 90℃ for 1 minute and baked at 110℃ for 2 minutes.

[0049] (6) Washing: The fabric after finishing in step (5) was washed 5 times under ultrasonic conditions, the ratio of fabric to water was 1 g: 100 mL, the frequency of the ultrasonic wave was 5 Mz, and the sound intensity was 40 W / cm 2 , and then dried to obtain super hydrophobic modal fabric.

[0050] Example 3

[0051] In this embodiment, a method for preparing a super hydrophobic modal fabric is provided, and the preparation method comprises the following steps:

[0052] (1) Preparation of graphene oxide containing double bonds: Under ice bath conditions, 1 g of graphene oxide and 2.0 g of acryloyl chloride were weighed and dissolved in 200 mL of tap water to prepare a reaction solution; the pH of the reaction solution was adjusted to 11 with a 30% by mass aqueous sodium hydroxide solution, and the reaction was stirred for 90 minutes to prepare a reaction solution containing graphene oxide containing double bonds.

[0053] (2) Preparation of coating agent: 4 mL of the reaction solution prepared in step (1), 1 g of sodium dodecylbenzene sulfonate, 2.0 g of octylphenol polyoxyethylene ether (OP-10), 0.2 mol of acrylic acid, 0.2 mol of styrene, 0.2 mol of butyl acrylate and 1 g of ammonium persulfate are taken, and all of the sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10) and 1 / 3 of the total amount of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator are dissolved in 200 mL of deionized water, and the mixture is stirred evenly. The temperature is controlled to be 85° C. and stirred for 2 h. Then, the remaining 2 / 3 of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator are dissolved in 200 mL of deionized water and then added dropwise to the stirred mixed solution. The dropping time is controlled to be 3 h. After the dropping is completed, the mixture is kept warm for 3 h. The emulsion is left for one month. If no stratification or precipitation occurs, the graphene oxide modified polyacrylic acid coating agent is obtained.

[0054] (3) Preparation of pore-forming agent solution: Dissolve 1 g of pore-forming agent fatty alcohol polyoxyethylene ether (AEO-9) in 200 mL of tap water to prepare a pore-forming agent solution.

[0055] (4) Blending: 100 mL of the graphene oxide modified polyacrylic acid coating agent prepared in step (2) and 30 mL of the pore-forming agent solution prepared in step (3) were uniformly mixed by a high-speed disperser homogenizer at a speed of 175,000 r / min for a mixing time of 10 min to obtain a composite coating agent.

[0056] (5) Coating finishing: Stretch the modal fabric tightly on the stretcher, and evenly apply the composite coating agent on the fabric with a scraper. The dry weight of the coating is 15g / m 2 , dried at 90℃ for 3 minutes and baked at 120℃ for 3 minutes.

[0057] (6) Washing: The fabric treated in step (5) was washed 7 times under ultrasonic conditions, with the ratio of fabric to water being 1 g: 200 mL, the frequency of the ultrasonic wave being 7 MHz, and the sound intensity being 60 W / cm 2 , and then dried to obtain super hydrophobic modal fabric.

[0058] Comparative Example A

[0059] Taking Example 1 as a comparison, in this comparative example, graphene oxide is not added to the raw materials of the coating agent, that is, step (1) is not implemented, and the "reaction solution prepared in step (1)" in step (2) is removed, and the other preparation methods are implemented according to the preparation method of Example 1.

[0060] Comparative Example B

[0061] Taking Example 1 as a comparison, in this comparative example, no pore-forming agent is added, that is, step "(3) preparation of pore-forming agent solution" is removed, and the other preparation methods are implemented according to the preparation method of Example 1.

[0062] Comparative Example C

[0063] Taking Example 1 as a comparison, in this comparative example, ultrasound is not applied during washing, that is, the step (6) of "washing the fabric after the treatment in step (5) 6 times under ultrasonic conditions" is changed to "washing the fabric after the treatment in step (5) 6 times", and the other preparation methods are implemented according to the preparation method of Example 1.

[0064] Super hydrophobic performance test:

[0065] In order to better detect the super-hydrophobicity of the super-hydrophobic modal fabric prepared in the present invention, the super-hydrophobic modal fabrics a, b, c, d, e, and f prepared in the above-mentioned specific embodiments 1 to 3 and comparative examples A to C of the present invention are selected. The apparent contact angle of a water drop on the surface of the super-hydrophobic modal fabric is measured using an XG-CAMA1 basic contact angle tester, and no less than 30 test samples are tested, and the test average value is taken. The fabric to be tested is subjected to standard washing with reference to the washing method of the washing color fastness tester of GB / T 20944.1-2007, and the super-hydrophobicity of the initial sample and the sample after washing 10 times is tested. The test results are shown in Table 1.

