WO2018227751A1 - 一种超疏水织物及其制备方法 - Google Patents

一种超疏水织物及其制备方法 Download PDF

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WO2018227751A1
WO2018227751A1 PCT/CN2017/097649 CN2017097649W WO2018227751A1 WO 2018227751 A1 WO2018227751 A1 WO 2018227751A1 CN 2017097649 W CN2017097649 W CN 2017097649W WO 2018227751 A1 WO2018227751 A1 WO 2018227751A1
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pickering emulsion
fabric
surface energy
low surface
amphiphilic
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PCT/CN2017/097649
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English (en)
French (fr)
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毛志平
刘伶俐
谢汝义
隋晓峰
徐红
张琳萍
钟毅
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东华大学
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Priority to US16/349,295 priority Critical patent/US11421377B2/en
Publication of WO2018227751A1 publication Critical patent/WO2018227751A1/zh

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Definitions

  • the invention belongs to the field of functional textiles, and particularly relates to a superhydrophobic fabric and a one-step method for preparing a durable superhydrophobic fabric by using Pickering emulsion technology.
  • Bionic superhydrophobic fabrics have been favored by academic circles and industry and commerce for their good self-cleaning, anti-fouling, water-repellent and anti-adhesive properties.
  • a low surface energy compound such as a long-chain alkane, silicone or organic fluorine is usually introduced into the surface of the fabric by physical or chemical surface treatment, or a rough structure is formed on the surface of the fabric, and then treated with a low surface energy compound to impart excellent properties.
  • Super hydrophobic performance In practical applications, the finished fabric has poor water wash and soap washability.
  • a conventional method for improving durability is to introduce a crosslinking agent such as a silane coupling agent, a urea aldehyde crosslinking agent, an epoxy compound crosslinking agent, etc. in a system for crosslinking a finishing coating or a fabric and a coating. A covalent bond is introduced between them.
  • a crosslinking agent such as a silane coupling agent, a urea aldehyde crosslinking agent, an epoxy compound crosslinking agent, etc.
  • Pickering emulsion technology is a new technology that uses solid particles instead of traditional surfactants to stabilize emulsions.
  • the solid particles form irreversible adsorption at the incompatible two-phase interface, thereby enhancing the emulsion interface stability.
  • Most of Pickering emulsions are also environmentally friendly, low cost, and easy to operate. They are widely used in food, cosmetics, pharmaceuticals, etc., and there are few applications on textiles.
  • the object of the present invention is to provide a superhydrophobic fabric and a preparation method thereof, which can impart superhydrophobicity to a fabric through a quick and simple finishing process, solve the problem of poor durability of the product, and increase the added value of the fabric and Practicality, broaden its application range.
  • the present invention provides a superhydrophobic fabric characterized in that it is obtained by Pickering emulsion emulsification using amphiphilic particles, a low surface energy substance and water.
  • the invention also provides a one-step method for preparing the above-mentioned durable superhydrophobic fabric by using Pickering emulsion technology, which comprises: emulsifying amphiphilic particles, low surface energy substances and water to form a Pickering emulsion, and using the above Pickering emulsion in one step. Finishing textiles, drying, and obtaining super-hydrophobic fabrics.
  • Pickering emulsion technology comprises: emulsifying amphiphilic particles, low surface energy substances and water to form a Pickering emulsion, and using the above Pickering emulsion in one step. Finishing textiles, drying, and obtaining super-hydrophobic fabrics.
  • the Pickering emulsion is an oil-in-water emulsion.
  • the amphiphilic particles are amphiphilic silica, amphiphilic graphene oxide, amphiphilic graphene, amphiphilic carbon nanotubes, amphiphilic calcium carbonate, amphiphilic ferric oxide, cellulose microcrystals, At least one of lignin crystallites and starch nanocrystals.
  • the low surface energy substance is at least one of a silicone oil, a long-chain alkane compound having a carbon number of n ⁇ 16 and a perfluoroalkyl compound having a carbon number of n ⁇ 6.
  • the textile is cellulose fiber, polyester, nylon, acrylic, acetate, wool fiber fabric or a blend fabric of two or more of the fibers.
