CN115536893B - Super-hydrophobic ice-proof film capable of realizing photo-thermal conversion and preparation method and application thereof - Google Patents

Super-hydrophobic ice-proof film capable of realizing photo-thermal conversion and preparation method and application thereof Download PDF

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CN115536893B
CN115536893B CN202211405415.8A CN202211405415A CN115536893B CN 115536893 B CN115536893 B CN 115536893B CN 202211405415 A CN202211405415 A CN 202211405415A CN 115536893 B CN115536893 B CN 115536893B
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CN115536893A (en
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刘毅彬
高珊
郭瑞雲
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Xian University of Science and Technology
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Abstract

The invention discloses a superhydrophobic anti-icing film capable of realizing photothermal conversion, and a preparation method and application thereof, and belongs to the technical field of anti-icing film preparation. The preparation method of the super-hydrophobic ice-preventing film capable of realizing photo-thermal conversion comprises the following steps: taking a polar solution A as a solvent, an alkaline compound as a catalyst, an aminated carbon nanotube as a raw material, and 2-bromoisobutyryl bromide as a brominating agent, and performing an acylation reaction in an ice-water bath to obtain a brominated carbon nanotube; uniformly coating PDMS prepolymer on a quartz plate, heating, uniformly coating carbon bromide nano tubes on the surface of the quartz plate, curing, and demolding to obtain a PDMS film with the surface adhered with the carbon bromide nano tubes; the super-hydrophobic anti-icing film is prepared by horizontally placing the super-hydrophobic anti-icing film on a glass plate, taking a polar solution B as a solvent, a nitrogen-containing compound as a ligand, a perfluoroalkyl ethyl methacrylate compound as a monomer and a copper plate as a catalyst, and initiating monomer polymerization on the surface of a PDMS film. The super-hydrophobic anti-icing film has good durability and excellent anti-icing effect.

Description

Super-hydrophobic ice-proof film capable of realizing photo-thermal conversion and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of anti-icing films, in particular to a super-hydrophobic anti-icing film capable of realizing photo-thermal conversion, and a preparation method and application thereof.
Background
The icing phenomenon may greatly hinder the normal operation of highways, airplanes, ships, power lines, telecommunication equipment, etc. At present, deicing methods mainly comprise physical and chemical deicing methods, but both of the deicing methods can bring about a great deal of energy and resource consumption. In the past few years, the anti-icing properties of superhydrophobic surfaces have gained increasing attention from scientists inspired by the superhistiness of the surface of biological materials. The larger the contact angle value on the superhydrophobic surface is, the smaller the contact area between the liquid drop on the surface and the solid surface is. Therefore, the heat transfer effect of the liquid drop on the superhydrophobic surface and the substrate surface is poorer than that of the common surface, the icing time is delayed, and the excellent anti-icing effect is realized.
However, superhydrophobic materials also have some drawbacks as anti-icing materials. In a low-temperature and high-humidity environment, a large amount of condensed water can damage the hydrophobicity of the superhydrophobic surface. After the condensed water on the surface is frozen, the ice often forms a mechanical interlocking structure with the superhydrophobic surface, and the superhydrophobic surface is nailed on the surface of the ice so as to improve the adhesive strength of the ice on the surface. Thus, during deicing, the structure of the superhydrophobic surface is broken, thereby affecting long-term durability.
In addition, the surface-initiated hydrophobic monomer polymerization grafting hydrophobic polymer method is a common method for preparing super-hydrophobic materials. However, the existing surface initiated polymerization technology has the following disadvantages when preparing the super-hydrophobic material: 1. the super-hydrophobic membrane prepared by grafting the hydrophobic polymer method by using the traditional surface initiation-atom transfer radical polymerization method has poor mechanical properties, and is unfavorable for long-term use, which is probably caused by poor mechanical strength of the polymer PFMA. 2. In the surface initiation-atom transfer radical polymerization process, a large amount of solvent and copper salt are needed, so that resource waste and environmental pollution are easily caused, the polymerization process is required to be carried out under an anaerobic condition, and the reaction condition is severe.
