CN115028874B - Waterproof and antifouling polyethylene plastic film and preparation method thereof - Google Patents
Waterproof and antifouling polyethylene plastic film and preparation method thereof Download PDFInfo
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- CN115028874B CN115028874B CN202210912975.6A CN202210912975A CN115028874B CN 115028874 B CN115028874 B CN 115028874B CN 202210912975 A CN202210912975 A CN 202210912975A CN 115028874 B CN115028874 B CN 115028874B
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 68
- -1 polyethylene Polymers 0.000 title claims abstract description 68
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 68
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 27
- 239000002985 plastic film Substances 0.000 title claims abstract description 19
- 229920006255 plastic film Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 57
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 57
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 57
- 239000002121 nanofiber Substances 0.000 claims abstract description 49
- 239000012528 membrane Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract 13
- 229920001410 Microfiber Polymers 0.000 claims description 52
- 239000003658 microfiber Substances 0.000 claims description 52
- 239000000956 alloy Substances 0.000 claims description 36
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000010041 electrostatic spinning Methods 0.000 claims description 20
- 230000010355 oscillation Effects 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 7
- 239000004702 low-density polyethylene Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012785 packaging film Substances 0.000 abstract description 5
- 229920006280 packaging film Polymers 0.000 abstract description 5
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Abstract
The invention relates to the technical field of functional films, and provides a waterproof and antifouling polyethylene plastic film and a preparation method thereof. The method constructs a micro-nano coarse structure by using the polyvinylpyrrolidone porous nanofiber membrane and the porous micro-nanofiber membrane which are soluble in deionized water, so that the surface of the polyethylene film is provided with one-dimensional linear nanoscale protrusions and micron-scale depressions, and the 1H, 2H-perfluoro decyl mercaptan is adopted for low surface energy modification, so that the surface of the film is endowed with good super-hydrophobic performance, and the film has good waterproof and antifouling performances. When the film is used as a packaging film for products in the fields of foods, medicines, electric appliances and the like, the film has higher use value, is favorable for realizing repeated use and reduces resource waste.
Description
Technical Field
The invention belongs to the technical field of functional films, and provides a waterproof and antifouling polyethylene plastic film and a preparation method thereof.
Background
With the development of the plastic industry, the plastic film is widely used as a packaging film or a film coating layer, the share of the plastic film in the packaging film is larger and larger, and particularly, the plastic flexible package is widely used in the fields of food, medicine, chemical industry, electric appliances and the like, and great convenience is brought to the production and life of people. The polyethylene film has the characteristics of translucency, luster and soft texture, and has good chemical stability, heat sealing property and low temperature resistance, so that the polyethylene film is widely used.
The plastic film is subjected to surface modification, has certain functionality, and can be further expanded in application range, such as improving adhesion, wettability, surface hardness, corrosion resistance, wear resistance, printability and the like. Wherein, the super-hydrophobic surface modification is an important direction, which can endow the film with good waterproof property, antifouling self-cleaning property, frost resistance, corrosion resistance, drag reduction capability and the like. For the polyethylene film used as the packaging film, the improvement of the waterproof and antifouling performance is beneficial to ensuring the quality of the packaged product and can realize the repeated use of the film.
The super-hydrophobic surface is a surface with a static water contact angle of more than 150 degrees and a rolling angle of less than 10 degrees, and the micro-nano rough structure and the low surface energy are two aspects of constructing the super-hydrophobic surface, and the following approaches are generally adopted: firstly, constructing a micro-nano rough surface, and then modifying the rough surface by using a low-surface energy substance; and secondly, constructing a rough structure on the surface of the low-surface-energy material.
Disclosure of Invention
The invention provides a waterproof and antifouling polyethylene plastic film and a preparation method thereof, wherein the film has good waterproof and antifouling performance by improving the superhydrophobicity of the surface of the film, so that the use value of the polyethylene film can be improved, and the application range is enlarged.
In order to achieve the above purpose, the specific technical scheme related to the invention is as follows:
the invention firstly provides a preparation method of a waterproof and antifouling polyethylene plastic film, which comprises the following specific steps:
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning;
(2) Heating low-melting-point alloy to be molten, coating the low-melting-point alloy on the surface of a quartz plate, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of an alloy coating, carrying out ultrasonic oscillation to enable the alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, and immersing with deionized water to remove the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying a release agent on a substrate with nanoscale depressions, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, heating polyethylene to be molten, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation to enable the polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale depressions of the substrate, cooling to room temperature, demolding, and immersing with deionized water to remove the microfibers, thereby obtaining a polyethylene film with nanoscale protrusions and microscale depressions;
(4) Adding 1H, 2H-perfluoro decyl mercaptan into diethyl ether, immersing the polyethylene film obtained in the step (3), taking out after 1-3h, and vacuum drying to obtain the waterproof and antifouling polyethylene film.
