CN107630365B - Preparation method of super-wet fabric - Google Patents
Preparation method of super-wet fabric Download PDFInfo
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- CN107630365B CN107630365B CN201710662068.XA CN201710662068A CN107630365B CN 107630365 B CN107630365 B CN 107630365B CN 201710662068 A CN201710662068 A CN 201710662068A CN 107630365 B CN107630365 B CN 107630365B
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Abstract
The invention provides a preparation method of a super-wetting fabric, which aims at fabrics formed by various hydrophilic or hydrophobic thermoplastic polymer fibers and utilizes supercritical CO2The foaming method is used for manufacturing a micro-nano multilevel microstructure on the surface of the polymer fiber, so that the fabric has super-wetting property. The fabric after the foaming treatment provided by the invention has super-wettability such as super-hydrophilicity or super-hydrophobicity, and the like, and the functions and the purposes of the fabric are greatly expanded. By using supercritical CO2The foaming technology is environment-friendly and simple to operate, and the morphology of the fiber surface nanostructure can be adjusted through pressure, temperature, soaking time and pressure relief. The invention is suitable for various thermoplastic high-molecular polymer fabrics and has wide applicability.
Description
Technical Field
The invention relates to the technical field of functionalized polymer fibers, in particular to a fiber prepared by supercritical CO2A process for preparing the thermoplastic polymer fabric with special micron and nano structure on its surface and super wetting performance by foaming.
Background
The self-cleaning effect of lotus leaves is widely concerned in recent years, people find that the waxiness with the micron and nanometer multilevel structure on the lotus leaf surface is the reason of the super-hydrophobic property, and accordingly a Cassie model with the micro-nano structure is established. Many researches show that the hydrophilic material with the surface micro-nano multilevel structure shows super-hydrophilic performance, and the hydrophobic material shows super-hydrophobic performance. Based on the method, a plurality of physical and chemical methods such as plasma etching, mechanical friction, chemical etching, chemical modification and the like are adopted to form micro and nano structures on the surface of the fabric fiber, so that the fabric fiber has super-wetting performance, and the fabrics can be used for oil-water separation, self-cleaning clothing materials, mist collection and the like, thereby expanding the application of the fabric. However, the above method is complicated in process and difficult to prepare in a large area. Some methods use harmful chemical substances for treatment, and have high cost and no environmental friendliness. In addition, these methods often result in damage to the mechanical properties of the fabric.
By using supercritical CO2The technology of preparing the microporous polymer material by the foaming technology is widely applied, and the method enables the material to have an adjustable microporous structure and endows the material with good mechanical property, thermal stability and the like. CO 22The supercritical state can be achieved at a temperature of 34 ℃ and a pressure of 7 MPa. And CO2The chemical property is inactive, the product is colorless, tasteless and nontoxic, the safety is good, and the price is cheap. The technology is to make supercritical CO under a certain temperature and pressure2Dissolved in the polymer to form a homogeneous polymer/gas saturated system, CO2The gas forms gas nuclei in the polymer. Then, the system is quickly supersaturated through rapid depressurization, gas in the system diffuses out, and gas nuclei grow. As the gas escapes, the driving force for gas core growth continues to decrease, while the temperature decreases and the polymer matrix stiffness gradually increases. The two functions are combined to regulate the growth of the foam pores, and finally, the foam pores are fixed and formed to form a microporous structure.
Disclosure of Invention
The invention aims to provide a preparation method of a super-wetting fabric.
The invention adopts supercritical CO2The foaming method can form a special nano structure on the surface of the thermoplastic polymer fiber in one step, and a super-wetting structure on the surface of the fabric is constructed by combining the micron-sized pore structure of the fiber, so that the surface of the fabric can have super-hydrophilic or super-hydrophobic performance under the condition of not influencing the mechanical performance of the material.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a super-wetting fabric, which adopts a fabric formed by thermoplastic polymer fibers and supercritical CO2Foaming is carried out, and the foaming process conditions are as follows: the pressure is 7-25 MPa, the temperature is 30-180 ℃, the soaking time is 30-180 min, and the pressure relief rate is as follows: 0.5 to 8 MPa/s.
Preferably, the diameter of the thermoplastic polymer fiber is 1 to 80 micrometers, and the pore diameter of the thermoplastic polymer fiber is 0.5 to 200 micrometers.