Disclosure of Invention
Aiming at the problems, the invention provides the super-hydrophobic ice-preventing film capable of realizing photo-thermal conversion, and the preparation method and the application thereof, and the durability of the super-hydrophobic ice-preventing film is improved.
The first object of the invention is to provide a preparation method of a light-heat convertible super-hydrophobic ice-proof film, which comprises the following steps:
step 1, preparation of carbon bromide nanotubes
Taking polar solution A as a solvent, an alkaline compound as a catalyst, an aminated carbon nanotube as a raw material, and 2-bromoisobutyryl bromide as a brominating agent, and performing acylation reaction in ice water bath to obtain a brominated carbon nanotube for later use;
step 2, preparing super-hydrophobic anti-icing film by surface initiation-Cu (0) catalyzed controllable free radical polymerization method
Uniformly coating the polydimethylsiloxane prepolymer on a quartz plate, heating for 15-60min at 50-80 ℃, uniformly coating the surface of the quartz plate with carbon bromide nanotubes, curing and demolding to obtain a polydimethylsiloxane film with the surface adhered with the carbon bromide nanotubes;
and (3) horizontally placing the polydimethylsiloxane film on a glass plate, taking the polar solution B as a solvent, a nitrogen-containing compound as a ligand and a perfluoroalkyl ethyl methacrylate compound as a monomer, taking a copper plate as a catalyst, and initiating monomer polymerization on the surface of the polydimethylsiloxane film to prepare the super-hydrophobic ice-preventing film.
Preferably, in step 1, the reaction time of the acylation reaction is 12 to 24 hours, wherein the ratio of the aminated carbon nanotube, the polar solution A, the basic compound and the 2-bromoisobutyryl bromide is 0.05 to 0.2g:30-50ml:1-5ml:4-8ml;
the polar solvent A is one of N, N-dimethylformamide, N, N-dimethylacetamide, toluene, xylene, dichloroethane and dioxane; the basic compound is one of triethylamine, diphenyl phosphine, tributylphosphine and diethylenetriamine.
Preferably, in step 2, the polydimethylsiloxane prepolymer is applied at a thickness of 50 to 500 μm per 1625mm 2 The addition amount of the brominated carbon nanotubes is 50-80mg on the quartz plate.
Preferably, in the step 2, the curing treatment is performed at 70-100 ℃ for 0.5-4 hours.
Preferably, in the step 2, the polar solution B, the nitrogen-containing compound and the perfluoroalkyl ethyl methacrylate compound are mixed to obtain a reaction solution for standby;
and (3) putting the polydimethylsiloxane film on a glass plate horizontally, adding a reaction solution on the surface of the glass plate, then covering a copper plate, standing for reaction for 30min-2h, washing the modified polydimethylsiloxane film, and finally drying at room temperature to obtain the super-hydrophobic ice-preventing film.
Preferably, in the step 2, the volume ratio of the polar solution, the perfluoroalkyl ethyl methacrylate compound and the nitrogen-containing compound is 1:0.05-0.5:0.01-0.04;
the perfluoroalkyl ethyl methacrylate compound is CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) n CF 3 Wherein n is a natural number from 3 to 10; the polar solution B is N, N-dimethylformamide, N, N-dimethylAcetamide, dimethyl sulfoxide, dioxane, N-methyl pyrrolidone; the nitrogen-containing compound is one of pentamethyldiethylenetriamine, pyridine and 2, 2-bipyridine.
Preferably, in step 2, the distance between the copper plate and the brominated polydimethylsiloxane film is 0.2-1mm, every 1625mm 2 The amount of the reaction solution added to the brominated polydimethylsiloxane film was 10 to 15. Mu.L.
The second object of the invention is to provide the super-hydrophobic anti-icing film which can be subjected to photo-thermal conversion and is prepared by the preparation method.
The third purpose of the invention is to provide the application of the super-hydrophobic ice-preventing film capable of realizing photo-thermal conversion in aircrafts, power transmission lines and wind power blades.
