CN115232507B - Super-hydrophobic coating material with photo-thermal and sound absorption functions and preparation method thereof - Google Patents

Super-hydrophobic coating material with photo-thermal and sound absorption functions and preparation method thereof Download PDF

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CN115232507B
CN115232507B CN202210893782.0A CN202210893782A CN115232507B CN 115232507 B CN115232507 B CN 115232507B CN 202210893782 A CN202210893782 A CN 202210893782A CN 115232507 B CN115232507 B CN 115232507B
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thermal
hydrophobic
coating material
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CN115232507A (en
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施铭德
段辉
周春爱
万义辉
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Hubei Tieshen New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Abstract

The invention discloses a super-hydrophobic coating material with photo-thermal and sound absorption functions and a preparation method thereof, wherein the method comprises the following steps: dissolving red phosphorus and iodine in absolute ethyl alcohol, adding carbon nano tubes, and performing ultrasonic treatment to obtain a carbon nano tube mixed solution; adding tetraethoxysilane into the carbon nano tube mixed solution at the temperature of 2-5 ℃, adding a silane coupling agent after reaction, and continuing the reaction to obtain a hydrophobic photo-thermal composite material; and heating to room temperature, adding the IPN polymer into the hydrophobic photo-thermal composite material, and stirring for reaction to obtain the super-hydrophobic coating material with the photo-thermal and sound absorption functions. On the basis of keeping excellent surface hydrophobic property, on one hand, the photo-thermal conversion efficiency of the super-hydrophobic coating material is remarkably improved by adopting the carbon nano tube to load red phosphorus and iodine; on the other hand, P/I by IPN Polymer pairs 2 The @ CNTS carries out the cladding, gives super hydrophobic coating material acoustic-thermal conversion function, makes it can utilize environmental sound further to promote surface temperature, has greatly promoted anti-icing and deicing function.

Description

Super-hydrophobic coating material with photo-thermal and sound absorption functions and preparation method thereof
Technical Field
The invention relates to the field of super-hydrophobic coating materials, in particular to a super-hydrophobic coating material with photo-thermal and sound absorption functions and a preparation method thereof.
Background
The super-hydrophobic surface mainly comprises a micro-nano structure and a low surface energy substance, and the contact area of water drops on the super-hydrophobic surface is very small, so that the phenomena of chlorination, corrosion, frost, current conduction and the like of the surface can be effectively inhibited, and the super-hydrophobic surface has wide application scenes. For example, in a scene that water drops drop, because the water drops cannot stably stay on a super-hydrophobic surface, when the inclination angle is larger than 5 degrees, the water drops naturally roll off without adhesion, and meanwhile, dust and dirt on the surface can be taken away, so that the surface has a self-cleaning function; when the super-hydrophobic surface is applied to the wind power generation blade, the ice coating amount can be reduced, the energy consumption is reduced, and the safety coefficient is improved; the super-hydrophobic surface is applied to the ship, so that the resistance of the ship in the running process can be reduced, and the corrosion resistance of the ship can be improved.
The existing super-hydrophobic coating mainly utilizes the super-hydrophobicity of the surface to realize the effects of delaying the icing of the surface and accelerating the falling of melted water drops, and the temperature of the surface of the coating does not change obviously, so that the coating still can ice when facing the extremely low temperature condition and cannot play roles in anti-icing and deicing. In addition, some novel photothermal effect and super-hydrophobic and super-hydrophilic anti-icing and deicing functional coatings can not be remarkably exerted under the severe conditions of ice and snow climate and wind and rain, so that better anti-icing and deicing effects are difficult to exert. Therefore, it is necessary to provide a new design of super-hydrophobic coating to solve the problems in the prior art.
Disclosure of Invention
The invention aims to provide a super-hydrophobic coating material with photo-thermal and sound absorption functions and a preparation method thereof, and aims to solve the problem that the anti-icing and deicing effects of a super-hydrophobic coating in the prior art are poor.