  • the finishing method is a padding method, a dipping method, a coating method or a spraying method.
  • the total concentration of the amphiphilic particles and the low surface energy substance in the Pickering emulsion is 0 to 300 mg/mL, and is not 0; more preferably 80 to 120 mg/mL.
  • the mass ratio of the amphiphilic particles to the low surface energy material in the Pickering emulsion is 1:0-30, and is not 0; more preferably 1:1-10.
  • the emulsification method is homogeneous dispersion, cell pulverization or ultrasonic dispersion.
  • the drying is pre-baked for 1-3 min at 60-80 ° C and 1-3 min at 120-160 ° C, or dried for 30-60 min at 120-150 ° C.
  • the invention firstly utilizes the amphiphilic particles to coat the low surface energy material to form a stable oil-in-water Pickering emulsion, and then the above-mentioned oil-in-water Pickering emulsion is applied by padding, dipping, coating or spraying the fabric, and is baked. Dry and baked, stabilized emulsion particles can form a rough interface on the surface of the fabric. Hydrophobic silicone oils, long-chain alkane compounds and short-chain fluorocarbon compounds can impart a rough interfacial hydrophobic property, so that a durable superhydrophobic fabric can be quickly obtained.
  • the invention adopts Pickering emulsion technology to finish the fabric, and applies low specific surface substance
  • the coarse structure is constructed by solid particles to achieve superhydrophobic purpose; the other amphiphilic solid particles contain reactive functional groups, which can form chemical bonds with the fabric matrix or low surface energy compound to improve the durability of the superhydrophobic finishing.
  • the preparation method of the invention is simple and feasible, and has wide applicability.
  • the superhydrophobic properties of the fabric are quickly achieved by introducing a low surface energy substance and a coarse structure simultaneously by a one-step method. After repeated standard soaping, the fabric still retains excellent water repellency.
  • the preparation process does not involve any toxic and harmful reagents and gases, is environmentally friendly, and has good product uniformity and reproducibility, which is conducive to promotion.
  • the durable superhydrophobic cotton fabric prepared according to the method of the present invention has a static contact angle of up to 156° with 5 ⁇ L of water droplets; the durable superhydrophobic polyester fabric prepared according to the method of the present invention has a static contact angle with VL of 5 ⁇ L of water droplets; And the droplets are easy to roll off. After finishing, the fabric can be soaped at least 30 times.
  • the preparation method of the invention is simple and feasible, and has wide applicability
  • the present invention rapidly realizes the superhydrophobic property of the fabric by simultaneously introducing a low surface energy substance and a rough structure by a one-step method;
  • the preparation process of the invention does not involve any toxic and harmful reagents and gases, is environmentally friendly, and has good product uniformity and reproducibility, and is favorable for promotion.
  • Figure 1 is a flow diagram of a one-step process for preparing a durable superhydrophobic fabric using the Pickering emulsion technique.
  • Figure 2 is a diagram showing the lyophobicity of the finished fabric of the fabric of Example 1, 2 for different liquids prior to soaping.
  • Figure 3 is a diagram showing the lyophobicity of different fabrics after finishing the fabric of the fabric of Example 1, 2 of the present invention after 30 times of standard soaping.
  • the static contact angle in the present invention adopts the hanging drop method, the German KRUSS GmbH DSA30 contact angle measurement The meter method is tested.
  • the volume of the water droplets was 5 ⁇ L.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion conditions.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 80 mg/mL, amphiphilic particles and The mass ratio of the low surface energy material was 1:1, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the bleached cotton woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 155°, and the static contact angle was still as high as 153° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the lyophobic effect of the cotton fabric subjected to conventional padding finishing in this embodiment is as shown in Fig. 2(I), and the cotton fabric is provided for deionized water, red dye liquor, juice, coca cola, tea, coffee and milk droplets. Excellent lyophobic effect, the droplets are spherical on the finished fabric and easy to roll off.
  • the durable lyophobic effect of the cotton fabric which has been subjected to conventional padding finishing in this embodiment is as shown in Fig. 3(I).
