Goose down surface super-hydrophobic modification treatment method and water-repellent goose down

Abstract

The invention relates to a method for super-hydrophobic modification treatment of the surface of goose down and water-repellent goose down. 0.1 to 5 parts of surface modified g-C3N4, 0.5 to 5 parts of wool keratin, 0.2 to 2 parts of nano silicon dioxide, 0.5 to 2 parts of cellulose nanocrystals, 0.1 to 1 part of an accelerant, 1 to 2 parts of a coupling agent, 6 to 10 parts of waterborne polyurethane and 80 to 85 parts of deionized water are stirred and mixed together to obtain a super-hydrophobic finishing agent; wherein the surface modified g-C3N4 is obtained by carrying out modification by utilizing methyl trimethoxy silane and / or carnauba wax; the super-hydrophobic finishing agent is used for carrying out staged heating dipping treatment on goose down, and then drying treatment is carried out to obtain the water-repellent goose down. According to the preparation method, methyltrimethoxysilane and carnauba wax are combined to sequentially carry out surface modification on g-C3N4 to obtain surface modified g-C3N4, the surface modified g-C3N4 is added into a super-hydrophobic finishing agent system containing wool keratin, and the water resistance, washing resistance and lasting antibacterial property of goose down can be remarkably improved through synergistic use of the surface modified g-C3N4 and the super-hydrophobic finishing agent system.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of down processing, and particularly relates to a method for super-hydrophobic modification treatment of goose down surface and water-repellent goose down. BACKGROUND

[0002] As a natural animal protein fiber, goose down has excellent loftiness, warmth retention and lightweight characteristics due to its three-dimensional spherical structure, is known as one of the best natural warmth retention materials, and is widely used in high-end down clothing, bedding and outdoor equipment fields. However, goose down has the following inherent defects: in a high humidity environment, it is easy to absorb water, resulting in an increase in the moisture regain, which not only reduces the warmth retention performance, but also easily breeds mold and mites, produces odor and causes allergic reactions; after absorbing moisture, it needs to be dried, and a dehumidified environment needs to be provided for long-term storage, which significantly increases the storage cost; natural goose down itself does not have antibacterial and bacteriostatic performance, and is easy to become a breeding ground for microorganisms in a humid environment. In order to solve the above problems, the application provides a method for super-hydrophobic modification treatment of goose down surface and water-repellent goose down. SUMMARY

[0003] The purpose of the application is to provide a method for super-hydrophobic modification treatment of goose down surface and water-repellent goose down to solve the above problems.

[0004] The application achieves the above purpose by the following technical scheme: A method for super-hydrophobic modification treatment of goose down surface, comprising the following steps: Step 1: 0.1-5 parts of surface modified g-C3N4, 0.1-3 parts of Grifola frondosa hydrophobic protein HGFI, 0.5-2 parts of wool keratin, 0.2-2 parts of nano silicon dioxide, 0.5-2 parts of cellulose nanocrystals, 0.1-1 parts of an accelerator, 1-2 parts of a coupling agent, 5-10 parts of waterborne polyurethane, and 80-85 parts of deionized water are stirred and mixed together according to weight parts to obtain a super-hydrophobic finishing agent; The surface modified g-C3N4 is obtained by modification with a modifier, and the modifier is at least one of methyltrimethoxysilane and Brazil palm wax; Step 2: the goose down is subjected to stage-wise temperature rising immersion treatment with the super-hydrophobic finishing agent, and then subjected to drying treatment to obtain water-repellent goose down.

[0005] As a further optimization scheme of the application, the method for obtaining surface modified g-C3N4 by modification with methyltrimethoxysilane is as follows: (1) g-C3N4 is ground and sieved, and then dispersed in a 0.05M NaOH solution at a mass ratio of 1:35-45, heated and stirred, washed by centrifugation until neutral, and vacuum dried to obtain CN-OH; (2) mixing methyltrimethoxysilane (MTMS), water and anhydrous ethanol according to mass ratio (3-4):1:(24-28), adjusting pH to 4-5, and obtaining MTMS sol after hydrolysis; (3) dispersing CN-OH in toluene according to mass ratio (2-4):1 under ultrasonic, heating to 75-85℃ under nitrogen atmosphere, and adding dropwise into MTMS sol, refluxing for 3-5h, and obtaining MTMS-g-C3N4 after cooling, washing and drying; and obtaining surface modified g-C3N4 after drying and curing treatment.

