CN113388273A - Fluorinated silica nanoparticles and applications - Google Patents
Fluorinated silica nanoparticles and applications Download PDFInfo
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- CN113388273A CN113388273A CN202110655550.7A CN202110655550A CN113388273A CN 113388273 A CN113388273 A CN 113388273A CN 202110655550 A CN202110655550 A CN 202110655550A CN 113388273 A CN113388273 A CN 113388273A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention relates to a fluorinated silica nanoparticle and application thereof, wherein the technical scheme is that vinyl triethoxysilane, ethyl orthosilicate, alkali and a solvent are mixed, deionized water is dripped, and the mixture is stirred at room temperature for reaction for 1-24 hours to obtain vinyl silica; mixing fluorine-containing acrylate, vinyl silicon dioxide, an initiator and a solvent, heating to 70-85 ℃, stirring and reacting for 2-24h to obtain fluorinated silicon dioxide nano particles; the water contact angle of the coating prepared by copolymerizing fluorine-containing acrylate and vinyl silicon dioxide is more than 150 degrees, the rolling angle is less than 8 degrees, and the coating has good anti-icing performance; belongs to the technical field of nano material modification and application.
Description
Technical Field
The invention belongs to the technical field of nano material modification and application, and particularly relates to a preparation method and application of fluorinated silica nanoparticles.
Technical Field
Icing is a common phenomenon in daily life, but in some fields (aviation, highways, power transmission, communication and the like), icing can block normal operation of instruments and equipment, and serious accidents and even disasters are caused. Therefore, the anti-icing coating is constructed on the surface of the substrate, and the application value is great. In recent years, super-hydrophobic materials are receiving attention, and have extremely wide application prospects in industrial and agricultural production, medical biology and the like. However, the anti-icing materials reported at present have many defects and cannot meet the use requirements of products, so that the research of efficient and reliable anti-icing coatings has become a hot problem. The anti-icing coating is generally prepared by compounding organic polymer, nano particles and other inorganic coatings. Wherein the organic polymer imparts a low surface energy to the coating and the nanoparticles provide a certain roughness to the surface of the coating. The organic combination of the two makes the prepared coating have super-hydrophobic and anti-icing characteristics. However, the prepared nano particles have the problems of easy agglomeration, poor dispersibility and the like, so that the super-hydrophobic and anti-icing performances of the coating are reduced, and further popularization of the coating is influenced.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a fluorinated silica nanoparticle.
The invention also aims to provide application of the fluorinated silica nanoparticles in preparing a super-hydrophobic anti-icing material.
The purpose of the invention is realized by the following technical scheme:
a fluorinated silica nanoparticle is prepared by the following steps:
(1) mixing vinyl triethoxysilane, ethyl orthosilicate, ammonia water and ethanol, dropwise adding deionized water, and stirring at room temperature to react to obtain vinyl silicon dioxide;
(2) mixing fluorine-containing acrylate, vinyl silica nanoparticles, azobisisobutyronitrile and ethanol, and heating and stirring for reaction to obtain the fluorinated silica nanoparticles.
The raw materials in the step (1) are respectively vinyl triethoxysilane and tetraethyl orthosilicate; the alkali is ammonia water; the solvent is ethanol; the temperature of the reaction is room temperature; the reaction time is 1-24 h; the molar ratio of the vinyl triethoxysilane to the ethyl orthosilicate is 1: (1-3); the mole ratio of tetraethyl orthosilicate to alkali is 1: (0.1-0.5).
More preferably, the reaction time of the step (1) is 12 h; the molar ratio of the vinyl triethoxysilane to the ethyl orthosilicate is 1: 1; the mole ratio of tetraethyl orthosilicate to alkali is 1: 0.1.
the fluorine-containing acrylate in the step (2) is perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorodecyl ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate or 2- (perfluorodecyl) ethyl methacrylate; the initiator is azobisisobutyronitrile; the solvent is ethanol; the temperature of the reaction is 78 ℃; the reaction time is 2-24 h; the molar ratio of the fluorine-containing acrylate to the vinyl silicon dioxide is (0.3-3): 1; the molar ratio of the fluorine-containing acrylate to the azobisisobutyronitrile is 1: (0.01-0.3), and the stirring speed is 400-450 r/min.
More preferably, 18h in step (2); the molar ratio of the fluorine-containing acrylate to the vinyl silica is 1: 1; the molar ratio of the fluorine-containing acrylate to the azobisisobutyronitrile is 1: 0.01, and the stirring speed is 400 revolutions per minute.
The preparation principle of the fluorinated silica nanoparticles of the invention is as follows:
firstly, synthesizing vinyl silicon dioxide by taking vinyl triethoxysilane and ethyl orthosilicate as raw materials, ammonia water as a catalyst and ethanol as a solvent:
then, the fluorinated silica nanoparticles are prepared by taking fluorine-containing acrylate and vinyl silica nanoparticles as raw materials, taking azodiisobutyronitrile as an initiator and ethanol as a solvent.