  • the cotton fabric is cleaned against deionized water,
  • the red dye liquor, juice, coca cola, tea, coffee and milk droplets still have excellent lyophobic effect, and the droplets are spherical on the finished fabric and are easy to roll off.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion conditions.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 120 mg/mL, amphiphilic particles and The mass ratio of the low surface energy material was 1:1, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the polyester woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 152°, and after 30 washings in accordance with the ISO 105-C10:2007 test method, the static contact angle was 150°.
  • the lyophobic effect of the polyester fabric which has been subjected to conventional padding finishing in this embodiment is as shown in Fig. 2(II), and the polyester fabric has the functions of deionized water, red dye liquor, juice, coca cola, tea, coffee and milk droplets. Excellent lyophobic effect, the droplets are spherical on the finished fabric and easy to roll off.
  • the durable lyophobic property of the polyester fabric which has been subjected to conventional padding finishing in this embodiment is shown in Fig. 3(II).
  • the polyester fabric is subjected to deionized water, The red dye liquor, juice, coca cola, tea, coffee and milk droplets still have excellent lyophobic effect, and the droplets are spherical on the finished fabric and are easy to roll off.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. mixed with water, emulsified under ultrasonic cell pulverization to form oil-in-water Pickering emulsion, amphiphilic nanoparticles in emulsion
  • the total concentration of the low surface energy substance was 120 mg/mL, the mass ratio of the amphiphilic particles to the low surface energy material was 1:2, the cell pulverization power was 540 W, and the emulsification time was 3 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the bleached cotton woven fabric, and the rolling ratio is 70%;
  • Drying then prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 155°, and the static contact angle was still as high as 154° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified under ultrasonic cell pulverization to form an oil-in-water Pickering emulsion.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 120 mg/mL, amphiphilic particles and low
  • the surface energy mass ratio was 1:2
  • the cell pulverization power was 540 W
  • the emulsification time was 3 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to two-dip two-rolling finishing of the polyester woven fabric, and the rolling ratio is 70%;
  • Drying then prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 150°, and the static contact angle was still as high as 148° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises aqueous phase 1 and oil.
  • Phase, the oil phase is a low surface energy material 2
  • the amphiphilic particles 3 enclose a low surface energy material 2 .
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion conditions.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 80 mg/mL, amphiphilic particles and The mass ratio of the low surface energy material was 1:2, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • One-step method of finishing textiles by using the above Pickering emulsion immersing the bleached cotton woven fabric in the above-mentioned stable oil-in-water Pickering emulsion at room temperature for 10 minutes, and then taking out;
  • Drying drying at 135 ° C for 30 min, to obtain durable super-hydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 156°, and after 30 washings in accordance with the ISO 105-C10:2007 test method, the static contact angle was still as high as 153°.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion conditions.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 120 mg/mL, amphiphilic particles and The mass ratio of the low surface energy material was 1:2, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the polyester woven fabric is immersed in a stable oil-in-water Pickering emulsion at room temperature for 10 minutes, and then taken out;
  • Drying drying at 135 ° C for 30 min, to obtain durable super-hydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets is 154° according to ISO 105-C10: After the 2007 test method was washed 30 times, the static contact angle was 150°.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified under ultrasonic cell pulverization to form an oil-in-water Pickering emulsion.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 80 mg/mL, amphiphilic particles and low.
  • the surface energy mass ratio was 1:2
  • the cell pulverization power was 540 W
  • the emulsification time was 3 min.
  • One-step method of finishing textiles by using the above Pickering emulsion immersing the bleached cotton woven fabric in the above-mentioned stable oil-in-water Pickering emulsion at room temperature for 10 minutes, and then taking out;
  • Drying drying at 135 ° C for 30 min, to obtain durable super-hydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 154°, and the static contact angle was still as high as 151° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion Amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy organic silicone oil (PDMS 4000, Shanghai, China) Figure Silicone Material Co., Ltd. is mixed with water and emulsified under ultrasonic cell pulverization to form an oil-in-water Pickering emulsion.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 120 mg/mL, amphiphilic particles and low
  • the surface energy mass ratio was 1:5, the cell pulverization power was 540 W, and the emulsification time was 3 min.