The mechanism of the invention: according to the invention, a surface-initiated-Cu (0) catalyzed controllable free radical polymerization method is utilized to initiate monomer perfluorooctyl ethyl methacrylate polymerization to prepare the hydrophobic polymer brush on the brominated carbon nano tube on the surface of the super-hydrophobic anti-icing film under the action of a catalyst copper plate and ligand pentamethyl diethylenetriamine and in a room temperature air environment, so that the anti-icing film shows super-hydrophobic performance, and the anti-icing-deicing effect of the super-hydrophobic anti-icing film is achieved by cooperating with the photo-thermal conversion capability of the carbon nano tube.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the super-hydrophobic anti-icing membrane by utilizing the surface initiation-Cu (0) catalyzed controllable free radical polymerization grafted hydrophobic polymer method can initiate monomer polymerization in a limited space between a copper plate and a substrate, has the advantages of less use of chemical solvents, high polymer brush growth rate, simple preparation process and the like, and achieves the effect of optimizing the surface initiation polymerization process;
(2) The invention can not only construct organic-inorganic composite structure to obviously improve the wear resistance of the super-hydrophobic ice-proof film, but also generate heat under the irradiation of near infrared light by utilizing the photothermal conversion capability to achieve the deicing effect;
(3) The anti-icing/deicing effect of the super-hydrophobic anti-icing film prepared by the invention is obviously improved; the anti-icing effect is mainly due to the super-hydrophobic property of the super-hydrophobic anti-icing film, and the deicing effect is mainly due to the photothermal conversion capability of the carbon nano tube;
(4) The invention uses the organic-inorganic composite structure constructed by the carbon nano tube and the Polydimethylsiloxane (PDMS) to obviously improve the wear resistance of the super-hydrophobic film, and the super-hydrophobic performance still exists when the super-hydrophobic film is rubbed for 12 meters under the pressure of 9.8kPa under 1000-mesh sand paper.
Drawings
FIG. 1 is a schematic diagram of the preparation of a superhydrophobic ice-repellent film according to the invention;
fig. 2 is a graph showing the deicing effect of the superhydrophobic anti-icing film prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified. The PDMS precursor and the curing agent matched with the PDMS precursor are the Dow Corning 184, wherein the curing agent is hydrogen-containing silicone oil. In addition, DMF represents N, N-dimethylformamide, PMDETA represents pentamethyldiethylenetriamine, FMA represents perfluorooctylethyl methacrylate, DMAc is N, N-dimethylacetamide, DMSO represents dimethyl sulfoxide, NMP represents N-methylpyrrolidone, and PDMS represents polydimethylsiloxane. The temperature of the ice water bath in the invention is 0-4 ℃.
Example 1
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of DMF and 3mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, uniformly coating 50mg of carbon bromide nanotube on the surface of PDMS, then transferring into an oven at 80 ℃ for continuous curing for 3h, taking out, and demolding to obtain the PDMS film with the surface adhered with the carbon bromide nanotube. As shown in fig. 1, DMF, FMA, PMDETA is prepared into a reaction solution according to the volume ratio of 1:0.05:0.02 for standby; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 30min, the modified PDMS film is put into DMF for three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature. As shown in fig. 1.
The contact angle of the super-hydrophobic anti-icing film, which is rubbed by applying 9.8kPa under 1000 meshes of sand paper for 12 meters, is still kept at 161 degrees; the surface ice of the super-hydrophobic anti-icing film can be melted under the irradiation of near infrared light for 60 seconds.
Example 2
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of DMF and 3mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
Firstly, uniformly coating PDMS prepolymer (PDMS precursor and curing agent are mixed according to the weight ratio of 10:1) on a quartz plate with the thickness of 65mm multiplied by 25mm, placing the quartz plate on a heating plate with the temperature of 70 ℃ for 30min, uniformly coating 50mg of carbon bromide nano tubes on the surface of the PDMS when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, then transferring the PDMS precursor and curing agent into an oven with the temperature of 80 ℃ for curing for 3h, taking out the quartz plate, and demolding to obtain the PDMS film with the surface adhered with the carbon bromide nano tubes. As shown in fig. 1, DMF, FMA, PMDETA is prepared into a reaction solution according to the volume ratio of 1:0.1:0.01 for standby; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10 μl of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.2mm by a spacer. After standing for 30min, the modified PDMS film is put into DMF for three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature.