The preparation thinking of the invention is to construct a micro-nano coarse structure first and then modify the micro-nano coarse structure by adopting a low-surface energy substance. When the micro-nano coarse structure is constructed, a porous film formed by nano-scale diameter fibers is covered on the surface of a low-melting-point alloy melt coating, the alloy melt is promoted to be immersed into gaps among the nano fibers through ultrasonic oscillation, the nano fibers are removed after the melt is cooled, nano-scale depressions are formed on the surface of the alloy, and the depressions are in a one-dimensional linear shape; then spraying a release agent on the alloy substrate, covering a porous film formed by micron-sized diameter fibers on the surface of the substrate, coating a layer of polyethylene melt, promoting the polyethylene melt to be immersed into gaps among the micron fibers and nanometer depressions of the substrate through ultrasonic oscillation, cooling the melt, demolding, separating the polyethylene film layer from the alloy substrate, and removing the micron fibers on the polyethylene film layer, thereby forming a micro-nano coarse structure on the surface of the polyethylene film. The micro-nano coarse structure comprises nano-scale protrusions and micro-scale depressions, wherein the nano-scale protrusions are formed by taking the nano-scale depressions of an alloy substrate as templates, and the micro-scale depressions are formed by dissolving micro-fibers in deionized water. The nano-scale protrusions and the micro-scale depressions are one-dimensional linear structures.
In order to ensure that the nanofibers and microfibers are effectively removed when immersed in deionized water, it is preferred that the polyvinylpyrrolidone have a number average molecular weight of 40000±5000.
Because the melting point of the polyvinylpyrrolidone is lower (130 ℃), when the low-melting-point alloy melt is coated, the temperature of the alloy melt is required to be ensured to be lower than a certain value of the melting point of the polyvinylpyrrolidone in order to prevent the structure of the polyvinylpyrrolidone from being influenced; similarly, when coating the polyethylene melt, it is also necessary to ensure that the temperature of the polyethylene melt is below the melting point of the alloy by a certain value. Preferably, the melting point of the low-melting-point alloy is 120 ℃, and the heating temperature is 122-125 ℃; the polyethylene is low density polyethylene or linear low density polyethylene, the melting point is 108-110 ℃, and the heating temperature is 112-115 ℃.
In the preparation process, the porous nanofiber membrane and the porous microfiber membrane are stretched in advance before being covered, so that the fibers are aligned in the stretching direction to have certain orientation, and the stretching multiple in the stretching direction is preferably 1.1-1.2 times. Further, the stretching directions of the microfiber film and the nanofiber film are mutually perpendicular during covering. The function is as follows: when the microfiber film and the nanofiber film are covered in a direction perpendicular to each other, the one-dimensional linear structures formed by the nanofibers and the microfibers are more prone to overlap each other than to overlap each other, so that, on one hand, the polyethylene melt can better penetrate into the nano-scale recesses of the substrate through the voids of the microfibers when the polyethylene melt is coated, and on the other hand, the nano-scale protrusions on the surface of the film can be ensured to have structural support after the microfibers are removed.
In addition, the polyvinylpyrrolidone porous nanofiber membrane and the polyvinylpyrrolidone porous microfiber membrane are prepared by adopting electrostatic spinning. It is known that, under certain spinning process conditions, the concentration of polyvinylpyrrolidone in the spinning solution influences the fiber forming diameter, when the concentration of the spinning solution is low, nano-sized fibers can be formed, when the concentration of the spinning solution is high, micro-sized fibers can be formed, and by utilizing the characteristic, the electrostatic spinning porous membrane of the nano-sized fibers and the micro-sized fibers can be prepared.
Preferably, the electrostatic spinning solution of the polyvinylpyrrolidone porous nanofiber membrane consists of polyvinylpyrrolidone and ethanol, wherein the mass concentration of polyvinylpyrrolidone is 35-40%, the spinning process parameters are that the applied voltage is 18-22kV, the receiving distance is 8-12cm, the ambient temperature is 20-25 ℃, the relative humidity is 30-40%, and the injection speed is 0.1-0.12mL/h.