  • the polyester woven fabric is immersed in a stable oil-in-water Pickering emulsion at room temperature for 10 minutes, and then taken out;
  • Drying drying at 135 ° C for 30 min, to obtain durable super-hydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 154°, and the static contact angle was 150° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsifying amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion amphiphilic silica particles (Bindzil CC40, Eka Chemical Company, Sweden) and low surface energy substance perfluoroalkyl compounds (1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, Hangzhou Anjiarui Technology Co., Ltd., China, mixed with water, emulsified under the homogenizer dispersion conditions to form an oil-in-water Pickering emulsion, amphiphilic particles in the emulsion and
  • the total concentration of the low surface energy substance was 80 mg/mL, the mass ratio of the amphiphilic particles to the low surface energy substance was 1:30, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the bleached cotton woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 160°, and the static contact angle was still as high as 158° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion amphiphilic silica particles (Bindzil CC40, Eka Chemical Co., Sweden) and low surface energy materials Paraffinic compounds (n-hexadecane, China Shanghai Sinopharm Chemical Reagent Co., Ltd.) are mixed with water and emulsified to form oil-in-water Pickering emulsion, amphiphilic particles and low surface energy substances in the emulsion under homogenizer dispersion conditions.
  • the total concentration was 300 mg/mL
  • the mass ratio of the amphiphilic particles to the low surface energy material was 1:10
  • the homogenizer speed was 15,000 rpm
  • the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the polyester woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 120 ° C for 3 min, to obtain a durable superhydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 150°, and the static contact angle was still as high as 148° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsifying amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion combining amphiphilic ferroferric oxide particles (PuriMag200Si-Epoxy, Xiamen Purimag Biotech Co., Ltd.) with low surface energy substances Silicone oil (PDMS 4000, Shanghai Momentive Silicone Material Co., Ltd., China) is mixed with water and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion is 80 mg/mL, the mass ratio of the amphiphilic particles to the low surface energy material was 1:1, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the bleached cotton woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 153°, and after 30 washings in accordance with the ISO 105-C10:2007 test method, the static contact angle was still as high as 150°.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion amphiphilic cellulose microcrystals (CNC-C, Guangxi Guilin Qihong Technology Co., Ltd.) and low surface energy substance perfluoroalkyl
  • CNC-C amphiphilic cellulose microcrystals
  • the compound (1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, Hangzhou Anjiarui Technology Co., Ltd., China) is mixed with water and emulsified to form an oil-in-water Pickering emulsion and emulsion under homogenizer dispersion conditions.
  • the total concentration of the middle amphiphilic particles and the low surface energy substance was 300 mg/mL, the mass ratio of the amphiphilic particles to the low surface energy material was 1:0.5, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the bleached cotton woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 160 ° C for 3 min, to obtain a durable superhydrophobic cotton fabric.
  • the static contact angle of the above durable superhydrophobic cotton fabric with water droplets was 152°, and the static contact angle was still as high as 149° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsifying amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion aqueous amphiphilic graphene oxide dispersion (XF020, Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) and low surface energy organic silicone oil (PDMS 4000, Shanghai Momentive Silicone Material Co., Ltd., China, was mixed and emulsified to form an oil-in-water Pickering emulsion under homogenizer dispersion conditions.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion was 80 mg/mL.
  • the mass ratio of the amphiphilic particles to the low surface energy material was 1:0.5, the homogenizer speed was 15,000 rpm, and the emulsification time was 5 min.
  • the polyester woven fabric is immersed in a stable oil-in-water Pickering emulsion at room temperature for 10 minutes, and then taken out;
  • Drying drying at 135 ° C for 30 min, to obtain durable super-hydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 150°, and the static contact angle was 144° after washing 30 times in accordance with the ISO 105-C10:2007 test method.
  • the Pickering emulsion comprises an aqueous phase 1 and an oil phase, the oil phase is a low surface energy substance 2, and the amphiphilic particles 3 enclose a low surface energy substance 2.
