CN114854243A - Preparation method and application of modified silicon dioxide for environment-friendly water-repellent oil-repellent coating - Google Patents
Preparation method and application of modified silicon dioxide for environment-friendly water-repellent oil-repellent coating Download PDFInfo
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Abstract
The invention relates to the field of water and oil repellent coatings, and discloses a preparation method and application of modified silicon dioxide for an environment-friendly water and oil repellent coating. The preparation method of the modified silicon dioxide comprises the following steps: (1) uniformly mixing cetyl trimethyl ammonium bromide, urea and water to obtain a water phase; mixing tetraethoxysilane and an oil phase solvent uniformly to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide; (2) and (2) grafting a silane coupling agent to the surface of the porous nano-silica obtained in the step (1) to obtain the environment-friendly modified silica for the water-repellent and oil-repellent coating. The invention adopts a special method to prepare the nano silicon dioxide, and can ensure that the surface of nano silicon dioxide particles has a porous structure, thereby improving the roughness of the surface of the coating and endowing the coating with better water and oil repellency.
Description
Technical Field
The invention relates to the field of water and oil repellent coatings, in particular to a preparation method and application of modified silicon dioxide for an environment-friendly water and oil repellent coating.
Background
The super-hydrophobic surface shows that the static water Contact Angle (CA) is more than 150 degrees and the contact lag angle of water is extremely low, and has higher potential application value in the aspects of self-cleaning, oil-water separation, ice resistance, antibiosis, corrosion resistance and the like. It is reported that when the surface is rich in-CF 3 When the group is a fluorinated compound, the surface tension can be reduced to 6.7mJ/m 2 This is considered to be the lowest surface free energy of all solids. In recent years, extensive research has been conducted to develop superhydrophobic and oleophobic surfaces with different prepolymers, such as Fluorinated Alkyl Silanes (FAS).
Long fluorocarbon chain (C) n F 2n+1 N is more than or equal to 8) the oil-proof finishing agent can reduce the surface tension of the fabric to 10-15 mN/m, has excellent oil-proof effect, and the finished fabric has good hand feeling and excellent air permeability and moisture permeability. However, long fluorocarbon chains are not degradable, easily release perfluorooctyl sulfonyl compounds (PFOS) and perfluorooctyl compounds (PFOA), are harmful to human health and the environment, and require zero emission at present. Therefore, research and development of alternative finishing agents or alternative finishing methods for PFOS/PFOA have been receiving attention. Using short fluorocarbon chains or polymers (e.g. perfluorobutyl-like C) 4 F. Perfluorohexans C 6 F) The substitution of long fluorocarbon chain compounds is one of the main research directions. However, in comparison with PFOS/PFOA-containing products, C 4 F and C 6 F has poor oil repellency; and, C 6 F is superior to C in oil repellency 4 F, but the research reports indicate that the performance of C is better 6 The class F substitute is still not safe because of C 6 F and C 8 F is as difficult to decompose as well as for someToxicity ratio of aquatic organisms C 8 F is 3-5 times larger. Research and development of a waterproof and oilproof finishing agent which is environment-friendly, pollution-free and excellent in water and oil repellency is urgent.
The silicon dioxide has no pollution to the environment, and the rough structure on the microscopic scale is constructed on the surface of the material, so that the surface cannot be completely soaked when liquid drops are contacted with the surface, air is reserved in the microstructure to form air pockets, and the liquid drops can easily slide off from the surface due to the air pockets, thereby improving the water and oil repellent performance of the surface of the material. Patent CN201410693047.0 discloses a transparent super-hydrophobic coating material, which comprises fumed silica nanoparticle dispersion liquid and hydrophobic treatment agent, wherein the fumed silica nanoparticle dispersion liquid is composed of fumed silica nanoparticles and solvent; the hydrophobic treatment agent is an alkyl silane coupling agent, a fluorine-containing methacrylate polymer, a fluorine-containing acrylate polymer, an organic silicon compound or a fluorine-containing organic silicon compound. According to the patent, the fumed silica nanoparticles are coated on the surface of the substrate through a wiping method, a porous microstructure can be formed on the surface of the substrate after a solvent is quickly volatilized, but the fumed silica nanoparticles do not have a high-roughness surface structure, so that the effect of improving the water and oil repellency of the surface of the substrate is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating. In the preparation process of the modified silicon dioxide, the nano silicon dioxide is prepared by adopting a special method, so that the surface of nano silicon dioxide particles has a porous structure, and the modified silicon dioxide is endowed with better water and oil repellency.