Preferably, the thermoplastic polymer fibers comprise hydrophilic thermoplastic polymer fibers and hydrophobic thermoplastic polymer fibers;
the hydrophilic thermoplastic polymer fibers are comprised of one or more of the following materials:
polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), Polyacrylamide (PAM);
the hydrophobic thermoplastic polymer fibers are comprised of one or more of the following materials:
polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polylactic acid (PLA), polyethylene terephthalate (PET), nylon (PA).
Preferably, the fabric made of the hydrophilic thermoplastic polymer fibers is prepared by an electrostatic spinning method, and the preparation process conditions are as follows: concentration of the spinning solution: 10-30 wt%, voltage: 10-25 KV, the distance between the injection needle head and the receiving plate: 8-15 cm, the diameter of the thermoplastic polymer fiber is 0.5-5 μm, and the diameter of the hole formed by overlapping the thermoplastic polymer fiber is 2-50 μm.
By supercritical CO2After foaming treatment, the surfaces of the polymer fibers form micro and nano multilevel microstructures, and the microstructures are combined with the micron-sized pore structures of the fabric, so that the fabric has super-wetting performance under the combined action. Using hydrophilic polymer fabric, passing through supercritical CO2After foaming treatment, the fabric obtains super-hydrophilic performance; using hydrophobic polymer fabric, passing through supercritical CO2After the foaming treatment, the fabric obtains super-hydrophobic performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fabric after the foaming treatment has super-wetting properties such as super-hydrophilicity or super-hydrophobicity, and the like, and the functions and the purposes of the fabric are greatly expanded.
(2) The invention adopts supercritical CO2The foaming technology is environment-friendly and simple to operate, and the morphology of the fiber surface nanostructure can be adjusted through pressure, temperature, soaking time and pressure relief.
(3) The invention is suitable for various thermoplastic high-molecular polymer fabrics and has wide applicability.
Drawings
FIG. 1 SEM image of PVP fiber prepared in example 1 and water contact angle of its non-woven fabric, A is supercritical CO2The fiber morphology before foaming, the fiber morphology after foaming, the water contact angle of the PVP non-woven fabric before foaming and the water contact angle of the PVP non-woven fabric after foaming are shown in the specification.
FIG. 2 SEM image of PMMA fiber prepared in example 2 and water contact angle of non-woven fabric thereof, A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the PMMA non-woven fabric before foaming, and D is the water contact angle of the PMMA non-woven fabric after foaming.
FIG. 3 SEM image of PP fiber prepared in example 3 and water contact angle of non-woven fabric thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the PP non-woven fabric before foaming, and D is the water contact angle of the PP non-woven fabric after foaming.
FIG. 4 SEM image of nylon 66 fiber prepared in example 4 and water contact angle of woven cloth thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the nylon cloth before foaming, and D is the water contact angle of the nylon cloth after foaming.
FIG. 5 SEM image of PLA fiber prepared in example 5 and water contact angle of non-woven fabric thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is PLA before foamingThe water contact angle of the woven fabric is D, and the water contact angle of the foamed PLA non-woven fabric is D.
FIG. 6 SEM image of PAN fiber prepared in example 6 and water contact angle of nonwoven fabric thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the PAN non-woven fabric before foaming, and D is the water contact angle of the PAN non-woven fabric after foaming.
FIG. 7 SEM image of PAN fiber prepared in example 7 and water contact angle of nonwoven fabric thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the PAN non-woven fabric before foaming, and D is the water contact angle of the PAN non-woven fabric after foaming.
FIG. 8 SEM image of PET fiber prepared in example 8 and water contact angle of nonwoven fabric thereof, wherein A is supercritical CO2The fiber morphology before foaming, B is the fiber morphology after foaming. C is the water contact angle of the PET non-woven fabric before foaming, and D is the water contact angle of the PET non-woven fabric after foaming.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. The materials, reagents and equipment used in the present invention are those conventional in the art unless otherwise specified.
Unless otherwise specified, materials and reagents used in the present invention are commercially available.
Example 1
The PVP non-woven fabric is prepared by adopting an electrostatic spinning method, and the preparation process conditions are as follows: ethanol is used as a solvent, and the concentration of a spinning solution is as follows: 25wt%, voltage: 20KV, distance between the injection needle and the receiving plate: 10cm, fiber diameter of the obtained hydrophilic polymer electrospun nonwoven fabric: 1-2 μm, and the diameter of the holes formed by lapping the fibers in the non-woven fabric is 5-20 μm.
