WO2020134836A1 - 一种多维度亲疏水结构复合纳米纤维膜及其制备方法 - Google Patents
一种多维度亲疏水结构复合纳米纤维膜及其制备方法 Download PDFInfo
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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- A62B18/02—Masks
Definitions
- the invention relates to a nano-fiber membrane, in particular to a multi-dimensional hydrophobic composite nano-fiber membrane and a preparation method thereof.
- CN103894077A discloses a multi-dimensional pore structure composite filter membrane and a preparation method thereof.
- the composite filter membrane includes a nonwoven base fabric and a porous composite nanofiber layer, the two are hot-rolled composite, the porous composite nanofiber layer Composed of polymers and additives.
- CN105392544A discloses a gradient nanofiber filter medium, which is formed of a multi-layer dielectric material, and the multi-layer dielectric material includes a layer of nano-fiber media, wherein the multiple layers are laminated, combined, or otherwise compounded with each other.
- the composite filter medium may include at least one nanofiber layer, the nanofiber layer includes a polymer medium material with a geometric average fiber diameter of about 100 nm to 1 ⁇ m and a plurality of fibers, the plurality of fibers are configured with such a gradient, upstream of the nanofiber layer
- the ratio of the geometric mean diameter of each fiber at the face to the geometric mean diameter of each fiber at the downstream face of the nanofiber layer is about 1.1 to 2.8.
- CN106731229A discloses an electret nanofiber air filter material with a waterproof function and a preparation method thereof, including a base material and a nanofiber membrane provided on the base material, and the nanofiber in the nanofiber membrane is distributed with an electret functional substance, nano The fiber has a multilayer structure, and the outermost layer contains a hydrophobic polymer.
- CN104207390A discloses a waterproof moisture-permeable membrane, a preparation method thereof, a waterproof moisture-permeable fabric, and a preparation method thereof, wherein the waterproof moisture-permeable membrane includes: a nanofiber hydrophilic layer, the nanofiber hydrophilic layer is made of a hydrophilic polymer through static electricity Made by spinning; and a nanofiber hydrophobic layer provided on the nanofiber hydrophilic layer, the nanofiber hydrophobic layer is made of a hydrophobic polymer by electrostatic spinning.
- CN107059251A discloses a method for preparing a unidirectional wetting nanofiber multilayer composite film with a wetting gradient, including the following steps: dispersing hydrophilic nanomaterials in a solvent, ultrasonically dispersing the nanomaterials uniformly, and then dispersing the hydrophilic polymer Dissolve in the dispersion to obtain the spinning solution A1, and deposit a layer of hydrophilic nanofiber film on the receiving substrate by electrostatic spinning; disperse the hydrophilic nanomaterial in the solvent, and ultrasonically disperse the nanomaterial uniformly.
- hydrophilic/hydrophobic nanofiber membranes have their unique advantages.
- the research team of Donghua University used polyacrylonitrile, silica, and polyvinylidene fluoride materials to construct a composite fiber membrane with a gradient structure (Small, 2017, 13, 1603306). Achieving better water vapor transmission rate is of great significance for personal protective materials.
- the prior art mainly designs the nanofiber filter membrane from the angles of fiber diameter, fiber surface structure, and void structure of the fiber combination.
- the only hydrophilic/hydrophobic gradient structure is also to improve the water vapor transmission rate, rather than to enhance filtration and adsorption of particulate matter.
- the object of the present invention is to provide a multi-dimensional hydrophobic composite nanofiber membrane and its preparation method.
- This multi-dimensional hydrophobic composite nanofiber membrane is based on the surface wetting properties of the material.
- a composite nanofiber membrane with multi-dimensional hydrophilic-hydrophobic structure including a first hydrophobic layer, a first hydrophilic layer, a second hydrophilic layer, and a second hydrophobic layer arranged in order from top to bottom; wherein, the first hydrophobic layer and the first The water contact angles of the two hydrophobic layers are respectively greater than 90 degrees, and the water contact angles of the first hydrophilic layer and the second hydrophilic layer are respectively less than 70 degrees; the second hydrophobic layer is a nanofiber-based membrane.
- the thickness of the first hydrophobic layer is 5 ⁇ m to 30 ⁇ m; further preferably, the thickness of the first hydrophobic layer is 5 ⁇ m to 20 ⁇ m.