In order to solve the technical problems, a first solution provided by the invention is a preparation method of a super-hydrophobic coating material with photo-thermal and sound absorption functions, which specifically comprises the following steps: s1, dissolving red phosphorus and iodine in absolute ethyl alcohol, adding a carbon nano tube, and performing ultrasonic treatment to obtain a carbon nano tube mixed solution; s2, adding tetraethoxysilane into the carbon nano tube mixed solution at the temperature of 2-5 ℃, adding a silane coupling agent after reacting for 1-1.5 h, and continuing to react for 3-4 h to obtain the hydrophobic photo-thermal composite material P/I 2 @ CNTS; s3, heating to room temperature, and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 And adding IPN polymer into the @ CNTS, and stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
Preferably, the mass ratio of the red phosphorus to the iodine to the carbon nanotubes is 0.1: (0.8-1.2): (9 to 12).
Further preferably, the mass ratio of red phosphorus, iodine and carbon nanotubes is 0.1:1:10.
preferably, the ratio of the carbon nano tube to the tetraethoxysilane to the silane coupling agent is 20g: (2.8-3.2) mL: (6-8) mL.
Further preferably, the ratio of the carbon nano tube, the ethyl orthosilicate and the silane coupling agent is 20g:3mL of: 7mL.
Preferably, the silane coupling agent is any one of KH550, KH560, KH570 and KH 590.
Preferably, the mass ratio of the carbon nanotubes to the IPN polymer is 1: (0.85-1.15).
Further preferably, the mass ratio of the carbon nanotubes to the IPN polymer is 1:1.
preferably, the IPN polymer is any one of polysiloxane/acrylic resin interpenetrating network polymer, polyurethane interpenetrating network polymer, modified epoxy resin/isocyanate interpenetrating network polymer.
In order to solve the above technical problems, a second solution provided by the present invention is a superhydrophobic coating material having photo-thermal and sound absorption functions, which is prepared by the method for preparing the superhydrophobic coating material having photo-thermal and sound absorption functions according to the first solution, and is applied to a plastic or metal surface.
The invention has the beneficial effects that: the invention provides a super-hydrophobic coating material with photo-thermal and sound absorption functions and a preparation method thereof, which are different from the conditions of the prior art, on the basis of keeping excellent surface hydrophobic performance, on one hand, the photo-thermal conversion efficiency of the super-hydrophobic coating material is obviously improved by adopting carbon nano tubes to load red phosphorus and iodine; on the other hand, P/I by IPN Polymer pairs 2 The @ CNTS is coated, so that the super-hydrophobic coating material has an acoustic-thermal conversion function, the surface temperature can be further increased by using environmental sound, the super-hydrophobic coating material is not frozen in an extremely cold environment at-50 ℃, and the anti-icing and deicing functions of the super-hydrophobic coating material under the extremely cold condition are greatly improved.
Drawings
Fig. 1 is a schematic view of an embodiment of the superhydrophobic coating material having photothermal and sound absorption functions in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
For the first solution provided by the invention, the preparation method of the super-hydrophobic coating material with photo-thermal and sound absorption functions specifically comprises the following steps:
s1, dissolving red phosphorus and iodine in absolute ethyl alcohol, adding carbon nano tubes (CNTS for short) and then carrying out ultrasonic treatment to obtain a carbon nano tube mixed solution. In this step, the mass ratio of red phosphorus, iodine and carbon nanotubes is preferably 0.1: (0.8-1.2): (9 to 12), and more preferably, the mass ratio of red phosphorus, iodine and carbon nanotubes is 0.1:1:10.
s2, adding tetraethoxysilane into the carbon nano tube mixed solution at the temperature of 2-5 ℃, reacting for 1-1.5 h, adding a silane coupling agent KH550, and continuously reacting for 3-4 h to obtain the hydrophobic photo-thermal composite material P/I 2 @ CNTS. In the step, the proportion of the carbon nano tube, the ethyl orthosilicate and the silane coupling agent is 20g: (2.8-3.2) mL: (6 to 8) mL, and more preferably, the ratio of the carbon nanotubes, tetraethoxysilane and silane coupling agent is 20g:3mL of: 7mL.