  • Emulsion of amphiphilic particles and low surface energy materials to form a stable oil-in-water Pickering emulsion amphiphilic calcium carbonate particles (VK-CaC112-1, Hangzhou Wanjing New Materials Co., Ltd., China) and low surface energy materials long-chain alkanes
  • the compound (n-hexadecane, China Shanghai Sinopharm Chemical Reagent Co., Ltd.) is mixed with water and emulsified under ultrasonic cell pulverization to form an oil-in-water Pickering emulsion.
  • the total concentration of amphiphilic particles and low surface energy substances in the emulsion At 80 mg/mL, the mass ratio of the amphiphilic particles to the low surface energy material was 1:5, the cell pulverization power was 540 W, and the emulsification time was 3 min.
  • the one-step method uses the above Pickering emulsion to finish the textile: the stable oil-in-water Pickering emulsion is subjected to conventional two-dip two-rolling finishing of the polyester woven fabric, and the rolling ratio is 70%;
  • Drying prebaking at 80 ° C for 3 min, baking at 120 ° C for 3 min, to obtain a durable superhydrophobic polyester fabric.
  • the static contact angle of the above durable superhydrophobic polyester fabric with water droplets was 150°, and the static contact angle was still as high as 147° after washing 30 times in accordance with the ISO 105-C10:2007 test method.

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Abstract

提供了一种超疏水织物及其制备方法，属于纺织领域。所述的超疏水织物，其特征在于，利用双亲性粒子和低表面能物质乳化形成的Pickering乳液整理得到。以Pickering乳液技术整理方法实现了一步法快速制备耐久超疏水织物，水滴在整理织物表面的静态接触角大于150°，且易滚落；经30次标准皂洗试验后，该织物仍保持优异的拒水性能。此外Pickering乳液制备及整理过程环保无污染、操作简易且适用性强。

Description

一种超疏水织物及其制备方法 技术领域
本发明属于功能纺织品领域，具体涉及超疏水织物及一步法利用Pickering乳液技术制备耐久超疏水织物的整理方法。
背景技术
表面润湿性是自然界最常见的现象之一，在日常生活和工农业生产中起到重要作用。仿生超疏水织物由于其良好的自清洁、防污、拒水及抗粘附性能，一直以来深受学术界和工商业的亲睐。通常采用物理或化学表面处理的方法，将长链烷烃、有机硅或有机氟等低表面能化合物引入织物表面，或是在织物表面构建粗糙结构，然后经过低表面能化合物处理，赋予其优异的超疏水性能。在实际应用中，整理后织物的耐水洗和皂洗性不佳。常规提高耐久性的方法是在体系中引入交联剂，如硅烷类偶联剂，脲醛类交联剂，环氧化合物交联剂等，用于交联整理涂层或在织物与涂层之间引入共价键。
此外，工业生产中大多直接采用低表面能物质对织物表面进行整理，这种处理可以赋予织物一定的疏水性(接触角120°左右)，但是要达到超疏水(接触角大于150°)的效果则必须要引入一定的粗糙结构，而这有可能增加整理工艺的复杂性。超疏水整理过程中还会使用一些对人体、环境有害的溶剂，或产生有毒有害的气体。因此，研究开发一种快速、环保的耐久超疏水织物的整理方法就显得特别重要。
Pickering乳液技术是一种利用固体粒子代替传统表面活性剂稳定乳液的新技术。固体粒子在不相容的两相界面形成不可逆的吸附，从而增强了乳液界面稳定性。大部分Pickering乳液还具有环保可再生、成本低廉及操作简单等优势，其广泛应用于食品、化妆品、医药等行业，而目前在纺织品上的应用研究很少。
发明内容
本发明的目的是提供一种超疏水织物及其制备方法，通过快速简单的整理工艺赋予织物超疏水性，并解决产品耐久性不佳的问题，提高织物的附加值及 实用性，拓宽其应用范畴。
为了达到上述目的，本发明提供了一种超疏水织物，其特征在于，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。
本发明还提供了一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法，其特征在于，包括：将双亲性粒子、低表面能物质和水进行乳化形成Pickering乳液，一步法利用上述Pickering乳液整理纺织品，烘干，获得超疏水织物。
优选地，所述的Pickering乳液为水包油型乳液。
优选地，所述的双亲性粒子为双亲性二氧化硅、双亲性氧化石墨烯、双亲性石墨烯、双亲性碳纳米管、双亲性碳酸钙、双亲性四氧化三铁、纤维素微晶、木质素微晶和淀粉纳米晶中的至少一种。