[0006] As a further optimization scheme of the application, the method for obtaining surface modified g-C3N4 by modifying methyltrimethoxysilane and carnauba wax (Wax) is as follows: after obtaining MTMS-g-C3N4, preparing carnauba wax, anhydrous ethanol and MTMS-g-C3N4 according to mass ratio 1:(55-65):1-3, dissolving carnauba wax in anhydrous ethanol, adding MTMS-g-C3N4, constant temperature stirring, cooling in ice water bath, suction filtration and vacuum drying to obtain MTMS-Wax-g-C3N4; and obtaining surface modified g-C3N4 after drying and curing treatment.

[0007] As a further optimization scheme of the application, in the method for obtaining surface modified g-C3N4 by modifying, the heating and stirring is specifically 55-65℃, 150-200r / min stirring speed for 2-3h; The hydrolysis is specifically 30-40℃ for 45-60min; The constant temperature stirring is specifically 75-90℃, 500-700r / min stirring speed for 45-60min; The drying and curing treatment is specifically 120-130℃ for 2-3h.

[0008] As a further optimization scheme of the application, in step two, the stage-wise temperature rising immersion treatment is specifically as follows: adding super-hydrophobic finishing agent into deionized water to prepare an immersion liquid, and using the immersion liquid for stage-wise temperature rising immersion treatment of goose down, first stage: 30-40℃ for 1-2h; second stage: 40-55℃ for 2-3h; third stage: 55-65℃ for 1-3h; and carrying out padding after immersion, with padding rate of 75-80%.

[0009] As a further optimization scheme of the application, the addition amount of the hydrophobic finishing agent in deionized water is 20-30g / kg, and 70-100g goose down is added per 1kg of immersion liquid.

[0010] As a further optimization scheme of the application, the promoter includes at least one of maleimide and dimethyl imine ester.

[0011] As a further optimization of the present application, the coupling agent comprises at least one of a silane coupling agent, a phosphate ester coupling agent.

[0012] A water-repellent goose down is prepared by the method as described above.

[0013] The present application has the following advantages: 1) In the present application, methyltrimethoxysilane (MTMS) is combined with carnauba wax to sequentially modify g-C3N4, and the surface-modified g-C3N4 is added to a super-hydrophobic finishing agent system containing wool keratin, which can significantly improve the water resistance, wash resistance, and long-lasting antibacterial properties of goose down, and also make the goose down have a low moisture regain, facilitating storage and reducing storage costs. 2) The surface-modified g-C3N4 modified by methyltrimethoxysilane and carnauba wax in sequence can be uniformly dispersed in the super-hydrophobic finishing agent system, and the wool keratin has a certain specific affinity with the goose down, which promotes the formation of a film layer with strong interfacial stability on the surface of the goose down, thereby improving the water resistance, moisture resistance, and antibacterial properties, as well as the wash resistance. DETAILED DESCRIPTION

[0014] The following further describes the present application, and it is necessary to point out that the following detailed description is only used to further illustrate the present application, and cannot be understood as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above application content.

[0015] I. Materials 1. g-C3N4 (powder): purchased from Xi'an Qiyue Biological Technology Co., Ltd., purity 98%; 2. Methyltrimethoxysilane (MTMS), polydimethylsiloxane (PDMS): purchased from Jiangxi Hongbai New Material Co., Ltd., purity 99%; 3. Carnauba wax (Wax): purchased from Wuhan Jixinyibang Biological Technology Co., Ltd., purity 99%; 4. Wool keratin (powder): purchased from Shanghai Gadel Chemical Technology Co., Ltd., purity 99%; 5. Nano-silicon dioxide: purchased from Yumu (Ningbo) New Material Co., Ltd., purity 99.9%; 6. Cellulose nanocrystals: purchased from Xi'an Qiyue Biological Technology Co., Ltd., purity 99%; 7. Accelerator: at least one of maleimide and dimethyl imine ester, maleimide is used in the following experiment; 8. Coupling agent: at least one of silane coupling agent (KH550, KH560), phosphate coupling agent (JS-311), in the following experiment, silane coupling agent KH560 (purchased from Hubei Wande Chemical Co., Ltd., purity 99%) is used; 9. Waterborne polyurethane: waterborne polyurethane emulsion with solid content of 50% purchased from Beijing Kemite Science and Technology Development Co., Ltd.; 10. pH regulator: acetic acid; 11. Commercially available cleaning and degreasing treated goose down: goose down with a loft of 650+ and above is used, and in the following experiment, white goose down with a loft of 650 is used; Unless otherwise specified, the specific methods in the following examples can be carried out according to conventional methods, and other materials and reagents used can be obtained through commercial channels.