The specific technical scheme of the invention is as follows:
the invention provides a preparation method of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating, which comprises the following steps:
(1) uniformly mixing hexadecyl trimethyl ammonium bromide, urea and water to obtain a water phase; mixing tetraethoxysilane and an oil phase solvent uniformly to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide;
(2) grafting a silane coupling agent to the surface of the porous nano-silica obtained in the step (1), wherein the silane coupling agent comprises SiCH-containing 3 The silane coupling agent and the silane coupling agent containing perfluorobutyl to obtain the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating.
In the step (1), the nano silicon dioxide is prepared by a special method, so that the surface of nano silicon dioxide particles has a porous structure, and higher surface roughness is endowed to the nano silicon dioxide particles, and the specific mechanism is as follows: after the water phase and the oil phase in the step (1) of the invention are mixed, a water-in-oil emulsion can be formed, the formation of porous nano-silica mainly occurs on a water-in-oil interface, due to the internal concentration difference of reverse micelles, Tetraethoxysilane (TEOS) molecules are driven to be close to the tail part of Cetyl Trimethyl Ammonium Bromide (CTAB) in the oil phase, and when the TEOS is close to the boundary and contacts with water, hydrolysis reaction immediately occurs to generate silicate molecules. CTAB acts as a template, and negatively charged silicate molecules will penetrate into the interior of the reverse micelle and aggregate in the free radial and restricted tangential directions. Condensation of the final self-assembled silicate to SiO 2 The material crystallizes in the reverse micelles, forming porous nanosilica particles. Through the method, the dendritic, coral-shaped, flower-shaped and raspberry-shaped nano silicon dioxide can be obtained, and a large number of pores are distributed on the surface of the nano silicon dioxide.
In step (2), compared with perfluorooctyl (C) 8 F) Or perfluorohexyl (C) 6 F) In particular, perfluorobutyl (C) 4 F) Has short fluorocarbon chains, is easy to degrade, has no harm to human bodies and environment, and has relatively poor oil repellency. In order to ensure safe and environment-friendly property and simultaneously endow the coating with better oil repellency, the invention uses SiCH 3 The silane coupling agent is matched with a silane coupling agent containing perfluorobutyl for use, and the orientation and the arrangement of the perfluorobutyl can be limited by utilizing the chemical incompatibility between methyl and the perfluorobutyl and the mutual exclusion of different groups on the special surface of the porous silica, thereby being beneficial to-CF 3 Stacking on the outermost layer, and the chain length of methyl group is short and notThe outermost perfluoro group is masked. In this way, the methyl group and the perfluorobutyl group can generate the synergistic action of '1 +1 > 2' to endow the coating with lower surface energy, thereby leading the coating to have better oil-repellent performance. In addition, containing SiCH 3 The silane coupling agent and the silane coupling agent containing perfluorobutyl are both easy to degrade, do no harm to human health, and are safe and environment-friendly to the environment.
When the modified silica is used for the water-repellent and oil-repellent coating, the porous micro-nano structure can be endowed to the coating by utilizing the pores among the modified silica particles, and simultaneously, the roughness of the micro-nano structure can be further improved by utilizing a large number of pores on the surface of each modified silica particle. By utilizing the micro-nano structure, the liquid/solid interface buffering can be reduced by establishing balanced air, the adhesive force of oil and water on the surface of the substrate is reduced, and the water and oil repellency of the surface of the substrate is improved. When the micro-nano structure is formed, the silane coupling agent grafted on the surface of the silicon dioxide particle can reduce the surface tension of the substrate, and the silane coupling agent and the micro-nano structure act synergistically to endow the substrate with better water and oil repellency.
Preferably, in the step (2), the-SiCH-containing compound 3 The mass ratio of the silane coupling agent to the silane coupling agent containing perfluorobutyl is 1: 1-2.
When containing SiCH 3 When the ratio of the amount of the silane coupling agent to the amount of the perfluorobutyl-containing silane coupling agent is too large or too small, the oil-repellent effect of the modified silica is not satisfactory, specifically: when the amount is too small, the methyl group has a weak effect on limiting the orientation and arrangement of the perfluorobutyl group, and the oil-repellent effect of the perfluorobutyl group is difficult to effectively improve, so that the oil-repellent effect of the modified silica is poor; when the amount ratio is too large, the outermost layer of-CF is caused 3 Too little will also affect the oil repellency of the modified silica.