优选地，所述的低表面能物质为有机硅油、碳原子个数n≥16的长链烷烃类化合物和碳原子个数n≤6的全氟烷基类化合物中的至少一种。
优选地，所述的纺织品为纤维素纤维、涤纶、锦纶、腈纶、醋酸纤维、羊毛纤维织物或其中两种以上纤维的混纺织物。
优选地，所述的整理方法为浸轧法、浸渍法、涂层法或喷涂法。
优选地，所述的Pickering乳液中双亲性粒子和低表面能物质的总浓度为0～300mg/mL，且不为0；更优选80～120mg/mL。
优选地，所述的Pickering乳液中双亲性粒子和低表面能物质的质量比为1：0-30，且不为0；更优选1:1-10。
优选地，所述的乳化方法为均质分散、细胞粉碎或超声分散。
优选地，所述的烘干为60-80℃预烘1-3min及120-160℃焙烘1-3min，或120-150℃烘干30-60min。
本发明首先利用双亲性粒子包覆低表面能物质形成稳定的水包油型Pickering乳液，然后将上述形成的水包油型Pickering乳液对织物进行浸轧、浸渍、涂层或喷涂施加，经烘干和焙烘，稳定乳液的粒子可在织物表面形成粗糙界面，疏水性有机硅油、长链烷烃化合物和短链氟烃化合物可赋予粗糙界面疏水性能，从而可快速获得一种耐久超疏水织物。
本发明采用Pickering乳液技术对织物进行整理，在施加低比表面物质的 同时，通过固体粒子构造粗糙结构，达到超疏水的目的；另外部分双亲性固体粒子含有活性官能团，可以与织物基体或者低表面能化合物形成化学键合，提高超疏水整理的耐久性。
本发明制备方法简单易行，适用性广。通过一步法同时引入低表面能物质和粗糙结构，快速实现织物的超疏水性能。经多次标准皂洗之后，织物仍保持着优异的拒水性能。该制备过程中不涉及任何有毒有害试剂及气体，绿色环保，且产品均匀性及重现性佳，利于推广。
根据本发明方法制得的耐久超疏水棉织物，其与5μL水滴的静态接触角高达156°；根据本发明方法制得的耐久超疏水涤纶织物，其与5μL水滴的静态接触角高达154°；且液滴易于滚落。整理后织物至少可耐标准皂洗30次。
与现有技术相比，本发明的有益效果是：
1.本发明制备方法简单易行，适用性广；
2.本发明通过一步法同时引入低表面能物质和粗糙结构，快速实现织物的超疏水性能；
3.本发明按照ISO 105-C10:2007测试方法洗涤30次后，织物仍保持着优异的拒水性能；
4.本发明制备过程中不涉及任何有毒有害试剂及气体，绿色环保，且产品均匀性及重现性佳，利于推广。
附图说明
图1是本发明一步法利用Pickering乳液技术制备耐久超疏水织物的流程图。
图2是本发明实施例1，2整理织物在皂洗前对不同液体的疏液性图。
图3是本发明实施例1，2整理织物经30次标准皂洗后对不同液体的疏液性图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明中的静态接触角采用悬滴法，德国KRUSS GmbH DSA30接触角测 量仪方法测试。水滴体积为5μL。
实施例1
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：1，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对漂白棉机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，160℃焙烘3min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为155°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达153°。
本实施例中经过常规浸轧整理的棉织物的疏液效果如图2(Ⅰ)所示，整理棉织物对去离子水、红色染液、果汁、可口可乐、茶、咖啡及牛奶液滴都具有优异的疏液效果，液滴在整理织物上呈球状，且易于滚落。
本实施例中经过常规浸轧整理的棉织物的耐久疏液效果如图3(Ⅰ)所示，按照ISO 105-C10:2007测试方法，经过30次洗涤之后，整理棉织物对去离子水、红色染液、果汁、可口可乐、茶、咖啡及牛奶液滴仍具有优异的疏液效果，液滴在整理织物上呈球状，且易于滚落。
实施例2
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为120mg/mL，双亲性粒子和低表面能物质的质量比为1：1，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对涤纶机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，160℃焙烘3min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为152°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角为150°。
本实施例中经过常规浸轧整理的涤纶织物的疏液效果如图2(Ⅱ)所示，整理涤纶织物对去离子水、红色染液、果汁、可口可乐、茶、咖啡及牛奶液滴都具有优异的疏液效果，液滴在整理织物上呈球状，且易于滚落。
本实施例中经过常规浸轧整理的涤纶织物的耐久疏液性能如图3(Ⅱ)所示，按照ISO 105-C10:2007测试方法，经过30次洗涤之后，整理涤纶织物对去离子水、红色染液、果汁、可口可乐、茶、咖啡及牛奶液滴仍具有优异的疏液效果，液滴在整理织物上呈球状，且易于滚落。
实施例3
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在超声波细胞粉碎条件下，乳化形成水包油型Pickering乳液，乳液中双亲性纳米粒子 和低表面能物质的总浓度为120mg/mL，双亲性粒子和低表面能物质的质量比为1：2，细胞粉碎功率为540W，乳化时间为3min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对漂白棉机织物进行常规二浸二轧整理，轧余率70％；
烘干：然后于80℃预烘3min，160℃焙烘3min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为155°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达154°。
实施例4