[0066] Table 1 Apparent contact angles of water droplets on superhydrophobic modal fabrics a, b, c, d, e, f

[0067] Apparent contact angle (°) a b c d e f Unwashed 154.7 155.2 153.6 89.3 112.5 123.5 Wash 10 times 151.5 151.7 150.2 66.8 105.4 134.9

[0068] As can be seen from Table 1, the apparent contact angle of water droplets on super-hydrophobic modal fabrics a, b, and c ranges from 153° to 156°, respectively; after 10 washings, the hydrophobicity of fabrics a, b, and c has not been significantly weakened. Normally, when the apparent contact angle is greater than 150°, it means that the fabric has super-hydrophobicity. It can be considered that the super-hydrophobic modal fabric prepared by the present invention has super-hydrophobicity. The super-hydrophobicity of super-hydrophobic modal fabrics d, e, and f prepared by Comparative Examples AC is significantly poor, which shows that the selection of graphene oxide, the selection of pore-forming agent solution, and the application of ultrasonic waves during washing all have an important influence on the super-hydrophobic properties of modal fabrics.

Claims

1. A method for preparing a super hydrophobic modal fabric, characterized in that: The preparation method comprises the following steps: (1) Preparation of graphene oxide containing double bonds: Under ice bath conditions, weigh graphene oxide and acryloyl chloride, dissolve in tap water, and prepare a reaction solution; adjust the pH of the reaction solution to 9 to 11 with a 30% by mass sodium hydroxide aqueous solution, stir and react, and prepare a reaction solution containing graphene oxide containing double bonds; (2) Preparation of coating agent: taking the reaction solution prepared in step (1), sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10), acrylic acid, styrene, butyl acrylate and ammonium persulfate, dissolving all the sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10) and 1 / 3 of the total amount of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator in deionized water, stirring evenly, controlling the temperature to 75-85° C., and stirring for 1-2 hours; then, dissolving the remaining 2 / 3 of the reaction solution prepared in step (1), acrylic acid, styrene, butyl acrylate and ammonium persulfate initiator in deionized water and dripping into the stirred mixed solution, controlling the dripping time to 2-3 hours, and keeping the temperature for 2-3 hours after the dripping is completed; the emulsion is left for one month, and if no stratification or precipitation occurs, the graphene oxide modified polyacrylic acid coating agent can be obtained; (3) Preparation of pore-forming agent solution: dissolving the pore-forming agent in tap water to prepare a pore-forming agent solution; (4) blending: uniformly mixing the graphene oxide modified polyacrylic acid coating agent obtained in step (2) and the pore-forming agent solution obtained in step (3) by a high-speed dispersing homogenizer to obtain a composite coating agent; (5) Coating finishing: Stretch the fabric tightly on the stretcher, and evenly apply the composite coating agent on the fabric with a scraper. The dry weight of the coating is 5-15g / m 2 , drying at 90℃ for 1-3 minutes, baking at 110-120℃ for 2-3 minutes; (6) Washing: The fabric treated in step (5) is washed 5 to 7 times under ultrasonic conditions, and then dried to obtain a super-hydrophobic modal fabric.

2. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that, The reaction time in step (1) is 60 to 90 minutes; the usage ratio of graphene oxide, acryloyl chloride and tap water is 1 g: (1 to 2) g: (100 to 200) mL.

3. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that, In the step (2), the dosage ratio of sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether (OP-10), acrylic acid, styrene, butyl acrylate, the reaction solution prepared in the step (1) and ammonium persulfate is 1g: (1-2)g: (0.1-0.2)mol: (0.1-0.2)mol: (0.1-0.2)mol: (2-4)mL: (0.5-1)g.

4. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that, In the step (3), the pore-forming agent is fatty alcohol polyoxyethylene ether (AEO-9); the dosage ratio of the pore-forming agent to tap water is 1 g: (100-200) mL.

5. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that, In the step (4), the amount ratio of the graphene oxide modified polyacrylic acid coating agent obtained in step (2) to the pore-forming agent solution obtained in step (3) is 1 mL: (0.1-0.3) mL; the rotation speed of the high-speed dispersing homogenizer is 15000-20000 r / min; and the mixing time is 5-15 min.

6. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that: The fabric in step (5) is modal fabric.

7. A method for preparing a super hydrophobic modal fabric according to claim 1, characterized in that: In the step (6), the ratio of the fabric to the water is 1 g: (100-200) mL; the frequency of the ultrasonic wave is 5-7 Mz, and the sound intensity is 40-60 W / cm 2 .

8. A super hydrophobic modal fabric, characterized in that: The invention is prepared by the method according to any one of claims 1 to 7.