Preferably, the electrostatic spinning solution of the polyvinylpyrrolidone porous microfiber membrane consists of polyvinylpyrrolidone and ethanol, wherein the mass concentration of the polyvinylpyrrolidone is 60-65%, the spinning process parameters are that the external voltage is 18-22kV, the receiving distance is 8-12cm, the ambient temperature is 20-25 ℃, the relative humidity is 30-40%, and the injection speed is 0.1-0.12mL/h.
Preferably, the ultrasonic oscillation frequency in the step (2) is 25-30kHz, the time is 10-15min, the temperature of the deionized water is 50-60 ℃, and the soaking time is 2-3 days.
Preferably, the release agent is polyethylene glycol.
Preferably, the ultrasonic oscillation frequency in the step (3) is 35-40kHz, the time is 20-30min, the temperature of the deionized water is 50-60 ℃, and the soaking time is 3-4 days.
Preferably, the mass ratio of the 1H, 2H-perfluorodecyl mercaptan to the diethyl ether is 2-3:100.
the invention also provides the waterproof and antifouling polyethylene plastic film prepared by the preparation method. The polyethylene film has micro-nano rough structure and low surface energy. The micro-nano coarse structure is formed by one-dimensional linear nanoscale protrusions and micron-scale depressions, and the low surface energy is modified by 1H, 2H-perfluoro decyl mercaptan.
The beneficial effects are that: the invention provides a waterproof and antifouling polyethylene plastic film and a preparation method thereof, wherein a micro-nano coarse structure is constructed by a polyvinylpyrrolidone porous nanofiber membrane and a porous micro-nanofiber membrane which are soluble in deionized water, so that the surface of the polyethylene film is provided with one-dimensional linear nanoscale protrusions and micron depressions, and 1H, 2H-perfluoro decyl mercaptan is adopted for low surface energy modification, so that the film has good super-hydrophobic performance, and therefore, the film has good waterproof and antifouling performance. When the film is used as a packaging film for products in the fields of foods, medicines, electric appliances and the like, the film has higher use value, is favorable for realizing repeated use and reduces resource waste.
Detailed Description
The following examples are further illustrative of the invention and are not to be construed as limiting the scope of the invention. Various substitutions and alterations are also within the scope of this disclosure, as will be apparent to those of ordinary skill in the art and by routine experimentation, without departing from the spirit and scope of the invention as defined by the foregoing description.
In the following examples and comparative examples, polyvinylpyrrolidone was a commercially available K30 product having a number average molecular weight of 40000; the low-melting-point alloy is a commercial alloy product, and the melting point is 120 ℃; the low density polyethylene is a commercial product with a melting point of 108 ℃.
Example 1
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning, and respectively stretching, wherein the stretching times in the stretching direction are 1.15 times;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous nanofiber membrane is 35wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous microfiber membrane is 65 wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
(2) Heating low-melting-point alloy to 122 ℃, coating the low-melting-point alloy on the surface of a quartz plate after complete melting, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of the alloy coating, carrying out ultrasonic oscillation at 25 kHz for 15min to enable alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, adopting deionized water at 50 ℃ to soak for 3 days, and removing the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying polyethylene glycol on a substrate with nanoscale recesses, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, enabling the stretching directions of the microfiber film and the nanofiber film to be mutually perpendicular during covering, heating low-density polyethylene to 112 ℃, completely melting, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation at 40kHz for 20min, enabling polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale recesses of the substrate, cooling to room temperature, demolding, soaking in deionized water at 50 ℃ for 4 days, and removing the microfibers to obtain a polyethylene film with nanoscale protrusions and microscale recesses;
(4) 1H, 2H-perfluoro decyl mercaptan with the mass ratio of 2.5:100 is added into diethyl ether, immersed into the polyethylene film obtained in the step (3), taken out after 2 hours, and dried in vacuum, thus obtaining the waterproof and antifouling polyethylene film.
The polyethylene film surface of example 1 was tested for water contact angle at room temperature using an OCA20 optical contact angle meter with water drop of 5 μl and an average value of 171.3 ° for 5 times; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded, namely the rolling angle, and the average value of 5 times of testing was 2.2 °.