[0016] II. Method Example 1 In this example, a method for modifying the surface of goose down to be super-hydrophobic is provided, which comprises the following steps: 1.1. Preparation of surface-modified g-C3N4 The surface-modified g-C3N4 is obtained by modification with methyltrimethoxysilane (MTMS), and the specific steps are as follows: 1.1.1. After grinding and sieving (200 mesh sieve, same below) g-C3N4, disperse it in 0.05M NaOH solution at a mass ratio of 1:40, heat to 58℃, stir at a speed of 180r / min for 2.5h, centrifugal wash until neutral, and vacuum dry to obtain CN-OH; 1.1.2. Mix methyltrimethoxysilane, water and anhydrous ethanol at a mass ratio of 3.5:1:25, adjust the pH to 4.5, and hydrolyze at 35℃ for 52min to obtain MTMS sol; 1.1.3. Disperse CN-OH in toluene at a mass ratio of 3:1 under ultrasonic, heat to 80℃ under nitrogen atmosphere, and drop into the MTMS sol, reflux for 4h; after cooling, washing and drying, MTMS-g-C3N4 is obtained, and after 2.5h of solidification treatment at 125℃, surface-modified g-C3N4 is obtained.

[0017] 1.2. Preparation of super-hydrophobic finishing agent The raw materials for preparing the super-hydrophobic finishing agent are as follows: 1.1 parts of surface-modified g-C3N4 prepared in step 1.1 above, 4 parts of wool keratin, 0.8 parts of nano-silicon dioxide, 0.5 parts of cellulose nanocrystal, 1 part of accelerator, 1.2 parts of coupling agent, 10 parts of waterborne polyurethane, and 81.4 parts of deionized water are mixed together at a temperature of 28℃±2℃ to obtain the super-hydrophobic finishing agent.

[0018] 1.3 Preparation of water-repellent goose down The super-hydrophobic finishing agent prepared in step 1.2 above is used for stage-wise temperature rising impregnation treatment of the goose down. Specifically, the super-hydrophobic finishing agent is added to deionized water to prepare an impregnation solution, and the amount of the super-hydrophobic finishing agent added to the deionized water is 25 g / kg. The goose down (80 g of goose down is added to every 1 kg of the impregnation solution) is subjected to stage-wise temperature rising impregnation treatment using the impregnation solution, and the first stage is soaking at 35°C for 1.5 h, the second stage is soaking at 48°C for 2.5 h, and the third stage is soaking at 60°C for 2 h. After soaking, padding is performed, and the pick-up rate is 76%. After drying treatment, water-repellent goose down is obtained.

[0019] Example 2 In this example, a method for super-hydrophobic modification treatment of the surface of goose down is provided, which comprises the following steps: 1.1 Preparation of surface-modified g-C3N4 The surface-modified g-C3N4 obtained by modification using methyltrimethoxysilane (MTMS) is prepared according to the following steps: 1.1.1 After grinding and sieving, g-C3N4 is dispersed in a 0.05M NaOH solution at a mass ratio of 1:40, heated to 58°C, stirred at a speed of 180 r / min for 2.5 h, washed by centrifugation until neutral, and vacuum dried to obtain CN-OH; 1.1.2 Methyltrimethoxysilane, water, and anhydrous ethanol are mixed at a mass ratio of 3.5:1:25, and the pH is adjusted to 4.5. After hydrolysis at 35°C for 52 min, MTMS sol is obtained; 1.1.3 CN-OH is ultrasonically dispersed in toluene at a mass ratio of 3:1, heated to 80°C under a nitrogen atmosphere, and added dropwise to the MTMS sol. After refluxing for 4 h, cooling, washing, and drying, MTMS-g-C3N4 is obtained. After 2.5 h of drying and curing at 125°C, surface-modified g-C3N4 is obtained.

[0020] 1.2 Preparation of super-hydrophobic finishing agent The raw materials for preparing the super-hydrophobic finishing agent are mixed together at a temperature of 28°C±2°C to obtain the super-hydrophobic finishing agent, with the proportions being, by weight, 3.5 parts of surface-modified g-C3N4 prepared in step 1.1 above, 2.8 parts of wool keratin, 1 part of nano-silicon dioxide, 1.2 parts of cellulose nanocrystals, 0.5 parts of a promoter, 1.5 parts of a coupling agent, 8 parts of water-based polyurethane, and 81.5 parts of deionized water.