The fluorinated silica nanoparticles are obtained by copolycondensation reaction of vinyl silica and fluorine-containing acrylate. The reaction has no side reaction, and pure target products are obtained, and the fluorinated silica nano particles account for 70-80%.
Compared with the prior art, the invention has the following advantages:
(1) the fluorinated silica nanoparticles with specific reaction functional groups are prepared based on functional derivatization of vinyl silica functional groups, and have the advantage of higher yield;
(2) the fluorinated silica nanoparticles are obtained from the vinyl silica, so that the range of the vinyl silica is widened, and the preparation method is simple in preparation process, convenient to operate and suitable for industrial production;
(3) the water contact angle of the coating prepared by copolymerizing the fluorine-containing acrylate and the vinyl silicon dioxide is more than 150 degrees, the rolling angle is less than 8 degrees, and the coating has good anti-icing performance. The coating had a 70% reduction in ice adhesion strength compared to the uncoated metallic aluminum surface; at 0 ℃, the ice coating is reduced by 60 percent; the delay time of water icing on the surface of the coating is more than 60 s.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol) and 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask to react for 12h at room temperature, the solvent is dried after the reaction is finished, and the product, namely the vinyl silica, is dried in vacuum at 50 ℃ to obtain 10.0g of white solid product.
(2) 10.0g of vinyl silica, 12.5g of perfluorohexylethyl acrylic acid (30mmol) and 50mL of ethanol are taken as solvents, 0.5g of azobisisobutyronitrile is added into a flask, the mixture reacts for 12 hours at 78 ℃, the solvent is dried in a spinning mode after the reaction is finished, and the white solid product, namely the fluorinated silica, is obtained by vacuum drying at 50 ℃.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
Example 2
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol), 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask, the mixture reacts for 12 hours at room temperature, the solvent is dried after the reaction is finished, and the mixture is dried in vacuum at 50 ℃ to obtain 13.2g of white solid product, namely vinyl silica.
(2) 10.0g of vinyl silica, 15.5g of perfluorooctyl ethyl acrylic acid (30mmol), 50mL of ethanol as a solvent and 0.5g of azobisisobutyronitrile are added into a flask, reacted at 78 ℃ for 12 hours, the solvent is dried after the reaction is finished, and vacuum drying is carried out at 50 ℃ to obtain 23.1g of white solid product, namely fluorinated silica.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
Example 3
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol), 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask, the mixture reacts for 12 hours at room temperature, the solvent is dried after the reaction is finished, and the mixture is dried in vacuum at 50 ℃ to obtain 13.2g of white solid product, namely vinyl silica.
(2) 10.0g of vinyl silica, 18.5g of perfluorodecyl ethyl acrylic acid (30mmol) and 50mL of ethanol are taken as solvents, 0.5g of azobisisobutyronitrile is added into a flask, and the mixture reacts for 12 hours at 78 ℃, after the reaction is finished, the solvents are dried in a spinning mode, and the white solid product, namely the fluorinated silica, is obtained by vacuum drying at 50 ℃.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
Example 4
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol), 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask, the mixture reacts for 12 hours at room temperature, the solvent is dried after the reaction is finished, and the mixture is dried in vacuum at 50 ℃ to obtain 13.2g of white solid product, namely vinyl silica.
(2) 10.0g of vinyl silica, 12.9g of 2- (perfluorohexyl) ethyl methacrylate (30mmol) and 50mL of ethanol are taken as a solvent, 0.5g of azobisisobutyronitrile is added into a flask, and the mixture reacts for 12 hours at 78 ℃, after the reaction is finished, the solvent is dried in a spinning mode, and vacuum drying is carried out at 50 ℃ to obtain 23.1g of white solid product, namely fluorinated silica.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
Example 5
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol), 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask, the mixture reacts for 12 hours at room temperature, the solvent is dried after the reaction is finished, and the mixture is dried in vacuum at 50 ℃ to obtain 13.2g of white solid product, namely vinyl silica.
(2) 10.0g of vinyl silica, 15.9g of 2- (perfluorooctyl) ethyl methacrylate (30mmol) and 50mL of ethanol are taken as a solvent, 0.5g of azobisisobutyronitrile is added into a flask, and the mixture reacts for 12 hours at 78 ℃, after the reaction is finished, the solvent is dried in a spinning mode, and vacuum drying is carried out at 50 ℃ to obtain 23.1g of white solid product, namely fluorinated silica.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
Example 6
(1) 5.7g of vinyltriethoxysilane (30mmol), 6.2g of tetraethyl orthosilicate (30mmol), 30mL of ethanol as a solvent and 3mL of ammonia water solution are added into a flask, the mixture reacts for 12 hours at room temperature, the solvent is dried after the reaction is finished, and the mixture is dried in vacuum at 50 ℃ to obtain 13.2g of white solid product, namely vinyl silica.