S3, heating to room temperature to form hydrophobic photo-thermal composite material P/I 2 And (3) adding an IPN polymer into the @ CNTS, and stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions. In this step, the IPN polymer is any one of a polysiloxane/acrylic resin interpenetrating network polymer, a polyurethane interpenetrating network polymer, and a modified epoxy resin/isocyanate interpenetrating network polymer, and in other embodiments, a similar interpenetrating network polymer material may be selected as this component according to actual conditions, which is not limited herein; the mass ratio of the carbon nano tube to the IPN polymer is 1: (0.85 to 1.15), and more preferably, the mass ratio of the carbon nanotubes to the IPN polymer is 1:1.
for the second solution provided by the present invention, the super-hydrophobic coating material having photothermal and sound absorption functions is prepared by the method for preparing the super-hydrophobic coating material having photothermal and sound absorption functions of the first solution. As shown in fig. 1, on the basis of maintaining good superhydrophobicity, the superhydrophobic coating material with photo-thermal and sound absorption functions of the invention endows the material with an enhancement effect on light by introducing red phosphorus and iodine, improves the photo-thermal efficiency, and further improves the anti-icing and deicing functions of the material by utilizing the photo-thermal conversion effect; the coating IPN also endows the material with a sound-heat conversion function, makes full use of wind and rain noise in severe weather, converts the noise into heat energy, and combines the heat energy with the super-hydrophobic surface of the coating, thereby further improving the anti-icing and deicing functions of the material; the good super-hydrophobicity of the material is kept, and meanwhile, the anti-icing and deicing functions of the material are obviously enhanced by enhancing the photo-thermal efficiency and the acoustic-thermal efficiency of the material, so that the material can be applied to more severe and lower-temperature environmental conditions. When the super-hydrophobic coating material with the photo-thermal and sound absorption functions is applied, the super-hydrophobic coating material is coated on the surface of plastic or metal, and the coating is coated on the surface of the plastic or metal by using a common coating process such as spraying, brushing or rolling coating. According to the experimental invention, after the material is coated, the surface temperature of the coating is 8 ℃ under the atmospheric condition of-50 ℃, and the surface is not frozen; after the surface is forcedly frozen, the ice is placed in an environment at 25 ℃ and is melted and rolled off within 300 seconds; namely, the material can keep excellent anti-icing and deicing functions in a lower temperature environment after being coated, and is easier to melt after being frozen.
Specifically, the preparation process and mechanism of the super-hydrophobic coating material with photothermal and sound absorption functions are explained in detail:
firstly, in the step S1, red phosphorus with photo-enhancement effect and iodine with photo-thermal characteristic are compounded in a cosolvent absolute ethyl alcohol and loaded in a carbon nano-tube with certain photo-thermal and sound absorption functions to obtain a photo-thermal composite material P/I with photo-enhancement effect 2 @ CNTS. Wherein P, I 2 The relative proportions of CNTS need to be strictly controlled if P and I 2 Compared with the CNTS, the CNTS pores are excessively filled, so that the hydrophobic effect of the subsequent photo-thermal composite material is influenced; if P and I 2 If the amount of CNTS is small, the light enhancement effect of P will not be obtainedFoot, while I 2 The amount of heat converted by the photothermal effect is also low.
Next, in step S2, P/I is added 2 The alkylation treatment of @ CNTS is carried out to obtain the hydrophobic photo-thermal composite material P/I 2 @ CNTS. The reason why the silane coupling agent is any one of KH550, KH560, KH570 and KH590 is that the amino group provided by KH550 can be combined on the surface of the carbon nanotube in the alkylation reaction process, thereby further improving the surface hydrophobic effect. Wherein, too much or too little relative proportion of the silane coupling agent can reduce the P/I of the hydrophobic photo-thermal composite material 2 @ CNTS, the relative proportion of silane coupling agent to CNTS also needs to be strictly controlled.
Finally, in the step S3, interpenetrating Polymer Network (IPN) is adopted as cross-linking resin to obtain the super-hydrophobic coating material P/I with photo-thermal and sound absorption functions 2 @ CNTS @ IPN; due to P and I 2 Loaded on the inner wall of carbon nanotube, cross-linked with high-molecular polymer, and cross-linked to form a network structure 2 The coating is carried out on the @ CNTS, so that on one hand, the CNTS and IPN composite structure can endow the prepared super-hydrophobic coating material with an acoustic-thermal conversion function, and the surface temperature can be further improved by utilizing environmental sound; on the other hand, can define P and I 2 Range of motion, not to P and I 2 Component losses during photothermal and photothermal conversion, respectively, i.e. the coating structure of the IPN enables P and I 2 The photoacoustic thermal vibration can be stably exerted for a long time. The relative proportions of IPN and CNTS, among other things, will also have an effect on the effectiveness of the final coating product. If the proportion of the IPN relative to the CNTS is too low, the first one can reduce the acoustic-thermal conversion efficiency brought by the composite structure of the CNTS and the IPN; second, it affects IPN and P/I 2 The mechanical property of the coated coating of the @ CNTS reduces the mechanical strength of the coated coating; third, it will affect IPN and P/I 2 The coating effect of @ CNTS makes the IPN coating structure pair P and I 2 So that P and I are reduced 2 The material is easier to dissipate in the motion process of the photothermal conversion, and the stability of the material and the photothermal conversion efficiency are further reduced. If the proportion of IPN to CNTS is too high and the crosslinking network density is too high, theWill make P/I 2 The hydrophobic effect of @ CNTS is reduced; therefore, in the actual preparation process, the ratio of IPN to CNTS also needs to be strictly controlled.