Preferably, in the step (1), the mass ratio of the cetyl trimethyl ammonium bromide to the urea to the water is 0.5-2: 0.6-2.4: 40-60.
Preferably, in the step (1), the oil phase solvent is cyclohexane and 1-pentanol; the mass ratio of the tetraethoxysilane to the cyclohexane to the 1-pentanol is 4-5: 10-40: 1-4.
Preferably, in the step (1), the mass ratio of the water phase to the oil phase is 1-2: 1.
Preferably, in the step (1), the temperature of the hydrolytic condensation is 60-80 ℃ and the time is 12-16 h.
Preferably, the specific process of step (2) comprises the following steps: dispersing the porous nano-silica obtained in the step (1) into an organic solvent, adding a silane coupling agent into the organic solvent, adjusting the mass ratio of the porous nano-silica to the silane coupling agent to the organic solvent to be 1: 1-2: 80-100, adjusting the pH to 9-10, reacting for 5-6 h at the temperature of 60-70 ℃, and separating out a product to obtain the environment-friendly modified silica for the water-repellent oil-repellent coating.
Secondly, the invention provides modified silicon dioxide prepared by the preparation method.
Thirdly, the invention provides the application of the modified silicon dioxide in a water-repellent and oil-repellent coating.
Preferably, the method for producing the water-and oil-repellent coating includes the steps of: spraying an adhesive on the surface of the substrate, and drying to form an adhesive layer; and dispersing the modified silicon dioxide into a solvent to prepare a suspension, spraying the suspension on the surface of the adhesive layer, and drying to form the water-repellent and oil-repellent coating.
The water-repellent and oil-repellent coating is suitable for different substrate materials such as cotton, paper, glass, terylene, aluminum sheets, iron sheets and the like. When the modified silicon dioxide is sprayed on the surface of the adhesive layer, the modified silicon dioxide can spontaneously enter the adhesive layer by utilizing good interface compatibility between the modified silicon dioxide and the adhesive layer to form firm combination with the substrate, so that a water-repellent and oil-repellent surface with a micro-nano structure is formed.
Preferably, the mass ratio of the modified silicon dioxide to the solvent is 1: 80-100.
Compared with the prior art, the invention has the following advantages:
(1) the nano silicon dioxide is prepared by a special method, so that the surface of nano silicon dioxide particles has a porous structure, the roughness of the surface of the coating is improved, and the coating is endowed with better water and oil repellency;
(2) will contain SiCH 3 The silane coupling agent and the silane coupling agent containing perfluorobutyl are used in a matching way, so that the coating can be endowed with better water and oil repellency by utilizing the synergistic action between methyl and perfluorobutyl while ensuring safety and environmental protection.
Drawings
FIG. 1 is an SEM image of flower-like porous silica nanoparticles prepared in example 1;
FIG. 2 is a photograph showing different substrates in comparative example 3, on which diiodomethane, water and disperse red dye were dropped;
FIG. 3 is a schematic diagram of a superhydrophobic dynamic;
fig. 4 shows contact angles and retardation angles of the water-and oil-repellent treated substrates of example 1 and comparative examples 2 to 5 with respect to oil.
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
The structure of the prepared flower-like porous nano silicon dioxide is shown in figure 1. Through tests, the particle size of the flower-shaped porous nano silicon dioxide is 200-300 nm, and the width of the pores is 25 nm.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain a silicon dioxide dispersion liquid, adding 0.5g of nonafluorohexyltriethoxysilane and 0.5g of methyltriethoxysilane, adjusting the pH to 9, and reacting at 70 ℃ for 6 hours. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Example 2
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
1g of flower-like porous nano silicon dioxide is added into 100g of ethanol, ultrasonic dispersion is carried out to obtain silicon dioxide dispersion liquid, 0.67g of nonafluorohexyltriethoxysilane and 0.33g of methyltriethoxysilane are added into the silicon dioxide dispersion liquid, the pH value is adjusted to 9, and the reaction is carried out for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Example 3
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
1g of flower-like porous nano silicon dioxide is added into 100g of ethanol, ultrasonic dispersion is carried out to obtain silicon dioxide dispersion liquid, 0.33g of nonafluorohexyltriethoxysilane and 0.67g of methyltriethoxysilane are added into the silicon dioxide dispersion liquid, the pH value is adjusted to 9, and the reaction is carried out for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Example 4
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain a silicon dioxide dispersion liquid, adding 0.8g of nonafluorohexyltriethoxysilane and 0.2g of methyltriethoxysilane, adjusting the pH to 9, and reacting at 70 ℃ for 6 hours. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Comparative example 1
(1) Grafting silane coupling agent:
adding 1g of commercially available spherical nano-silica with the particle size of 200-300 nm into 100g of ethanol, performing ultrasonic dispersion to obtain a silica dispersion liquid, adding 0.5g of nonafluorohexyltriethoxysilane and 0.5g of methyltriethoxysilane, adjusting the pH to 9, and reacting at 70 ℃ for 6 hours. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Comparative example 2
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain silicon dioxide dispersion liquid, adding 1g of methyltriethoxysilane, adjusting the pH value to 9, and reacting at 70 ℃ for 6 h. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the binder, to obtain water-and oil-repellent treated substrates.