[0021] 1.3 Preparation of water-repellent goose down The super-hydrophobic finishing agent prepared in step 1.2 above is used for phase-wise temperature rising impregnation treatment of the eiderdown. Specifically, the super-hydrophobic finishing agent is added to deionized water to prepare an impregnation solution, and the amount of the super-hydrophobic finishing agent added to the deionized water is 25 g / kg. The eiderdown (80 g of eiderdown is added to every 1 kg of the impregnation solution) is subjected to phase-wise temperature rising impregnation treatment using the impregnation solution, and the first phase is 35°C soaking for 1.5 h; the second phase is 48°C soaking for 2.5 h; and the third phase is 60°C soaking for 2 h. After soaking, padding is performed, and the pick-up rate is 76%. After drying treatment, water-repellent eiderdown is obtained.

[0022] Example 3 In this example, a method for super-hydrophobic modification treatment of the surface of eiderdown is provided, which comprises the following steps: 1.1, Preparation of surface-modified g-C3N4 The surface-modified g-C3N4 obtained by modification using methyltrimethoxysilane (MTMS) has the following specific steps: 1.1.1, After grinding and sieving, g-C3N4 is dispersed in 0.05M NaOH solution at a mass ratio of 1:40, heated to 58°C, stirred at a speed of 180 r / min for 2.5 h, washed by centrifugation until neutral, and vacuum dried to obtain CN-OH; 1.1.2, Methyltrimethoxysilane, water, and anhydrous ethanol are mixed at a mass ratio of 3.5:1:25, and the pH is adjusted to 4.5. After hydrolysis at 35°C for 52 min, MTMS sol is obtained; 1.1.3, CN-OH is ultrasonically dispersed in toluene at a mass ratio of 3:1, heated to 80°C under a nitrogen atmosphere, and added dropwise to the MTMS sol. After refluxing for 4 h, cooling, washing, and drying, MTMS-g-C3N4 is obtained. After 2.5 h of solidification treatment at 125°C, surface-modified g-C3N4 is obtained.

[0023] 1.2, Preparation of super-hydrophobic finishing agent The raw materials for preparing the super-hydrophobic finishing agent are mixed together at a temperature of 28°C±2°C to obtain the super-hydrophobic finishing agent, with the proportions being, by weight, 5 parts of the surface-modified g-C3N4 prepared in step 1.1 above, 0.5 parts of wool keratin, 1.5 parts of nano-silicon dioxide, 2 parts of cellulose nanocrystals, 0.4 parts of a promoter, 2 parts of a coupling agent, 6 parts of water-based polyurethane, and 82.6 parts of deionized water.

[0024] 1.3, Preparation of water-repellent eiderdown The super-hydrophobic finishing agent prepared by the above step 1.2 is used for phase-wise temperature rising impregnation treatment of the eiderdown. Specifically, the super-hydrophobic finishing agent is added to deionized water to prepare an impregnation solution, and the addition amount of the super-hydrophobic finishing agent in the deionized water is 25 g / kg. The eiderdown is added to the impregnation solution (80 g of eiderdown is added to 1 kg of the impregnation solution) for phase-wise temperature rising impregnation treatment, the first phase: 35°C for 1.5 h; the second phase: 48°C for 2.5 h; the third phase: 60°C for 2 h. After soaking, liquid padding is performed, and the pick-up rate is 76%. After drying treatment, water-repellent eiderdown is obtained.