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在超声波细胞粉碎条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为120mg/mL，双亲性粒子和低表面能物质的质量比为1：2，细胞粉碎功率为540W，乳化时间为3min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对涤纶机织物进行二浸二轧整理，轧余率70％；
烘干：然后于80℃预烘3min，160℃焙烘3min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为150°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达148°。
实施例5
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油 相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：2，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：室温条件下，将漂白棉机织物浸渍于上述稳定的水包油型Pickering乳液中，浸渍时间10min,然后取出；
烘干：于135℃烘干30min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为156°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达153°。
实施例6
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为120mg/mL，双亲性粒子和低表面能物质的质量比为1：2，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：室温条件下，将涤纶机织物浸渍于稳定的水包油型Pickering乳液中，浸渍时间10min,然后取出；
烘干：于135℃烘干30min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为154°，按照ISO 105-C10: 2007测试方法洗涤30次之后，静态接触角为150°。
实施例7
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在超声波细胞粉碎条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：2，细胞粉碎功率为540W，乳化时间为3min。
一步法利用上述Pickering乳液整理纺织品：室温条件下，将漂白棉机织物浸渍于上述稳定的水包油型Pickering乳液中，浸渍时间10min,然后取出；
烘干：于135℃烘干30min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为154°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达151°。
实施例8
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在超声波细胞粉碎条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为120mg/mL，双亲性粒子和低表面能物质的质量比为1：5，细胞粉碎功率为540W，乳化时间为3min。
一步法利用上述Pickering乳液整理纺织品：室温条件下，将涤纶机织物浸渍于稳定的水包油型Pickering乳液中，浸渍时间10min,然后取出；
烘干：于135℃烘干30min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为154°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角为150°。
实施例9
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质全氟烷基类化合物(1H,1H,2H,2H-全氟辛基三甲氧基硅烷,中国杭州安嘉睿科技有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：30，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对漂白棉机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，160℃焙烘3min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为160°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达158°。
实施例10
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性二氧化硅粒子(Bindzil CC40,瑞典Eka化学公司)与低表面能物质长 链烷烃类化合物(正十六烷,中国上海国药集团化学试剂有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为300mg/mL，双亲性粒子和低表面能物质的质量比为1：10，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对涤纶机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，120℃焙烘3min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为150°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达148°。
实施例11