The effects of the above-described superhydrophobic coating materials are characterized and analyzed by specific examples and comparative examples below, wherein the following examples and comparative examples both select a polysiloxane/acrylic resin interpenetrating network polymer as the IPN polymer.
Example 1
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of tetraethoxysilane into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
Example 2
The preparation procedure of this example is as follows:
(1) Dissolving 0.1g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the amount of red phosphorus added in step (1) was changed to 0.1g only in this example, and the other preparation processes were kept the same as in example 1.
Example 3
The preparation procedure of this example is as follows:
(1) Dissolving 0.15g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the red phosphorus addition amount in step (1) was changed to 0.15g only in this example, and the other preparation procedures were kept the same as in example 1.
Example 4
The preparation procedure of this example is as follows:
(1) Dissolving 0.25g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the red phosphorus addition amount in step (1) was changed to 0.25g only in this example, and the other preparation procedures were kept the same as in example 1.
Example 5
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 1.2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the iodine addition amount in step (1) was changed to 1.2g only in this example, and the other preparation procedures were kept the same as in example 1.
Example 6
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 1.8g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the iodine addition amount in step (1) was only changed to 1.8g in this example, and the other preparation processes were kept the same as in example 1.
Example 7
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2.8g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 7mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1:1, stirring and reacting to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the iodine addition amount in step (1) was only changed to 2.8g in this example, and the other preparation processes were kept the same as in example 1.
Example 8
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 5mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, in this example, the amount of the silane coupling agent KH550 added in step (2) was changed to 5mL, and the other preparation procedures were consistent with those of example 1.
Example 9
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 deg.C, adding into the carbon nanotube mixture3mL of tetraethoxysilane, reacting for 1 hour, adding 8mL of silane coupling agent KH550, and continuing to react for 3 hours to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, in this example, the amount of the silane coupling agent KH550 added in step (2) was changed to 8mL, and the other preparation procedures were consistent with those of example 1.
Example 10
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nanotube mixed solution, reacting for 1h, adding 10mL of silane coupling agent KH550, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, in this example, the amount of the silane coupling agent KH550 added in step (2) was changed to 10mL, and the other preparation procedures were consistent with those of example 1.
Example 11
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of tetraethoxysilane into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 15g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the amount of IPN polymer added in step (3) was only changed to 15g in this example, and the other preparation procedures were kept the same as in example 1.
Example 12
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 22g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the IPN polymer addition in step (3) was only changed to 22g in this example, and the other preparation procedures were consistent with example 1.
Example 13
The preparation procedure of this example is as follows:
(1) Dissolving 0.2g of red phosphorus and 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 Adding @ CNTS30g of IPN polymer, wherein the mass ratio of the carbon nano tube to the IPN polymer is 1:1, stirring and reacting to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the preparation procedure of example 1, the IPN polymer addition in step (3) was changed to 30g only in this example, and the other preparation procedures were kept the same as in example 1.
Comparative example 1
(1) Dissolving 0.2g of red phosphorus in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tubes, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and converting the temperature to the hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
Compared with the preparation steps of the example 1, only red phosphorus is added and iodine is not added in the comparative example, the prepared product is P @ CNTS @ IPN, and other preparation processes are consistent with those of the example 1.
Comparative example 2
(1) Dissolving 2g of iodine in 400mL of absolute ethyl alcohol, adding 20g of carbon nano tube, and carrying out ultrasonic treatment for 30min to obtain a carbon nano tube mixed solution.