The contact angle of the super-hydrophobic anti-icing film, which is rubbed by applying 9.8kPa under 1000 meshes of sand paper for 12 meters, is still kept at 153 degrees; the surface ice of the super-hydrophobic anti-icing film can be melted under the irradiation of near infrared light for 75 seconds.
Example 3
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of DMF and 3mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
Firstly, uniformly coating PDMS prepolymer (PDMS precursor and curing agent are mixed according to the weight ratio of 10:1) on a quartz plate with the thickness of 65mm multiplied by 25mm, placing the quartz plate on a heating plate with the temperature of 70 ℃ for 30min, uniformly coating brominated carbon nano tubes on the surface of the PDMS when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, then transferring the PDMS precursor and curing agent into an oven with the temperature of 80 ℃ for curing for 3h, taking out the PDMS film with the surface adhered with the brominated carbon nano tubes, and demolding the PDMS film. As shown in fig. 1, DMF, FMA, PMDETA is prepared into a reaction solution according to the volume ratio of 1:0.5:0.04 for standby; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 1mm by a spacer. After standing for 30min, the modified PDMS film is put into DMF for three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature.
The contact angle of the super-hydrophobic anti-icing film, which is rubbed by applying 9.8kPa under 1000 meshes of sand paper for 12 meters, is still kept at 156 degrees; the surface ice of the super-hydrophobic anti-icing film can be melted under the irradiation of near infrared light for 90 s.
Example 4
Into a three-necked flask, 0.05g of an aminated carbon nanotube, 50mL of an MF and 1mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 8mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 12 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed for 3 times by ethanol and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, PDMS prepolymer (PDMS precursor and curing agent were mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 100 μm and placed on a 50℃heating plate. After 60min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, 80mg of the brominated carbon nano tube is uniformly coated on the surface of the PDMS, then the PDMS film with the surface adhered with the brominated carbon nano tube is obtained after the PDMS prepolymer is taken out after being moved into a 70 ℃ oven to be continuously cured for 4h, and the PDMS film is obtained after demoulding. As shown in FIG. 1, DMF, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 9 CF 3 Preparing a reaction solution by PMDETA according to the volume ratio of 1:0.3:0.03 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 15. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 1mm by a spacer. After standing for 2 hours, the modified PDMS film is put into DMF for three times, and finally is dried at room temperature to obtain the super-hydrophobic anti-icing film.
Example 5
Into a three-necked flask, 0.2g of an aminated carbon nanotube, 30mL of DMF and 5mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 4mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 20 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed for 3 times by ethanol and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
Firstly, uniformly coating PDMS prepolymer (PDMS precursor and curing agent are mixed according to the weight ratio of 10:1) on a quartz plate with the thickness of 65mm multiplied by 25mm, placing the quartz plate on a heating plate with the temperature of 80 ℃ for 15min, uniformly coating 60mg of brominated carbon nano tubes on the surface of PDMS when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, then transferring the PDMS prepolymer into a baking oven with the temperature of 100 ℃ for curing for 0.5h, taking out the quartz plate, and demolding to obtain the surface adhesionPDMS films of brominated carbon nanotubes. As shown in FIG. 1, DMF, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 8 CF 3 Preparing a reaction solution by PMDETA according to the volume ratio of 1:0.02:0.05 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, and 12. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 1h, the modified PDMS film is put into DMF for three times, and finally is dried at room temperature to obtain the super-hydrophobic anti-icing film.
Example 6
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of MAc and 3mL of diphenylphosphine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, 80mg of the brominated carbon nano tube is uniformly coated on the surface of the PDMS, then the PDMS film with the surface adhered with the brominated carbon nano tube is obtained after the PDMS prepolymer is taken out after being moved into an oven at 80 ℃ to be continuously cured for 3h, and the PDMS film is obtained after demoulding. As shown in FIG. 1, DMAc, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 3 CF 3 Preparing a reaction solution by pyridine according to the volume ratio of 1:0.05:0.02 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 30min, the modified PDMS film is put into DMAc to be washed three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature.