Example 2
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning, and respectively stretching, wherein the stretching times in the stretching direction are 1.15 times;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous nanofiber membrane is 40wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous microfiber membrane is 60 wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
(2) Heating low-melting-point alloy to 122 ℃, completely melting, coating on the surface of a quartz plate, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of the alloy coating, carrying out ultrasonic oscillation for 10min at 30kHz to enable alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, soaking in deionized water at 55 ℃ for 2.5 days, and removing the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying polyethylene glycol on a substrate with nanoscale recesses, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, enabling the stretching directions of the microfiber film and the nanofiber film to be mutually perpendicular during covering, heating low-density polyethylene to 112 ℃, completely melting, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation for 30min at 35kHz, enabling polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale recesses of the substrate, cooling to room temperature, demolding, soaking in deionized water at 55 ℃ for 3.5 days, and removing the microfibers to obtain a polyethylene film with nanoscale protrusions and microscale recesses;
(4) 1H, 2H-perfluoro decyl mercaptan with the mass ratio of 2.5:100 is added into diethyl ether, immersed into the polyethylene film obtained in the step (3), taken out after 2 hours, and dried in vacuum, thus obtaining the waterproof and antifouling polyethylene film.
The surface of the polyethylene film of example 2 was tested at room temperature for a water contact angle of 166.8 ° on average for 5 times with 5 μl water drops using an OCA20 optical contact angle meter; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded as the rolling angle, and the average value of 5 times of testing was 3.1 °.
Example 3
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning, and respectively stretching, wherein the stretching times in the stretching direction are 1.15 times;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous nanofiber membrane is 35wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous microfiber membrane is 60 wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
(2) Heating low-melting-point alloy to 122 ℃, coating the low-melting-point alloy on the surface of a quartz plate after complete melting, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of the alloy coating, carrying out ultrasonic oscillation at 28 kHz for 12min to enable alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, adopting deionized water at 60 ℃ to soak for 2 days, and removing the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying polyethylene glycol on a substrate with nanoscale recesses, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, enabling the stretching directions of the microfiber film and the nanofiber film to be mutually perpendicular during covering, heating low-density polyethylene to 112 ℃, completely melting, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation at 38kHz for 25min to enable polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale recesses of the substrate, cooling to room temperature, demolding, soaking in deionized water at 60 ℃ for 3 days, and removing the microfibers to obtain a polyethylene film with nanoscale protrusions and microscale recesses;
(4) 1H, 2H-perfluoro decyl mercaptan with the mass ratio of 2.5:100 is added into diethyl ether, immersed into the polyethylene film obtained in the step (3), taken out after 2 hours, and dried in vacuum, thus obtaining the waterproof and antifouling polyethylene film.
The surface of the polyethylene film of example 3 was tested at room temperature for a water contact angle of 168.7 ° on average for 5 times with 5 μl water drops using OCA20 optical contact angle meter; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded, namely the rolling angle, and the average value of 5 times of testing was 2.6 °.
Example 4
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning, and respectively stretching, wherein the stretching times in the stretching direction are 1.15 times;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous nanofiber membrane is 40wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
the concentration of spinning solution for electrostatic spinning of the polyvinylpyrrolidone porous microfiber membrane is 65 wt%, the applied voltage is 20kV, the receiving distance is 10cm, the ambient temperature is 25 ℃, the relative humidity is 35%, and the injection speed is 0.1mL/h;
(2) Heating low-melting-point alloy to 122 ℃, coating the low-melting-point alloy on the surface of a quartz plate after complete melting, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of the alloy coating, carrying out ultrasonic oscillation at 28 kHz for 12min to enable alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, adopting deionized water at 60 ℃ to soak for 2 days, and removing the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying polyethylene glycol on a substrate with nanoscale recesses, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, enabling the stretching directions of the microfiber film and the nanofiber film to be mutually perpendicular during covering, heating low-density polyethylene to 112 ℃, completely melting, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation at 38kHz for 25min to enable polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale recesses of the substrate, cooling to room temperature, demolding, soaking in deionized water at 60 ℃ for 3 days, and removing the microfibers to obtain a polyethylene film with nanoscale protrusions and microscale recesses;
(4) 1H, 2H-perfluoro decyl mercaptan with the mass ratio of 2.5:100 is added into diethyl ether, immersed into the polyethylene film obtained in the step (3), taken out after 2 hours, and dried in vacuum, thus obtaining the waterproof and antifouling polyethylene film.
The surface of the polyethylene film of example 4 was tested at room temperature for a water contact angle of 168.1 ° on average for 5 times with 5 μl water drops using OCA20 optical contact angle meter; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded, namely the rolling angle, and the average value of 5 times of testing was 2.7 °.
Comparative example 1
In the preparation process, the polyvinylpyrrolidone porous nanofiber membrane is not used, other preparation conditions are the same as those of comparative example 1, and the surface of the prepared polyethylene film only has micron-sized depressions and does not have nanometer-sized protrusions.