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性四氧化三铁粒子(PuriMag200Si-Epoxy,中国厦门普瑞迈格生物技术有限公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：1，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对漂白棉机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，160℃焙烘3min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为153°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达150°。
实施例12
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性纤维素微晶(CNC-C,中国广西桂林奇宏科技有限公司)与低表面能物质全氟烷基类化合物(1H,1H,2H,2H-全氟辛基三甲氧基硅烷,中国杭州安嘉睿科技有限公司)与水混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为300mg/mL，双亲性粒子和低表面能物质的质量比为1：0.5，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对漂白棉机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，160℃焙烘3min，得到耐久超疏水棉织物。
上述耐久超疏水棉织物与水滴的静态接触角为152°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达149°。
实施例13
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性氧化石墨烯水性分散液(XF020,中国南京先丰纳米材料科技有限公司)与低表面能物质有机硅油(PDMS 4000,中国上海迈图有机硅材料有限公司)混合，在均质机分散条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：0.5，均质机转速为15,000rpm，乳化时间为5min。
一步法利用上述Pickering乳液整理纺织品：室温条件下，将涤纶机织物浸渍于稳定的水包油型Pickering乳液中，浸渍时间10min,然后取出；
烘干：于135℃烘干30min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为150°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角为144°。
实施例14
一种超疏水织物，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。如图1所示，所述的Pickering乳液包括水相1和油相，油相为低表面能物质2，双亲性粒子3包裹低表面能物质2。
一步法利用Pickering乳液技术制备上述的耐久超疏水织物的方法为：
将双亲性粒子和低表面能物质乳化形成稳定的水包油型Pickering乳液：将双亲性碳酸钙粒子(VK-CaC112-1,中国杭州万景新材料有限公司)与低表面能物质长链烷烃类化合物(正十六烷,中国上海国药集团化学试剂有限公司)与水混合，在超声波细胞粉碎条件下，乳化形成水包油型Pickering乳液，乳液中双亲性粒子和低表面能物质的总浓度为80mg/mL，双亲性粒子和低表面能物质的质量比为1：5，细胞粉碎功率为540W，乳化时间为3min。
一步法利用上述Pickering乳液整理纺织品：将稳定的水包油型Pickering乳液对涤纶机织物进行常规二浸二轧整理，轧余率70％；
烘干：于80℃预烘3min，120℃焙烘3min，得到耐久超疏水涤纶织物。
上述耐久超疏水涤纶织物与水滴的静态接触角为150°，按照ISO 105-C10:2007测试方法洗涤30次之后，静态接触角仍高达147°。

Claims (10)

  1. 一种超疏水织物，其特征在于，其利用双亲性粒子、低表面能物质和水进行乳化形成的Pickering乳液整理得到。
  2. 一步法利用Pickering乳液技术制备权利要求1所述的耐久超疏水织物的方法，其特征在于，包括：将双亲性粒子、低表面能物质和水进行乳化形成Pickering乳液，一步法利用上述Pickering乳液整理纺织品，烘干，获得超疏水织物。
  3. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的Pickering乳液为水包油型乳液。
  4. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的双亲性粒子为双亲性二氧化硅、双亲性氧化石墨烯、双亲性石墨烯、双亲性碳纳米管、双亲性碳酸钙、双亲性四氧化三铁、纤维素微晶、木质素微晶和淀粉纳米晶中的至少一种。
  5. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的低表面能物质为有机硅油、碳原子个数n≥16的长链烷烃类化合物和碳原子个数n≤6的全氟烷基类化合物中的至少一种。
  6. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的纺织品为纤维素纤维、涤纶、锦纶、腈纶、醋酸纤维、羊毛纤维织物或其中两种以上纤维的混纺织物。
  7. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的整理方法为浸轧法、浸渍法、涂层法或喷涂法。
  8. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的Pickering乳液中双亲性粒子和低表面能物质的总浓度为0～300mg/mL，且不为0；其中，低表面能物质与双亲性纳米粒子的质量比为1：0-30，且不为0。
  9. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的乳化方法为均质分散、细胞粉碎或超声分 散。
  10. 如权利要求2所述的一步法利用Pickering乳液技术制备耐久超疏水织物的方法，其特征在于，所述的烘干为60-80℃预烘1-3min及120-160℃焙烘1-3min，或120-150℃烘干30-60min。
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