- the thickness of the first hydrophilic layer is 10 ⁇ m-50 ⁇ m; further preferably, the thickness of the first hydrophilic layer is 15 ⁇ m-40 ⁇ m.
- the thickness of the second hydrophilic layer is 10 ⁇ m-80 ⁇ m; further preferably, the thickness of the second hydrophilic layer is 40 ⁇ m-75 ⁇ m.
- the thickness of the second hydrophobic layer is 50 ⁇ m-500 ⁇ m; further preferably, the thickness of the second hydrophobic layer is 100 ⁇ m-400 ⁇ m.
- the water contact angle of the first hydrophobic layer is 95 degrees to 150 degrees; further preferably, the water contact angle of the first hydrophobic layer is 100 degrees to 140 degrees.
- the water contact angle of the first hydrophilic layer is 20 degrees to 65 degrees; further preferably, the water contact angle of the first hydrophilic layer is 25 degrees to 60 degree.
- the water contact angle of the second hydrophilic layer is 10 degrees to 50 degrees; further preferably, the water contact angle of the second hydrophilic layer is 15 degrees to 40 degree.
- the water contact angle of the second hydrophobic layer is 95 degrees to 150 degrees; further preferably, the water contact angle of the second hydrophobic layer is 100 degrees to 130 degrees.
- the water contact angle ratio of the first hydrophilic layer and the second hydrophilic layer is (1.4-3.5): 1.
- the nanofiber base membrane is polysulfone, polyethersulfone, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyethylene, polypropylene, polyester. At least one nanofiber membrane formed.
- the preparation method of the composite nano-fiber membrane with multi-dimensional hydrophilic-hydrophobic structure includes the following steps:
- Electrospinning polymer is used for electrospinning film formation on the surface of the nanofiber base film, and the resulting film material is processed in a plasma atmosphere to obtain a composite semi-filming A;
- Electrospinning polymer is used for electrospinning film formation on the surface of the composite semi-film formation A, and the resulting membrane material is treated in a plasma atmosphere to obtain the composite semi-film formation B;
- a hydrophobic polymer is used for electrostatic spinning on the surface of the composite semi-film-forming B to obtain a multi-dimensional hydrophobic nanocomposite film with a hydrophobic structure.
- the composite semi-film formation A refers to a composite nanometer with a second hydrophilic layer formed on the surface of the nanofiber base membrane (second hydrophobic layer) Fiber membrane semi-finished products.
- composite semi-film formation B refers to a composite in which a first hydrophilic layer is formed on the surface of the second hydrophilic layer of composite semi-film formation
- a Nano-fibre membrane semi-finished products
- the hydrophobic polymer is independently selected from polymers containing at least one hydrophobic group, wherein the hydrophobic group is selected From a hydrocarbon group and/or an ester group; the hydrophobic polymer is preferably at least one of polysulfone, polyethersulfone, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyethylene, polypropylene, and polyester; further preferably The hydrophobic polymer is at least one of polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyethylene, polypropylene, and polyester; still further preferably, the hydrophobic polymer is polyacrylonitrile, polyphenylene At least one of ethylene and polyvinylidene fluoride.
- the electrospinning polymers are independently selected from polyacrylonitrile, polyamide, polylactic acid, polyurethane and polyvinyl alcohol , At least one of polyvinyl butyral, polyvinylpyrrolidone, polycaprolactone, polyethylene oxide, polystyrene, polyester, polyimide, chitosan, silk fibroin, collagen; further Preferably, the electrospinning polymer is polyacrylonitrile, polyamide, polylactic acid, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polystyrene, polyester, polyimide, chitosan, At least one of silk fibroin and collagen; still further preferably, the electrospinning polymer is at least one of polyacrylonitrile, polylactic acid, and polyvinyl butyral.
- the plasma is the plasma generated by the discharge gas through uniform glow discharge, and the discharge gas is nitrogen, argon, helium, or air
- the plasma atmosphere treatment time is 30s-300s; further preferably, step 2) the plasma atmosphere treatment time is 60s-180s.
- the plasma is the plasma generated by the discharge gas through uniform glow discharge, and the discharge gas is nitrogen, argon, helium, or air
- the plasma atmosphere treatment time is 10s-300s; further preferably, step 3) the plasma atmosphere treatment time is 30s-200s.