The surface of the polyethylene film of example 1 was tested at room temperature for a water contact angle of 134.5 ° in 5 μl water drops using an OCA20 optical contact angle meter; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded, namely the rolling angle, and the average value of 5 times of testing was 11.7 °.
Comparative example 2
In the preparation process, the polyvinylpyrrolidone porous microfiber membrane is not used, other preparation conditions are consistent with those of comparative example 2, and the surface of the prepared polyethylene film only has nanoscale protrusions and does not have micron-scale depressions.
The surface of the polyethylene film of example 1 was tested at room temperature for water contact angle with an OCA20 optical contact angle meter with 5 μl water drop, and the average value of 5 times was 137.2 °; the film was fixed on a slide glass, and the angle between the film and the horizontal plane when 5. Mu.L of water drops were rolled was recorded as the rolling angle, and the average value of 5 times of testing was 10.5 °.
Claims (8)
1. The preparation method of the waterproof and antifouling polyethylene plastic film is characterized by comprising the following specific steps of:
(1) Preparing a polyvinylpyrrolidone porous nanofiber membrane and a polyvinylpyrrolidone porous microfiber membrane by electrostatic spinning;
(2) Heating low-melting-point alloy to be molten, coating the low-melting-point alloy on the surface of a quartz plate, covering a polyvinylpyrrolidone porous nanofiber membrane on the surface of an alloy coating, carrying out ultrasonic oscillation to enable the alloy melt to be fully immersed in gaps among nanofibers, cooling to room temperature, and immersing with deionized water to remove the nanofibers to obtain a substrate with nanoscale depressions;
(3) Spraying a release agent on a substrate with nanoscale depressions, covering a polyvinylpyrrolidone porous microfiber film on the surface of the substrate, heating polyethylene to be molten, coating the surface of the porous microfiber film, carrying out ultrasonic oscillation to enable the polyethylene melt to be fully immersed in gaps among the microfibers and into the nanoscale depressions of the substrate, cooling to room temperature, demolding, and immersing with deionized water to remove the microfibers, thereby obtaining a polyethylene film with nanoscale protrusions and microscale depressions;
(4) Adding 1H, 2H-perfluoro decyl mercaptan into diethyl ether, immersing the polyethylene film obtained in the step (3), taking out after 1-3h, and vacuum drying to obtain a waterproof and antifouling polyethylene film;
the number average molecular weight of the polyvinylpyrrolidone is 40000+/-5000;
the melting point of the low-melting-point alloy is 120 ℃, and the heating temperature is 122-125 ℃;
the polyethylene is low-density polyethylene, the melting point is 108-110 ℃, and the heating temperature is 112-115 ℃;
the porous nanofiber membrane and the porous microfiber membrane are stretched before being covered, and the stretching multiple along the stretching direction is 1.1-1.2 times;
when in covering, the stretching directions of the micro fiber film and the nano fiber film are mutually perpendicular.
2. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the electrostatic spinning solution of the polyvinylpyrrolidone porous nanofiber membrane consists of polyvinylpyrrolidone and ethanol, wherein the mass concentration of the polyvinylpyrrolidone is 35-40%, the spinning process parameters are that the applied voltage is 18-22kV, the receiving distance is 8-12cm, the ambient temperature is 20-25 ℃, the relative humidity is 30-40%, and the injection speed is 0.1-0.12mL/h.
3. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the electrostatic spinning solution of the polyvinylpyrrolidone porous microfiber membrane consists of polyvinylpyrrolidone and ethanol, wherein the mass concentration of the polyvinylpyrrolidone is 60-65%, the spinning process parameters are that the applied voltage is 18-22kV, the receiving distance is 8-12cm, the ambient temperature is 20-25 ℃, the relative humidity is 30-40%, and the injection speed is 0.1-0.12mL/h.
4. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the ultrasonic oscillation frequency in the step (2) is 25-30kHz, the time is 10-15min, the temperature of the deionized water is 50-60 ℃, and the soaking time is 2-3 days.
5. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the release agent is polyethylene glycol.
6. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the ultrasonic oscillation frequency in the step (3) is 35-40kHz, the time is 20-30min, the temperature of the deionized water is 50-60 ℃, and the soaking time is 3-4 days.
7. The method for preparing the waterproof and antifouling polyethylene plastic film according to claim 1, wherein the method comprises the following steps: the mass ratio of the 1H, 2H-perfluorodecyl mercaptan to the diethyl ether is 2-3:100.
8. the waterproof and antifouling polyethylene plastic film prepared by the preparation method of any one of claims 1 to 7.
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