Example 7
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of toluene and 3mL of tributylphosphine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, uniformly coating 70mg of carbon bromide nanotube on the surface of PDMS, then transferring into an oven at 80 ℃ for continuous curing for 3h, taking out, and demolding to obtain the PDMS film with the surface adhered with the carbon bromide nanotube. As shown in FIG. 1, DMSO, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 4 CF 3 Preparing a reaction solution by pyridine according to the volume ratio of 1:0.05:0.02 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 30min, the modified PDMS film is put into DMSO for three times, and finally is dried at room temperature to obtain the super-hydrophobic anti-icing film.
Example 8
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of xylene and 3mL of diethylenetriamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, uniformly coating 50mg of carbon bromide nanotube on the surface of PDMS, then transferring into an oven at 80 ℃ for curing for 3h, taking out, and demolding to obtain the carbon bromide nanotube with the surface adheredIs a PDMS film of (C). As shown in FIG. 1, dioxane, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 5 CF 3 Preparing a reaction solution from 2, 2-bipyridine according to a volume ratio of 1:0.05:0.02 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 15. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. And standing for 30min, putting the modified PDMS film into a dioxane for washing for three times, and finally drying at room temperature to obtain the super-hydrophobic anti-icing film.
Example 9
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of dichloroethane and 3mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, uniformly coating 50mg of carbon bromide nanotube on the surface of PDMS, then transferring into an oven at 80 ℃ for continuous curing for 3h, taking out, and demolding to obtain the PDMS film with the surface adhered with the carbon bromide nanotube. As shown in FIG. 1, NMP, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 6 CF 3 Preparing a reaction solution by PMDETA according to the volume ratio of 1:0.05:0.02 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, and 12. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 30min, the modified PDMS film is put into NMP for three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature.
Example 10
Into a three-necked flask, 0.1g of an aminated carbon nanotube, 40mL of dichloroethane and 3mL of triethylamine were added, and after stirring uniformly, the mixture was immersed in an ice-water bath, and 6mL of 2-bromoisobutyryl bromide was added dropwise. After the dripping is finished, the reaction is carried out for 24 hours under ice water bath, then the reaction solution is poured into a buchner funnel to pump and filter black powder, and the black powder is washed with ethanol for 3 times and dried at room temperature, thus finally obtaining the carbon bromide nanotube.
First, a PDMS prepolymer (wherein a PDMS precursor and a curing agent are mixed in a weight ratio of 10:1) was uniformly coated on a 65mm by 25mm quartz plate to a thickness of 50 μm, and placed on a heating plate at 70 ℃. After 30min, when the PDMS prepolymer on the quartz plate loses fluidity but the surface is still sticky, uniformly coating 50mg of carbon bromide nanotube on the surface of PDMS, then transferring into an oven at 80 ℃ for continuous curing for 3h, taking out, and demolding to obtain the PDMS film with the surface adhered with the carbon bromide nanotube. As shown in FIG. 1, DMF, CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) 10 CF 3 Preparing a reaction solution by PMDETA according to the volume ratio of 1:0.05:0.02 for later use; then, a 65mm×25mm PDMS film was laid flat on a glass plate, 10. Mu.L of the reaction solution was dropped on the surface thereof, and then a copper plate was covered, and the distance between the copper plate and the brominated PDMS film was adjusted to 0.5mm by a spacer. After standing for 40min, the modified PDMS film is put into DMF for three times, and finally the super-hydrophobic anti-icing film is obtained by drying at room temperature.