Putting the prepared PVP non-woven fabric into a high-pressure reaction kettle, and performing supercritical CO treatment at the pressure of 12MPa and the temperature of 30 DEG C2Soaking for 30min, then quickly reducing the pressure (the pressure relief rate: 8 MPa/s), and foaming the PVP fiber to manufacture the PVP fiber containing nano pores. The water contact angle test shows that the non-woven fabricBefore and after foaming, the contact angle changed from 45 ° to almost complete spreading, achieving superhydrophilicity (fig. 1).
The untreated electrostatic spinning PVP fiber non-woven fabric is easy to break and can not be taken off from the receiving plate, and the supercritical CO is adopted2After treatment, the lap joint of the fibers is fused to a certain degree, the mechanical property is obviously improved, the fibers can be conveniently torn off, and the fibers have certain tensile property.
Example 2
The PMMA non-woven fabric is prepared by adopting an electrostatic spinning method, and the preparation process conditions are as follows: dichloromethane is used as a solvent, and the concentration of the spinning solution is as follows: 15wt%, voltage: 20KV, distance between the injection needle and the receiving plate: 15cm, fiber diameter of the obtained hydrophobic polymer electrospun nonwoven fabric: 1-5 μm, and the diameter of the holes formed by lapping the fibers in the non-woven fabric is 2-20 μm.
Placing the prepared PMMA non-woven fabric into a high-pressure reaction kettle, and performing supercritical CO at the pressure of 15MPa and the temperature of 100 DEG C2Soaking for 60min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), foaming the PMMA fiber, and manufacturing the PMMA fiber containing the nano holes. The water contact angle test shows that the contact angle is changed from 90 degrees to 160 degrees before and after the non-woven fabric is foamed, and super-hydrophobicity is realized (figure 2).
Example 3
Putting the purchased PP non-woven fabric into a high-pressure reaction kettle, and performing supercritical CO treatment at the pressure of 15MPa and the temperature of 130 DEG C2Soaking for 120min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), and foaming the PP fiber to manufacture the PP fiber containing the nano pores. The water contact angle test shows that the contact angle is changed from 100 degrees to 153 degrees before and after the non-woven fabric is foamed, and super-hydrophobicity is realized (figure 3).
Example 4
Putting the purchased nylon 66 woven cloth into a high-pressure reaction kettle, and performing supercritical CO treatment at the pressure of 18MPa and the temperature of 160 DEG C2Soaking for 120min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), and foaming the nylon 66 fiber to manufacture the nylon 66 fiber containing nano pores. The water contact angle test shows that the contact angle is changed from 85 degrees to 155 degrees before and after the woven fabric is foamed, and super-hydrophobicity is realized (figure 4).
Example 5
The polylactic acid PLA non-woven fabric is prepared by adopting an electrostatic spinning method, and the preparation process conditions are as follows: n, N-dimethylformamide is adopted as a solvent, and the concentration of a spinning solution is as follows: 20wt%, voltage: 20KV, distance between the injection needle and the receiving plate: 15cm, fiber diameter of the obtained hydrophobic polymer electrospun nonwoven fabric: 1-5 μm, and the diameter of the holes formed by lapping the fibers in the non-woven fabric is 2-20 μm.
Placing the prepared PLA non-woven fabric into a high-pressure reaction kettle, and performing supercritical CO treatment at the pressure of 15MPa and the temperature of 100 DEG C2Soaking for 60min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), foaming the PLA fiber, and manufacturing the PLA fiber containing nano pores. The water contact angle test shows that the contact angle is changed from 105 degrees to 155 degrees before and after the non-woven fabric is foamed, and super-hydrophobicity is realized (figure 5).
Example 6
The polyacrylonitrile PAN non-woven fabric is prepared by adopting an electrostatic spinning method, and the preparation process conditions are as follows: dimethyl acetamide is adopted as a solvent, and the concentration of a spinning solution is as follows: 15wt%, voltage: 20KV, distance between the injection needle and the receiving plate: 15cm, fiber diameter of the obtained hydrophobic polymer electrospun nonwoven fabric: 0.5 to 5 μm, and the diameter of the holes formed by lapping the fibers in the non-woven fabric is 2 to 20 μm.