- step 3) and step 4) of the multi-dimensional hydrophilic-hydrophobic structure composite nanofiber membrane the optional electrospinning conditions are: static voltage of 5kV-25kV, injection speed of 0.1 mL/h ⁇ 5mL/h, spinning distance 2cm ⁇ 20cm, ambient temperature 15°C ⁇ 30°C, ambient humidity 20% ⁇ 80%.
- the invention can use plasma technology and electrospinning technology to prepare a multi-dimensional hydrophobic gradient structure composite nanofiber membrane, and the membrane material can realize the directional adsorption and fixation of particles, and has a good filtration effect, and the filtration efficiency of particles exceeds 95%.
- the preparation process of the invention is safe and environmentally friendly, without waste water and waste chemical reagents, and the preparation method is simple and easy to implement.
- the present invention has the following advantages:
- the present invention is to form a multi-dimensional hydrophilic-hydrophobic gradient structure by designing the wettability of the surface of the nanofiber membrane.
- the first hydrophobic layer corresponds to the polluted air containing particulate matter.
- the particulate matter contacts the outer layer of hydrophobic nanofiber web, it is adsorbed on the surface of the nanofiber due to static electricity, while the first hydrophilic layer, the second hydrophilic layer and the There is a hydrophilic-hydrophobic gradient between the first hydrophobic layer, and the moisture in the particles causes the particles to move directionally from the first hydrophobic layer to the first hydrophilic layer and the second hydrophilic layer, thereby adsorbing the particles in the middle hydrophilic layer fibers Between the membranes. More important is the setting of the second hydrophobic layer. Under the strong hydrophobic effect, these particles no longer move and adsorb and fix the hydrophilic layer in the middle.
- the preparation method of the present invention is realized by plasma technology combined with electrospinning technology.
- the hydrophobic layer is formed by electrospinning a hydrophobic polymer.
- the polymer refers to one or more hydrophobic groups (such as Hydrocarbon group, ester structure) polymer.
- the hydrophilic layer is formed by electrospinning the polymer and forming a film after low-temperature plasma surface treatment.
- the method of the present invention is novel and unique, simple and efficient, and breaks through the limitation of the prior art that the fiber structure is used to design the filter membrane, and the design of the hydrophilic/hydrophobic gradient structure is used to achieve efficient adsorption and fixation of particulate matter.
- Figure 1 is a schematic diagram of the structure of a multi-dimensional hydrophobic composite nanofiber membrane
- Example 2 is a scanning electron microscope image of the nanofiber membrane after filtration in Example 1;
- Example 3 is a scanning electron microscope image of the nanofiber membrane after filtration in Example 2.
- Example 4 is a scanning electron microscope image of the nanofiber membrane after filtration in Example 3.
- FIG. 5 is a scanning electron microscope image of the nanofiber membrane after filtration in Comparative Example 1.
- FIG. 1 is a schematic structural diagram of a multi-dimensional hydrophobic composite nanofiber membrane of the present invention.
- the multi-dimensional hydrophilic-hydrophobic structure composite nanofiber membrane is a multilayer structure membrane composed of a first hydrophobic layer 1, a first hydrophilic layer 2, a second hydrophilic layer 3, and a second hydrophobic layer 4 arranged in this order from top to bottom; Among them, the second hydrophobic layer is a nanofiber-based membrane.
- a multi-dimensional hydrophilic-hydrophobic gradient structure composite nanofiber membrane is a multi-layer structure, including a first hydrophobic layer, a first hydrophilic layer, a second hydrophilic layer, and a second hydrophobic layer arranged in order from top to bottom Floor.
- the thickness of the first hydrophobic layer is 5 ⁇ m
- the thickness of the first hydrophilic layer is 20 ⁇ m
- the thickness of the second hydrophilic layer is 50 ⁇ m
- the thickness of the second hydrophobic layer is 300 ⁇ m.
- the water contact angle of the first hydrophobic layer is 100 degrees
- the water contact angle of the second hydrophobic layer is 110 degrees
- the water contact angle of the first hydrophilic layer is 50 degrees
- the water contact angle of the second hydrophilic layer is 35 degrees.
- the hydrophobic layer of this embodiment is formed by electrospinning of polyacrylonitrile.
- the electrospinning conditions are: static voltage 15kV, injection speed 0.2mL/h, spinning distance 5cm, ambient temperature 25°C, ambient humidity 60%.
- the hydrophilic layer is formed by polyacrylonitrile electrospinning and formed by low temperature plasma surface treatment.