(2) 10.0g of vinyl silica, 18.9g of 2- (perfluorodecyl) ethyl methacrylate (30mmol) and 50mL of ethanol are taken as a solvent, 0.5g of azobisisobutyronitrile is added into a flask, and the mixture reacts for 12 hours at 78 ℃, after the reaction is finished, the solvent is dried in a spinning mode, and vacuum drying is carried out at 50 ℃ to obtain 23.1g of white solid product, namely fluorinated silica.
(3) 1.0g of the prepared fluorinated nano silicon dioxide is dissolved in ethanol to prepare a 30% solution. And then spraying the prepared solution on a substrate, and drying at 100 ℃ for 6 hours to obtain the anti-icing coating.
In order to prove the effect of the technical scheme provided by the application, the performances of the fluorinated nano-silica and the anti-icing coating prepared in the examples 1 to 6 are shown in table 1, and the detection methods are as follows:
1. contact angle (°) and roll angle (°) test methods: the nanoparticles prepared in examples 1 to 6 were subjected to static contact angle and rolling angle measurements using a DSA30 static contact Angle apparatus from Kruss, Germany, with a water drop volume of 2. mu.L, and each sample was measured 5 times and averaged.
2. Method for testing ice shear strength (KPa): fixing the coating sample plate on a precise temperature control cold table, injecting water into a tubular container with the inner diameter of 1cm, the height of the tubular container is 1cm, freezing the tubular container into ice at a set temperature and maintaining the frozen container for 5 hours, and introducing high-purity nitrogen into an outer cover of the device to avoid frosting the surface of the coating and further avoid influencing a test result. And then controlling a dynamometer to push the sample to fall off by clinging to the surface of the coating along the horizontal direction at a speed of 5mm/s through a moving platform, wherein the maximum thrust recorded by the dynamometer is ice adhesion force F, and then calculating according to a formula tau-F/A to obtain the ice adhesion strength.
Wherein τ is ice adhesion strength; f is the ice adhesion obtained by the test; a is the apparent contact area of the frozen sample with the coating surface.
3. The method for testing the ice coating amount comprises the following steps: at normal temperature, smooth aluminum sheets of the same size of 10cm × 10cm and aluminum sheets coated with super-hydrophobic coatings were adhered to a cold stage at normal temperature with a heat-conductive adhesive. The cold stage is connected with a low-temperature cooling circulating pump. The entire substrate-bearing cold plate was placed in a closed 20cm by 20cm plexiglas container at an angle of about 30 ° to the horizontal plane of the container. The temperature of the cooling table is set to be-20 ℃, and the temperature is maintained for 1h after the surface of the cooling table reaches-20 ℃. Then, 100mL of deionized water previously placed in a-5 ℃ freezer at a height of about 7cm from the highest point of the surface was completely poured onto the test surface within 10 seconds. The states of the whole surface from the beginning of pouring water to the end of pouring water when icing occurs are recorded by a Nikon digital camera.
4. Icing extension time test: at room temperature, the smooth aluminum sheet and the aluminum sheet coated with the super-hydrophobic coating were placed on a cold stage at-20 ℃ and maintained for 1 hour. Then, the same volume of deionized water was dropped onto the two substrates, and the time t is recorded0. The water drop starts to be shot and recorded by a digital camera from the front of the low-falling surface, and the time when the water drop starts to freeze is recorded as t1. The icing time t ═ t of the surface at-15 ℃ is then1-t0The water drop volume was 50. mu.L.
TABLE 1 fluorinated nanosilica and its anti-icing coating Properties
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. Fluorinated silica nanoparticles, characterized by being prepared by the following steps:
(1) mixing vinyl triethoxysilane, ethyl orthosilicate, alkali and a solvent, dropwise adding deionized water, and stirring at room temperature for reaction for 1-24h to obtain vinyl silicon dioxide;
wherein: the molar ratio of the vinyl triethoxysilane to the ethyl orthosilicate is 1: (1-3);
(2) mixing fluorine-containing acrylate, vinyl silicon dioxide, an initiator and a solvent, heating to 70-85 ℃, stirring and reacting for 2-24h to obtain fluorinated silicon dioxide nanoparticles;
wherein: the molar ratio of the fluorine-containing acrylate to the vinyl silicon dioxide is (0.3-3): 1.
2. the fluorinated silica nanoparticles of claim 1, wherein the base of step (1) is aqueous ammonia.
3. The fluorinated silica nanoparticles of claim 1, wherein the solvent used in step (1) or step (2) is ethanol.
4. The method of claim 1, wherein the fluoroacrylate of step (2) is one or any combination of perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorodecylacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, or 2- (perfluorodecyl) ethyl methacrylate.
5. The fluorinated silica nanoparticles of claim 1, wherein the initiator of step (2) is azobisisobutyronitrile.
6. The fluorinated silica nanoparticles of claim 1, wherein the molar ratio of the fluoroacrylate and azobisisobutyronitrile of step (2) is 1: (0.01-0.3).
7. The fluorinated silica nanoparticles of claim 1, wherein the stirring speed in steps (1) and (2) is 400 to 450 rpm.
8. The fluorinated silica nanoparticles of claim 1 for use in preparing superhydrophobic anti-icing materials.
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Cited By (1)
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