Placing the prepared PAN non-woven fabric into a high-pressure reaction kettle, and performing supercritical CO treatment at the pressure of 15MPa and the temperature of 160 DEG C2Soaking for 60min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), and foaming the PAN fiber to manufacture the PAN fiber containing the nano-pores. The water contact angle test shows that the contact angle is changed from 105 degrees to 165 degrees before and after the non-woven fabric is foamed, and super-hydrophobicity is realized (figure 6).
Example 7
The purchased acrylic fibers (mainly polyacrylonitrile PAN) fibers are hot-pressed into non-woven fabrics, the diameter of the PAN fibers is 50 mu m, and the pore diameter formed by lapping the non-woven fabrics is 10-50 mu m. Placing into a high-pressure reaction kettle, and supercritical CO at the pressure of 18MPa and the temperature of 160 DEG C2Soaking for 120min, rapidly reducing pressure (pressure release rate: 7 MPa/s), foaming PAN fiber to obtain sodium-containing fiberPAN fibers of rice holes. The water contact angle test shows that before and after the foaming of the woven fabric, the contact angle is changed from 104 degrees to 154 degrees, and super-hydrophobicity is realized (figure 7).
Example 8
The diameter of PET fibers of a purchased Polyester (PET) non-woven fabric is 50 mu m, and the pore diameter formed by lapping the fibers of the non-woven fabric is 5-30 mu m. Placing into a high-pressure reaction kettle, and supercritical CO at the pressure of 18MPa and the temperature of 160 DEG C2Soaking for 120min, then quickly reducing the pressure (the pressure relief rate: 7 MPa/s), foaming the PET fiber, and manufacturing the PET fiber containing the nano pores. The water contact angle test shows that the contact angle is changed from 107 degrees to 158 degrees before and after the foaming of the woven fabric, and super-hydrophobicity is realized (figure 8).
Claims (3)
1. A method for preparing super-wetting fabric is characterized in that the fabric formed by thermoplastic polymer fibers adopts supercritical CO2Foaming is carried out under the following conditions: the pressure is 7-25 MPa, the temperature is 30-180 ℃, the soaking time is 30-180 min, and the pressure relief rate is as follows: 0.5-8 MPa/s;
wherein the diameter of the thermoplastic polymer fiber is 0.5-80 μm, and the pore diameter is 2-200 μm.
2. The method of claim 1, wherein the thermoplastic polymer fibers comprise hydrophilic thermoplastic polymer fibers and hydrophobic thermoplastic polymer fibers;
the hydrophilic thermoplastic polymer fibers are comprised of one or more of the following materials:
polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide;
the hydrophobic thermoplastic polymer fibers are comprised of one or more of the following materials:
polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polylactic acid, polyethylene terephthalate, nylon.
3. The method according to claim 2, wherein the fabric made of the hydrophilic thermoplastic polymer fiber is prepared by an electrospinning method under the following process conditions: concentration of the spinning solution: 10-30 wt%, voltage: 10-25 KV, the distance between the injection needle head and the receiving plate: 8-15 cm, the diameter of the thermoplastic polymer fiber is 0.5-5 μm, and the diameter of the hole formed by overlapping the thermoplastic polymer fiber is 2-50 μm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775744A (en) * | 2010-01-20 | 2010-07-14 | 天津工业大学 | Method for modifying super hydrophobicity of fabric |
| CN102534836A (en) * | 2011-12-14 | 2012-07-04 | 西安交通大学 | Method for preparing nano-fibers with special structures by using electrostatic spinning |
| CN103128973A (en) * | 2012-12-20 | 2013-06-05 | 华南理工大学 | Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775744A (en) * | 2010-01-20 | 2010-07-14 | 天津工业大学 | Method for modifying super hydrophobicity of fabric |
| CN102534836A (en) * | 2011-12-14 | 2012-07-04 | 西安交通大学 | Method for preparing nano-fibers with special structures by using electrostatic spinning |
| CN103128973A (en) * | 2012-12-20 | 2013-06-05 | 华南理工大学 | Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure |
Non-Patent Citations (1)
| Title |
|---|
| An investigation of the morphological changes in poly(ethylene terephthalate) fiber treated with supercritical carbon dioxide under various conditions;Kazumasa Hirogaki等;《J. of Supercritical Fluids》;20061031;第38卷(第3期);第399-405页 * |
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