- the polymer is subjected to electrostatic spinning to form a film, and then the film is placed in a helium plasma atmosphere for treatment for 60s;
- FIG. 2 is a scanning electron microscope image of the nanofiber membrane after filtration. It can be seen that the particles can be well fixed between the nanofibers.
- a multi-dimensional hydrophilic-hydrophobic gradient structure composite nanofiber membrane is a multi-layer structure, including a first hydrophobic layer, a first hydrophilic layer, a second hydrophilic layer, and a second hydrophobic layer arranged in order from top to bottom Floor.
- the thickness of the first hydrophobic layer is 10 ⁇ m
- the thickness of the first hydrophilic layer is 30 ⁇ m
- the thickness of the second hydrophilic layer is 60 ⁇ m
- the thickness of the second hydrophobic layer is 200 ⁇ m.
- the water contact angle of the first hydrophobic layer is 130 degrees
- the water contact angle of the second hydrophobic layer is 120 degrees
- the water contact angle of the first hydrophilic layer is 60 degrees
- the water contact angle of the second hydrophilic layer is 20 degrees.
- the hydrophobic layer of this embodiment is formed of polystyrene by electrostatic spinning.
- the electrospinning conditions are: static voltage 18 kV, injection speed 0.1 mL/h, spinning distance 8 cm, ambient temperature 27° C., and ambient humidity 75%.
- the hydrophilic layer is formed by electrospinning of polylactic acid and formed by low temperature plasma surface treatment.
- the polymer is subjected to electrostatic spinning to form a film, and then the film is placed in an argon plasma atmosphere for processing for 90s;
- FIG. 3 is a scanning electron microscope image of the nanofiber membrane after filtration. It can be seen that the particles can be well fixed between the multilayer nanofiber structures.
- a multi-dimensional hydrophilic-hydrophobic gradient structure composite nanofiber membrane is a multi-layer structure, including a first hydrophobic layer, a first hydrophilic layer, a second hydrophilic layer, and a second hydrophobic layer arranged in order from top to bottom Floor.
- the thickness of the first hydrophobic layer is 8 ⁇ m
- the thickness of the first hydrophilic layer is 35 ⁇ m
- the thickness of the second hydrophilic layer is 70 ⁇ m
- the thickness of the second hydrophobic layer is 350 ⁇ m.
- the water contact angle of the first hydrophobic layer is 105 degrees
- the water contact angle of the second hydrophobic layer is 125 degrees
- the water contact angle of the first hydrophilic layer is 40 degrees
- the water contact angle of the second hydrophilic layer is 15 degrees.
- the hydrophobic layer is formed by electrostatic spinning of polyvinylidene fluoride.
- the conditions of electrostatic spinning are: static voltage of 20 kV, injection speed of 0.3 mL/h, spinning distance of 12 cm, ambient temperature of 26° C., and ambient humidity of 65%.
- the hydrophilic layer is formed by electrospinning polyvinyl butyral and formed by surface treatment with low temperature plasma.
- the polymer is subjected to electrostatic spinning to form a film, and then the film is placed in a helium plasma atmosphere for processing for 120s;
- FIG. 4 is a scanning electron microscope image of the nanofiber membrane after filtration. It can be seen that the particles can be well fixed between the nanofiber multilayer structures.
- a nanofiber membrane is formed by electrospinning polyacrylonitrile only and has a thickness of 463 ⁇ m.
- the conditions of electrostatic spinning are: static voltage is 15kV, injection speed is 0.2mL/h, spinning distance is 5cm, ambient temperature is 25 °C, ambient humidity is 60%.
- FIG. 5 is a scanning electron microscope image of the nanofiber membrane after filtration. It can be seen that the particles are all attached to the surface of the nanofiber membrane and are not fixed between the nanofibers.