[0025] Example 4 In this example, a method for super-hydrophobic modification treatment of the surface of eiderdown is provided, comprising the following steps: 1.1, Preparation of surface modified g-C3N4 The surface modified g-C3N4 is prepared by modification of methyltrimethoxysilane and Brazil palm wax, and the specific steps are as follows: 1.1.1, After grinding and sieving, g-C3N4 is dispersed in 0.05M NaOH solution at a mass ratio of 1:40, heated to 58°C, stirred at a speed of 180r / min for 2.5h, washed by centrifugation until neutral, and vacuum dried to obtain CN-OH; 1.1.2, Methyltrimethoxysilane, water and anhydrous ethanol are mixed at a mass ratio of 3.5:1:25, and the pH is adjusted to 4.5. After hydrolysis at 35°C for 52 min, MTMS sol is obtained; 1.1.3, CN-OH is ultrasonically dispersed in toluene at a mass ratio of 3:1, heated to 80°C under nitrogen atmosphere, and added dropwise to the MTMS sol. After refluxing for 4h, MTMS-g-C3N4 is obtained after cooling, washing and drying. After 2.5h of drying and curing at 125°C, surface modified g-C3N4 is obtained; 1.1.4, Brazil palm wax, anhydrous ethanol and MTMS-g-C3N4 are prepared at a mass ratio of 1:58:2. The Brazil palm wax is dissolved in anhydrous ethanol, and then the MTMS-g-C3N4 is added. After constant temperature stirring at 82°C and a stirring speed of 650r / min for 48min, cooling is performed in an ice water bath, suction filtration and vacuum drying are performed to obtain MTMS-Wax-g-C3N4. After 2.5h of drying and curing at 125°C, surface modified g-C3N4 is obtained.

[0026] 1.2, Preparation of super-hydrophobic finishing agent Preparation of super-hydrophobic finishing agent, by weight parts, 3.5 parts of surface modified g-C3N4 prepared in step 1.1 above, 2.8 parts of wool keratin, 1 part of nano-silica, 1.2 parts of cellulose nanocrystal, 0.5 parts of accelerator, 1.5 parts of coupling agent, 8 parts of water-based polyurethane, 81.5 parts of deionized water are mixed together at a temperature of 28℃±2℃ to obtain a super-hydrophobic finishing agent.

[0027] 1.3, preparation of water-repellent goose down The goose down is subjected to stage-wise temperature rising impregnation treatment with the super-hydrophobic finishing agent prepared in step 1.2 above. Specifically, the super-hydrophobic finishing agent is added to deionized water to prepare an impregnation solution, and the amount of the super-hydrophobic finishing agent added to the deionized water is 25g / kg. The goose down (80g of goose down is added to every 1kg of the impregnation solution) is subjected to stage-wise temperature rising impregnation treatment with the impregnation solution. The first stage is soaking at 35℃ for 1.5h; the second stage is soaking at 48℃ for 2.5h; and the third stage is soaking at 60℃ for 2h. After soaking, padding is performed, and the pick-up rate is 76%. After drying treatment, water-repellent goose down is obtained.

[0028] Example 5 In this embodiment, a method for super-hydrophobic modification treatment of the surface of goose down is provided, which comprises the following steps: 1.1, preparation of surface modified g-C3N4 The surface modified g-C3N4 is obtained by modification of methyltrimethoxysilane and Brazil palm wax, and the specific steps are as follows: 1.1.1, after grinding and sieving, g-C3N4 is dispersed in 0.05M NaOH solution at a mass ratio of 1:40, heated to 58℃, stirred at a speed of 180r / min for 2.5h, washed by centrifugation until neutral, and vacuum dried to obtain CN-OH; 1.1.2, methyltrimethoxysilane, water and anhydrous ethanol are mixed at a mass ratio of 3.5:1:25, the pH is adjusted to 4.5, and MTMS sol is obtained after hydrolysis at 35℃ for 52min; 1.1.3, CN-OH is ultrasonically dispersed in toluene at a mass ratio of 3:1, heated to 80℃ under nitrogen atmosphere, and added dropwise to the MTMS sol, and refluxed for 4h; after cooling, washing and drying, MTMS-g-C3N4 is obtained, and after 2.5h of drying and curing treatment at 125℃, surface modified g-C3N4 is obtained; 1.1.4, prepare the mass ratio of 1:58:2 of the Brazilian palm wax, anhydrous ethanol, MTMS-g-C3N4, dissolve the Brazilian palm wax in anhydrous ethanol, then add MTMS-g-C3N4, constant temperature at 82℃, stirring at 650r / min for 48min, cooling in ice water bath, suction filtration, vacuum drying to obtain MTMS-Wax-g-C3N4, then oven drying and curing at 125℃ for 2.5h to obtain surface modified g-C3N4.

[0029] 1.2, preparation of super-hydrophobic finishing agent The preparation of super-hydrophobic finishing agent, by weight, 3.5 parts of the surface modified g-C3N4 prepared in step 1.1 above, 2.8 parts of wool keratin, 1 part of nano-silicon dioxide, 1.2 parts of cellulose nanocrystal, 0.5 parts of accelerator, 1.5 parts of coupling agent, 8 parts of water-based polyurethane, 81.5 parts of deionized water are mixed together at 28℃±2℃ to obtain the super-hydrophobic finishing agent.