Fig. 2 shows the deicing effect of the superhydrophobic film prepared in example 1, in which 30 μl of water droplets are first dropped on the surface of the superhydrophobic anti-icing film, and after the superhydrophobic anti-icing film is completely frozen at-10 ℃, the superhydrophobic anti-icing film is irradiated with near infrared light for 0, 20, 40, and 60s, and the result shows that the water droplets on the surface of the superhydrophobic anti-icing film are completely melted within 60s of the near infrared light irradiation.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (9)

1. The preparation method of the superhydrophobic ice-preventing film capable of realizing photothermal conversion is characterized by comprising the following steps of:
step 1, preparation of carbon bromide nanotubes
Taking polar solution A as a solvent, an alkaline compound as a catalyst, an aminated carbon nanotube as a raw material, and 2-bromoisobutyryl bromide as a brominating agent, and performing acylation reaction in ice water bath to obtain a brominated carbon nanotube for later use;
step 2, preparing super-hydrophobic anti-icing film by surface initiation-Cu (0) catalyzed controllable free radical polymerization method
Uniformly coating the polydimethylsiloxane prepolymer on a quartz plate, heating for 15-60min at 50-80 ℃, uniformly coating the surface of the quartz plate with carbon bromide nanotubes, curing and demolding to obtain a polydimethylsiloxane film with the surface adhered with the carbon bromide nanotubes;
and (3) horizontally placing the polydimethylsiloxane film with the surface adhered with the carbon bromide nano tube on a glass plate, taking the polar solution B as a solvent, a nitrogen-containing compound as a ligand and a perfluoroalkyl ethyl methacrylate compound as a monomer, taking a copper plate as a catalyst, and initiating monomer polymerization on the surface of the polydimethylsiloxane film to prepare the super-hydrophobic anti-icing film.
2. The method for preparing a photo-thermal convertible super hydrophobic ice preventing film according to claim 1, wherein in step 1, the reaction time of the acylation reaction is 12-24 hours, wherein the ratio of the aminated carbon nanotube to the polar solution A to the alkaline compound to the 2-bromoisobutyryl bromide is 0.05-0.2g:30-50ml:1-5ml:4-8ml;
the polar solvent A is one of N, N-dimethylformamide, N, N-dimethylacetamide, toluene, xylene, dichloroethane and dioxane; the basic compound is one of triethylamine, diphenyl phosphine, tributylphosphine and diethylenetriamine.
3. The method for preparing a photo-thermal convertible super hydrophobic ice preventing film according to claim 1, wherein in step 2, the coating thickness of the polydimethylsiloxane prepolymer is 50-500 μm every 1625mm 2 The addition amount of the brominated carbon nanotubes is 50-80mg on the quartz plate.
4. The method for preparing a light-heat convertible super hydrophobic ice preventing film according to claim 1, wherein in the step 2, the curing treatment is performed at 70-100 ℃ for 0.5-4 hours.
5. The preparation method of the photothermal conversion superhydrophobic ice-preventing film according to claim 1, wherein in the step 2, a polar solution B, a nitrogen-containing compound and a perfluoroalkyl ethyl methacrylate compound are mixed to obtain a reaction solution for standby;
and (3) putting the polydimethylsiloxane film on a glass plate horizontally, adding a reaction solution on the surface of the glass plate, then covering a copper plate, standing for reaction for 30min-2h, washing the modified polydimethylsiloxane film, and drying at room temperature to obtain the super-hydrophobic ice-preventing film.
6. The method for preparing a photothermal conversion superhydrophobic ice-preventing film according to claim 1, wherein in step 2, the volume ratio of the polar solution, the perfluoroalkyl ethyl methacrylate compound and the nitrogen-containing compound is 1:0.05-0.5:0.01-0.04;
the perfluoroalkyl ethyl methacrylate compound is CH 2 C(CH 3 )COO-(CH 2 ) 2 -(CF 2 ) n CF 3 Wherein n is a natural number from 3 to 10; the polar solution B is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, dioxane and N-methylpyrrolidone; the nitrogen-containing compound is one of pentamethyldiethylenetriamine, pyridine and 2, 2-bipyridine.
7. According to claimThe method for preparing a light-heat convertible super-hydrophobic ice-preventing film according to claim 1, wherein in step 2, the distance between the copper plate and the brominated polydimethylsiloxane film is 0.2-1mm, every 1625mm 2 The amount of the reaction solution added to the brominated polydimethylsiloxane film was 10 to 15. Mu.L.
8. A photothermal conversion superhydrophobic ice-preventing film prepared by the preparation method of any one of claims 1-7.
9. The application of the light-heat convertible super-hydrophobic ice-preventing film in an airplane, a power transmission line and a wind power blade.
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CN103819995A (en) * 2014-01-20 2014-05-28 浙江大学 Nano-composite superhydrophobic icing-proof coating material and preparation method thereof

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