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Abstract
Description
Claims (10)
- 一种多维度亲疏水结构复合纳米纤维膜,其特征在于:包括由上至下依次设置的第一疏水层、第一亲水层、第二亲水层、第二疏水层;其中,第一疏水层和第二疏水层的水接触角分别大于90度,第一亲水层和第二亲水层的水接触角分别小于70度;所述的第二疏水层为纳米纤维基膜。
- 根据权利要求1所述的一种多维度亲疏水结构复合纳米纤维膜,其特征在于:第一疏水层的厚度为5μm~30μm,第一亲水层的厚度为10μm~50μm,第二亲水层的厚度为10μm~80μm,第二疏水层的厚度为50μm~500μm。
- 根据权利要求1或2所述的一种多维度亲疏水结构复合纳米纤维膜,其特征在于:第一亲水层和第二亲水层的水接触角比值为(1.4~3.5):1。
- 根据权利要求1所述的一种多维度亲疏水结构复合纳米纤维膜,其特征在于:所述纳米纤维基膜为聚砜、聚醚砜、聚丙烯腈、聚苯乙烯、聚偏氟乙烯、聚乙烯、聚丙烯、聚酯中的至少一种形成的纳米纤维膜。
- 权利要求1~4任一项所述一种多维度亲疏水结构复合纳米纤维膜的制备方法,其特征在于:包括以下步骤:1)制备第二疏水层:采用疏水类聚合物进行静电纺丝,得到纳米纤维基膜;2)制备第二亲水层:采用静电纺丝聚合物在纳米纤维基膜表面进行静电纺丝成膜,所得的膜材置于等离子体氛围中处理,得到复合半成膜A;3)制备第一亲水层:采用静电纺丝聚合物在复合半成膜A的表面进行静电纺丝成膜,所得的膜材置于等离子体氛围中处理,得到复合半成膜B;4)制备第一疏水层:采用疏水类聚合物在复合半成膜B的表面进行静电纺丝成膜,得到多维度亲疏水结构复合纳米纤维膜。
- 根据权利要求5所述的一种多维度亲疏水结构复合纳米纤维膜的制备方法,其特征在于:步骤1)和步骤4)中,疏水类聚合物分别独立选自含有至少一个疏水基团的聚合物,所述疏水基团选自烃基和/或酯基。
- 根据权利要求5所述的一种多维度亲疏水结构复合纳米纤维膜的制备方法,其特征在于:步骤2)和步骤3)中,静电纺丝聚合物分别独立选自聚丙烯腈、聚酰胺、聚乳酸、聚氨酯、聚乙烯醇、聚乙烯醇缩丁醛、聚乙烯吡咯烷酮、聚己内酯、聚氧化乙烯、聚苯乙烯、聚酯、聚酰亚胺、壳聚糖、丝素蛋白、胶原蛋白中的至少一种。
- 根据权利要求5所述的一种多维度亲疏水结构复合纳米纤维膜的制备方法,其特征在于:步骤2)中,等离子体为放电气体经均匀辉光放电产生的等离子体,所述的放电气体为氮气、氩气、氦气、空气中的至少一种,等离子体氛围处理的时间为30s~300s。
- 根据权利要求5所述的一种多维度亲疏水结构复合纳米纤维膜的制备方法,其特征在于:步骤3)中,等离子体为放电气体经均匀辉光放电产生的等离子体,所述的放电气体为氮气、氩气、氦气、空气中的至少一种,等离子体氛围处理的时间为10s~300s。
- 权利要求1~4任一项所述一种多维度亲疏水结构复合纳米纤维膜作为吸附膜和/或过滤膜的应用。
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CN110592686B (zh) * | 2019-08-30 | 2020-06-26 | 河南亚都实业有限公司 | 一种负载生长因子的微纳米复合膜 |
CN110872741B (zh) * | 2019-09-12 | 2023-01-13 | 武汉工程大学 | 一种同时用于乳液分离和染料吸附的复合纳米纤维膜及其制备方法 |
CN111111458A (zh) * | 2019-12-19 | 2020-05-08 | 五邑大学 | 具有多级连通孔结构的单向导湿微纳米纤维膜及其制备方法 |
CN111036092A (zh) * | 2020-01-17 | 2020-04-21 | 湖南科技大学 | 一种亲水型复合膜的制备方法 |
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CN112354380B (zh) * | 2020-11-09 | 2021-08-06 | 大连理工大学 | 一种静电纺丝纳米纤维气体分离膜的制备方法 |
CN112829410A (zh) * | 2021-01-29 | 2021-05-25 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | 一种高效油水分离滤膜及其制备方法 |
CN112999886A (zh) * | 2021-03-03 | 2021-06-22 | 重庆中膜科技集团有限公司 | 一种夹层结构复合纤维透气膜及其制备方法 |
CN113215727A (zh) * | 2021-05-21 | 2021-08-06 | 南京工业大学 | 一种具有抗菌性能的空气净化膜的制备方法 |
CN113878960B (zh) * | 2021-09-17 | 2022-10-18 | 北京航空航天大学 | 双层纳米多孔功能面料及其制备方法 |
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