[0030] 1.3, preparation of water-repellent goose down The super-hydrophobic finishing agent prepared in step 1.2 above is used for constant temperature immersion treatment of goose down. The constant temperature immersion treatment is as follows: the super-hydrophobic finishing agent is added to deionized water to prepare an immersion solution, the amount of super-hydrophobic finishing agent added to deionized water is 25g / kg, the immersion solution is used for constant temperature immersion treatment of goose down (80g of goose down is added to 1kg of immersion solution), 48℃ soaking for 6h, then rolling after soaking, the rolling rate is 76%; then drying treatment to obtain water-repellent goose down.

[0031] Comparative Example 1 In this comparative example, a method for super-hydrophobic modification of the surface of goose down is provided. On the basis of Example 4, the preparation of super-hydrophobic finishing agent in step 1.2 is adjusted as follows: the preparation of super-hydrophobic finishing agent, by weight, 3.5 parts of the surface modified g-C3N4 prepared in step 1.1 above, 1 part of nano-silicon dioxide, 1.2 parts of cellulose nanocrystal, 0.5 parts of accelerator, 1.5 parts of coupling agent, 8 parts of water-based polyurethane, 84.3 parts of deionized water are mixed together to obtain the super-hydrophobic finishing agent. The rest is consistent with Example 4.

[0032] Comparative Example 2 In the present comparative example, a method for super-hydrophobic modification treatment of goose feather surface is provided, based on Example 4, step 1.1 is omitted, and the preparation raw materials of the super-hydrophobic finishing agent in step 1.2 are adjusted, and after adjustment, the preparation raw materials of the super-hydrophobic finishing agent are as follows: 3.5 parts of g-C3N4 (i.e. unmodified g-C3N4, ground through a 200-mesh sieve and used directly), 2.8 parts of wool keratin, 1 part of nano-silicon dioxide, 1.2 parts of cellulose nanocrystal, 0.5 part of accelerator, 1.5 parts of coupling agent, 8 parts of water-based polyurethane, and 81.5 parts of deionized water are mixed together to obtain the super-hydrophobic finishing agent; The rest are consistent with Example 4.

[0033] Comparative Example 3 In the present comparative example, a method for super-hydrophobic modification treatment of goose feather surface is provided, based on Example 4, the preparation raw materials of the super-hydrophobic finishing agent in step 1.2 are adjusted, and after adjustment, the preparation raw materials of the super-hydrophobic finishing agent are as follows: 3.5 parts of g-C3N4 (i.e. unmodified g-C3N4, ground through a 200-mesh sieve and used directly), 1 part of nano-silicon dioxide, 1.2 parts of cellulose nanocrystal, 0.5 part of accelerator, 1.5 parts of coupling agent, 8 parts of water-based polyurethane, and 84.3 parts of deionized water are mixed together to obtain the super-hydrophobic finishing agent; The rest are consistent with Example 4.

[0034] Comparative Example 4 In the present comparative example, a method for super-hydrophobic modification treatment of goose feather surface is provided, based on Example 4, step 1.1 is adjusted, and after adjustment, it is as follows: 1.1, preparation of surface-modified g-C3N4 The surface-modified g-C3N4 is obtained by modification of polydimethylsiloxane (PDMS) and Brazil palm wax, and the specific steps are as follows: 1.1.1, grind g-C3N4 through a sieve and disperse it in 0.05M NaOH solution at a mass ratio of 1:40, heat to 58℃, stir at a speed of 180r / min for 2.5h, centrifugal wash to neutral, vacuum dry to obtain CN-OH; 1.1.2, mix polydimethylsiloxane, water and toluene at a mass ratio of 3.5:1:25, adjust the pH to 4.5, hydrolyze at 35℃ for 52min to obtain PDMS sol; 1.1.3, ultrasonically disperse CN-OH in toluene at a mass ratio of 3:1, heat to 80℃ under nitrogen atmosphere, and drop into the PDMS sol, reflux for 4h; cool, wash and dry to obtain PDMS-g-C3N4, then treat with 125℃ drying and curing for 2.5h to obtain surface-modified g-C3N4; 1.1.4, prepare the mass ratio of 1:58:2 of the Carnauba wax, anhydrous ethanol, PDMS-g-C3N4, dissolve the Carnauba wax in anhydrous ethanol, then add PDMS-g-C3N4, constant temperature at 82℃, stirring at 650r / min for 48min, cooling in ice water bath, suction filtration, vacuum drying to obtain PDMS-Wax-g-C3N4, then oven drying and curing at 125℃ for 2.5h to obtain surface modified g-C3N4; The rest are the same as Example 4.