Diiodomethane, water and disperse red dye were dropped onto the surface of the water-and oil-repellent treated substrate, and as a result, as shown in fig. 2, none of the three droplets infiltrated the surface of the substrate.
Comparative example 3
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain silicon dioxide dispersion liquid, adding 1g of octadecyl triethoxy silane, adjusting the pH value to 9, and reacting for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the binder, to obtain water-and oil-repellent treated substrates.
Comparative example 4
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain silicon dioxide dispersion liquid, adding 1g of nonafluorohexyltriethoxysilane, adjusting the pH value to 9, and reacting at 70 ℃ for 6 h. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Comparative example 5
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain a silicon dioxide dispersion liquid, adding 0.5g of nonafluorohexyltriethoxysilane and 0.5g of octadecyltriethoxysilane, adjusting the pH to 9, and reacting at 70 ℃ for 6 hours. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare a suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Comparative example 6
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and stirred magnetically for 1h to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. The aqueous and oil phases were mixed and stirred at 80 ℃ for 16 h. Finally, centrifugal purification and drying at 65 ℃ are carried out, thus obtaining the flower-like porous nano silicon dioxide.
(2) Grafting silane coupling agent:
adding 1g of flower-like porous nano silicon dioxide into 100g of ethanol, performing ultrasonic dispersion to obtain silicon dioxide dispersion, adding 1g of heptadecafluorodecyltriethoxysilane, adjusting the pH value to 9, and reacting at 70 ℃ for 6 hours. Washing with pure water and ethanol, precipitating, centrifuging, and drying to obtain the modified silicon dioxide.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial binder (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., Ltd.) on the surfaces of different substrates (paper, cotton fabric, terylene, aluminum sheets and glass), and drying at room temperature for 30s to form a binder layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare a suspension, spraying the suspension on the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. The substrates were rubbed against each other to remove the modified silica which was not firmly bonded to the substrates by the adhesive, to obtain water-and oil-repellent treated substrates.
Test example
The water and oil repellency of the coatings in examples 1 to 4 and comparative examples 1 to 6 was tested by the following method: using a DSA100 (kruss, germany) contact angle measuring device (the measuring system of which measures the contact angle of the surface of an object based on an interface shape analysis method), the static contact angles of water and diiodomethane on the surface of a water-and oil-repellent substrate (cotton fabric), namely the water contact angle and the oil contact angle, are measured respectively. The results are shown in Table 1.
Fig. 3 is a schematic diagram showing the superhydrophobic dynamics of the substrate surface after water-and oil-repellent treatment. Fig. 4 shows the contact angle and the retardation angle of the water-and oil-repellent treated substrates of example 1 and comparative examples 2 to 5 with respect to oil.
TABLE 1 comparison of the Performance of examples 1-4 with comparative examples 1-6
As can be seen from table 1 and fig. 4:
(1) from the aspect of water repellency, the water contact angles of the examples 1 to 4 and the comparative examples 1 to 6 are larger than 145 degrees, which shows that the water repellency is better.