(2) Cooling to 3 ℃, adding 3mL of ethyl orthosilicate into the carbon nano tube mixed solution, reacting for 1h, adding 7mL of silane coupling agent, and continuing to react for 3h to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS。
(3) Heating to room temperature (25 ℃), and heating to hydrophobic photo-thermal composite material P/I 2 20g of IPN polymer is added into the @ CNTS, and the mass ratio of the carbon nano tube to the IPN polymer is 1: and 1, stirring for reaction to obtain the super-hydrophobic coating material with photo-thermal and sound absorption functions.
In contrast to the procedure of example 1, in this comparative example only iodine and no red phosphorus was added, resulting in a product I 2 @ CNTS @ IPN, other preparation processes were kept consistent with example 1.
Statistics of the raw materials for preparing the superhydrophobic coating materials in examples 1-13 and comparative examples 1-2 are shown in table 1.
TABLE 1
Red phosphorus/g Iodine/g Carbon nanotube/g Silane coupling agent/mL IPN/g
Example 1 0.2 2 20 7 20
Example 2 0.1 2 20 7 20
Example 3 0.15 2 20 7 20
Example 4 0.25 2 20 7 20
Example 5 0.2 1.2 20 7 20
Example 6 0.2 1.8 20 7 20
Example 7 0.2 2.8 20 7 20
Example 8 0.2 2 20 5 20
Example 9 0.2 2 20 8 20
Example 10 0.2 2 20 10 20
Example 11 0.2 2 20 7 15
Example 12 0.2 2 20 7 22
Example 13 0.2 2 20 7 30
Comparative example 1 0.2 - 20 7 20
Comparative example 2 - 2 20 7 20
Experiment 1
Coating the super-hydrophobic coating materials prepared in the above examples 1-13 and comparative examples 1-2 on the surface of a plastic plate made of the same material, and measuring the contact angle of each sample after dripping water at room temperature (25 ℃); and then drying surface water drops, placing all samples under the atmospheric condition of-50 ℃, and performing test statistics on the surface temperature and the icing condition of each sample, wherein the statistical result is shown in table 2, and the temperature rise represents the difference between the surface temperature of each sample and the ambient temperature.
TABLE 2
Figure BDA0003768591270000131
Based on the test data of examples 1 to 4 in table 2, it can be seen that when the amount of red phosphorus is small, the heat conversion efficiency is insufficient, and the surface is still frozen; with the increase of the added amount of red phosphorus, the temperature rise amount of the surface of the sample is in an increasing trend, namely the photothermal conversion efficiency of the coating on the surface of the sample is in an increasing trend, but after the added amount of red phosphorus exceeds a certain amount, the temperature rise amount gradually tends to be stable, so when the ratio of red phosphorus to carbon nanotubes is 0.1 (example 1). In contrast, in the test data of comparative examples 1 and 2, the temperature of two samples is far less increased than that of other examples because red phosphorus or iodine is not introduced, so that the anti-icing and deicing effects are difficult to be shown in an extremely cold environment.
Based on the test data of the examples 1 and 5 to 7 in the table 2, it can be seen that when the iodine addition amount is small, the heat conversion efficiency is insufficient, and the surface still freezes; with the increase of the addition of iodine, the temperature rise of the surface of the sample is in an increasing trend, and after the addition of iodine exceeds a certain amount, the increment of the temperature rise gradually slows down, but the microporous structure of the carbon nanotube is excessively filled, so that the contact angle is reduced, and the hydrophobic property of the surface of the sample is further realized; from this, it is understood that if it is necessary to ensure both of the hydrophobicity and the photothermal conversion efficiency to have a good effect, the amount of iodine to be added needs to be strictly controlled.
Based on the test data of examples 1, 8-10 in table 2, it can be seen that the relative ratio of the silane coupling agents affects the contact angle of the sample, and if too much or too little of the silane coupling agents decreases the hydrophobicity of the sample surface, the silane coupling agents need to be kept in a proper ratio to ensure better surface hydrophobicity.
Based on the test data of examples 1, 11 to 13 in table 2, it can be seen that the temperature rising amount tends to increase gradually with the increase of the relative proportion of the IPN, which indicates that the acoustic-thermal conversion efficiency gradually increases with the increase of the relative proportion of the IPN, and thus more excellent anti-icing and de-icing functions can be exhibited under the extremely cold condition. However, when the relative proportion of IPN is too high in example 13, the contact angle of the surface of the sample is remarkably reduced, which indicates that the relative proportion of IPN is too high to be beneficial to maintaining the hydrophobicity of the material; in example 11, when the IPN relative ratio is low, the contact angle and the temperature increase amount of the sample surface are reduced, because the cnt and IPN composite structure has reduced acoustic-thermal conversion efficiency and reduced coating effect, resulting in reduced surface hydrophobicity and thermal conversion performance. The material needs to be ensured to have both hydrophobicity and low-temperature anti-icing effect, and the IPN ratio needs to be controlled so as not to be too high or too low.