[0035] Comparative Example 5 In this comparative example, a method for super-hydrophobic modification treatment of goose down surface is provided, and step 1.1 is adjusted based on Example 4, and the adjusted step is as follows: 1.1, preparation of surface modified g-C3N4 The surface modified g-C3N4 is obtained by modification of methyltrimethoxysilane and Carnauba wax, and the specific steps are as follows: 1.1.1, grind g-C3N4 through a sieve and disperse in 0.05M NaOH solution at a mass ratio of 1:40, heat to 58℃, stir at 180r / min for 2.5h, centrifugal wash to neutral, vacuum drying to obtain CN-OH; 1.1.2, prepare the mass ratio of 1:58:2 of the Carnauba wax, anhydrous ethanol, CN-OH, dissolve the Carnauba wax in anhydrous ethanol, then add CN-OH, constant temperature at 82℃, stirring at 650r / min for 48min, cooling in ice water bath, suction filtration, vacuum drying to obtain Wax-g-C3N4, then oven drying and curing at 125℃ for 2.5h to obtain surface modified g-C3N4; The rest are the same as Example 4.

[0036] Blank group The commercially available goose down after cleaning and degreasing treatment is used as the blank group.

[0037] Three, performance test 3.2, waterproof and moisture-proof performance test Water washing 50 times goose down sample: according to the goose down washing method in IDFB-2017, the washing machine and dryer are required to meet the requirements in AATCC135 standard, 100% pure cotton fabric is used, two pieces of 10-inch diameter fabric are cut, two circular fabrics are sewn into a pillowcase, and a small opening for filling goose down is left, 80g goose down is weighed and filled into the circular pillowcase through the small opening, and finally the pillow is sewn up, and the goose down sample is sewn into a small circular pillow; the single water washing procedure is that the washing temperature is 25℃±2℃, the washing time is 24min, the dehydration time is 6min, and the drying is carried out at 46℃ for 30min; after repeating the single water washing procedure 50 times, the water washing 50 times goose down sample is obtained.

[0038] The surface contact angle of the goose down is tested by using a contact angle tester, 20 samples are tested in each group, the average value is taken, and the moisture regain of the goose down is detected according to the detection method in GB / T 10288-2016 after being stored in a humid environment (standard atmospheric conditions, temperature 24℃±2℃, humidity 80%±2%) for 6 months, and the results are shown in Table 1: Table 1 Water resistance and moisture resistance performance test data of goose down ; Experimental conclusion: from the data in Table 1, it can be known that the surface modified g-C3N4 is obtained by sequentially modifying g-C3N4 with methyltrimethoxysilane (MTMS) and Brazilian palm wax in the application, and the synergistic use of the surface modified g-C3N4 added to the super-hydrophobic finishing agent system containing wool keratin can significantly improve the water resistance of the goose down, so that the goose down has low moisture regain, is convenient to store and save, and reduces the storage cost. It is speculated that the surface modified g-C3N4 modified with methyltrimethoxysilane (MTMS) and Brazilian palm wax in sequence can be uniformly dispersed in the super-hydrophobic finishing agent system, the wool keratin has a certain specific affinity with the goose down, which promotes the formation of a membrane layer with strong interfacial stability on the surface of the goose down, thereby improving the water resistance, moisture resistance and washing resistance.

[0039] 3.2, antibacterial performance test Antibacterial performance test: the antibacterial performance of the above-mentioned examples 1-5, comparative examples 1-5 and the blank group is tested according to the experimental method in GB / T20944.2 2007 Evaluation of antibacterial properties of textiles Part 2: absorption method, the test bacteria are gram-positive bacteria (Staphylococcus aureus ATCC 6538) and gram-negative bacteria (Escherichia coli ATCC11229); the antibacterial test is carried out according to the standard, and the test results are recorded in Table 2: Table 2 Goose down antibacterial performance test data ; Experimental conclusion: Based on the analysis in Table 2, it is known that after the goose down is soaked and inclined and rolled by the super-hydrophobic finishing agent, the antibacterial property of the goose down can be significantly improved, wherein in the super-hydrophobic finishing agent, the lack of wool keratin leads to the significant decrease of the antibacterial property of the goose down, and the washing resistance also has a significant downward trend, which shows that the wool keratin can synergize with the surface modified g-C3N4 modified by methyltrimethoxysilane (MTMS) and Brazil palm wax in turn, and form a dense film layer to provide strong protection to the goose down.