Experiment 2
The super-hydrophobic coating materials prepared in the above example 1 and the comparative examples 1 to 2 are coated on the surfaces of plastic boards of the same material, and the plastic boards are cooled extremelyForced freezing was performed on the surface of each sample, and then the three groups of samples were placed at room temperature (25 ℃) to test the total melting time of each sample, and the test results are shown in table 3. It can be seen that the samples of example 1 have a much lower melt length than comparative examples 1 and 2, further illustrating the P/I 2 The @ CNTS @ IPN material can remarkably improve the photo-thermal conversion efficiency, and the melting time is remarkably shortened.
TABLE 3
Complete melting time/min
Example 1 5
Comparative example 1 15
Comparative example 2 14
The invention provides the super-hydrophobic coating material with photo-thermal and sound absorption functions and the preparation method thereof, which are different from the prior art, on the basis of keeping excellent surface hydrophobic property, on one hand, the photo-thermal conversion efficiency of the super-hydrophobic coating material is obviously improved by adopting the carbon nano tubes to load red phosphorus and iodine; on the other hand by the IPN polymer pair P/I 2 The @ CNTS is coated to endow the super-hydrophobic coating material with an acousto-thermal conversion function, so that the surface temperature can be further increased by utilizing environmental sound, the super-hydrophobic coating material is not frozen in an extremely cold environment at-50 ℃, and the anti-icing and anti-icing effects of the super-hydrophobic coating material under the extremely cold condition are greatly improvedAnd (5) deicing function.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (6)

1. A preparation method of a super-hydrophobic coating material with photo-thermal and sound absorption functions is characterized by comprising the following steps:
s1, dissolving red phosphorus and iodine in absolute ethyl alcohol, adding a carbon nano tube, and performing ultrasonic treatment to obtain a carbon nano tube mixed solution;
s2, adding tetraethoxysilane into the carbon nano tube mixed solution at 2~5 ℃, reacting for 1 to 1.5 hours, adding a silane coupling agent, and continuing to react for 3 to 4 hours to obtain the hydrophobic photo-thermal composite material P/I 2 @CNTS；
S3, heating to room temperature, adding an IPN polymer into the hydrophobic photo-thermal composite material, and stirring for reaction to obtain a super-hydrophobic coating material with photo-thermal and sound absorption functions;
the mass ratio of the red phosphorus to the iodine to the carbon nano tube is 0.1: (0.8 to 1.2): (9 to 12);
the mass ratio of the carbon nano tube to the IPN polymer is 1: (0.85 to 1.15);
the proportion of the carbon nano tube, the ethyl orthosilicate and the silane coupling agent is 20g: (2.8 to 3.2) mL: (6~8) mL;
the IPN polymer is any one of polysiloxane/acrylic resin interpenetrating network polymer, polyurethane interpenetrating network polymer and modified epoxy resin/isocyanate interpenetrating network polymer.
2. The method for preparing the super-hydrophobic coating material with photothermal and sound absorption functions as claimed in claim 1, wherein the mass ratio of the red phosphorus, the iodine and the carbon nanotubes is 0.1:1:10.
3. the method for preparing the super-hydrophobic coating material with photothermal and sound absorption functions as claimed in claim 1, wherein the ratio of the carbon nanotubes, the tetraethoxysilane and the silane coupling agent is 20g:3mL of: 7mL.
4. The method for preparing the super-hydrophobic coating material with photothermal and sound absorption functions as claimed in claim 1, wherein the silane coupling agent is any one of KH550, KH560, KH570 and KH 590.
5. The method for preparing the superhydrophobic coating material having the photothermal and sound absorption functions according to claim 1, wherein the mass ratio of the carbon nanotubes to the IPN polymer is 1:1.
6. the super-hydrophobic coating material with photo-thermal and sound absorption functions is prepared by the preparation method of the super-hydrophobic coating material with photo-thermal and sound absorption functions disclosed by any one of claims 1~5, and is applied to a plastic or metal surface.
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