[0040] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent of the present application. It should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application.

Claims

1. A method of lotus surface superhydrophobic modification treatment, characterized by: The method comprises the following steps: Step one: 0.1-5 parts of surface modified g-C3N4, 0.5-5 parts of wool keratin, 0.2-2 parts of nano silicon dioxide, 0.5-2 parts of cellulose nanocrystals, 0.1-1 parts of accelerant, 1-2 parts of coupling agent, 6-10 parts of water-based polyurethane, 80-85 parts of deionized water are stirred and mixed together to obtain a super-hydrophobic finishing agent; The surface modified g-C3N4 is obtained by modifying a modifier, and the modifier is at least one of methyltrimethoxysilane and Brazil palm wax; Step two: the super-hydrophobic finishing agent is used for stage-wise temperature rising impregnation treatment of goose down, and then drying treatment is performed to obtain water-repellent goose down.

2. The method of claim 1, wherein the method is characterized by: The method for obtaining the surface modified g-C3N4 by modifying methyltrimethoxysilane is as follows: (1) g-C3N4 is ground and sieved, and then dispersed in a 0.05M NaOH solution at a mass ratio of 1:35-45, heated and stirred, centrifuged and washed to neutral, and vacuum dried to obtain CN-OH; (2) methyltrimethoxysilane, water and anhydrous ethanol are mixed at a mass ratio of 3-4:1:24-28, and then the pH is adjusted to 4-5, and hydrolysis is performed to obtain MTMS sol; (3) CN-OH is ultrasonically dispersed in toluene at a mass ratio of 2-4:1, heated to 75-85°C in a nitrogen atmosphere, and then added dropwise to the MTMS sol, refluxed for 3-5h, cooled, washed and dried to obtain MTMS-g-C3N4; and then dried and solidified to obtain the surface modified g-C3N4.

3. A method of lotus surface superhydrophobic modification treatment according to claim 2, characterized in that: The method for obtaining the surface modified g-C3N4 by modifying methyltrimethoxysilane and Brazil palm wax is as follows: after obtaining the MTMS-g-C3N4, Brazil palm wax, anhydrous ethanol and MTMS-g-C3N4 are prepared at a mass ratio of 1:(55-65):1-3, the Brazil palm wax is dissolved in the anhydrous ethanol, then the MTMS-g-C3N4 is added, constant temperature stirring is performed, ice water bath cooling is performed, suction filtration is performed, and vacuum drying is performed to obtain MTMS-Wax-g-C3N4; and then dried and solidified to obtain the surface modified g-C3N4.

4. The method of claim 3, wherein the method is characterized by: In the method for obtaining the surface modified g-C3N4 by modifying the modifier, the heating and stirring is specifically 55-65°C, 150-200r / min stirring speed for 2-3h; The hydrolysis is specifically 30-40°C for 45-60min; The constant temperature stirring is specifically 75-90°C, 500-700r / min stirring speed for 45-60min; The drying and solidification treatment is specifically 120-130°C for 2-3h.

5. The method of claim 1, wherein the method is characterized by: In step two, the stage-wise temperature rising impregnation treatment is specifically that the super-hydrophobic finishing agent is added to deionized water to prepare an impregnation liquid, the goose down is impregnated with the impregnation liquid in a stage-wise temperature rising manner, the first stage is 30-40°C for 1-2h, the second stage is 40-55°C for 2-3h, and the third stage is 55-65°C for 1-3h; and then padding is performed, and the padding rate is 75-80%.

6. The method of claim 5, wherein the method is characterized by: The hydrophobic finishing agent is added in an amount of 20-30 g / kg in deionized water, and 70-100 g goose down is added per 1 kg of the impregnating solution.

7. The method of claim 1, wherein the method is characterized by: The accelerator includes at least one of maleimide and dimethyl imine ester.

8. The method of claim 1, wherein the method is characterized by: The coupling agent includes at least one of a silane coupling agent and a phosphate ester coupling agent.

9. A water repellent goose down characterized by: The method is prepared by any one of the above 1-8.