(2) From the viewpoint of oil-repellent effect, when nonafluorohexyltriethoxysilane and methyltriethoxysilane are used in combination (example 1), the oil-repellent effect is superior to that of other degradable silane coupling agents (comparative examples 2 to 5), and is comparable to that of heptadecafluorodecyltriethoxysilane (comparative example 6), which is difficult to degrade and highly contaminated. Moreover, under the condition that the total amount of the silane coupling agent is the same, compared with the condition that the single methyl triethoxysilane (comparative example 2) or the nonafluorohexyl triethoxysilane (comparative example 4) is adopted, the oil-repellent effect is better after the two are compounded, which shows that the nonafluorohexyl triethoxysilane and the methyl triethoxysilane can generate the synergistic effect of 1+1 > 2, because on the special surface of the porous silica, the orientation and the arrangement of the perfluorobutyl can be limited by utilizing the chemical incompatibility between the methyl and the perfluorobutyl and the mutual exclusion of different groups, and the-CF is facilitated 3 And stacking on the outermost layer. When methyltriethoxysilane was replaced with octadecyltriethoxysilane (comparative example 5), the oil-repellent effect of nonafluorohexyltriethoxysilane was rather reduced because, in the case of octadecyl side chains, on the surface of flower-like silica, although perfluorobutyl can be promoted to crystallize due to its special crystallization property, the surface having a lower surface tension, octadecyl side chains preferentially occupy the outermost layer, and the perfluoro groups would be masked.
(3) In example 1 and example 3, the mass ratio of methyltriethoxysilane to nonafluorohexyltriethoxysilane is 1: 1 and 1: 0.5, respectively, and the oil-repellent effect of example 1 is significantly better than that of example 3; in example 2 and example 4, the mass ratio of methyltriethoxysilane to nonafluorohexyltriethoxysilane was 1: 2 and 1: 4, respectively, and the oil-repellent effect of example 2 was significantly better than that of example 4. The reason why the oil-repellent effect of the modified silica is not satisfactory is that when the ratio of the amount of methyltriethoxysilane to nonafluorohexyltriethoxysilane is too large or too small, the methyl group has a weak effect of restricting the orientation and alignment of perfluorobutyl groups and is difficult to be used when the ratio is too smallSo as to effectively improve the oil-repellent effect of the perfluorobutyl, thereby causing poor oil-repellent effect of the modified silicon dioxide; when the amount ratio is too large, the outermost layer of-CF is caused 3 Too small a content also affects the oil-repellent effect of the modified silica.
(4) Compared with the commercially available spherical nano-silica (comparative example 1), the porous nano-silica prepared by the invention (example 1) can endow the coating with better water and oil repellency. The preparation method of the invention can lead the surface of the nano silicon dioxide particles to have a porous structure, thereby improving the roughness of the surface of the coating and endowing the coating with better water and oil repellency.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. A preparation method of modified silicon dioxide for an environment-friendly water-repellent oil-repellent coating is characterized by comprising the following steps:
(1) uniformly mixing hexadecyl trimethyl ammonium bromide, urea and water to obtain a water phase; mixing tetraethoxysilane and an oil phase solvent uniformly to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide;
(2) grafting a silane coupling agent to the surface of the porous nano-silica obtained in the step (1), wherein the silane coupling agent comprises SiCH-containing 3 The silane coupling agent and the silane coupling agent containing perfluorobutyl to obtain the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating.
2. The method according to claim 1, wherein in the step (2), the SiCH-containing compound is 3 The mass ratio of the silane coupling agent to the perfluorobutyl-containing silane coupling agent is 1: 1 to 2.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the cetyl trimethyl ammonium bromide to the urea to the water is 0.5-2: 0.6-2.4: 40-60.
4. The method according to claim 1, wherein in the step (1), the oil phase solvent is cyclohexane and 1-pentanol; the mass ratio of the tetraethoxysilane to the cyclohexane to the 1-pentanol is 4-5: 10-40: 1 to 4.
5. The method according to claim 1, 3 or 4, wherein in the step (1), the mass ratio of the water phase to the oil phase is 1-2: 1.
6. the method according to claim 1, 3 or 4, wherein in the step (1), the temperature of the hydrolytic condensation is 60-80 ℃ and the time is 12-16 h.
7. The preparation method according to claim 1, wherein the specific process of step (2) comprises the steps of: dispersing the porous nano-silica obtained in the step (1) into an organic solvent, and adding a silane coupling agent into the organic solvent, wherein the mass ratio of the porous nano-silica to the silane coupling agent to the organic solvent is 1: 1-2: 80-100, adjusting the pH value to 9-10, reacting at 60-70 ℃ for 5-6 h, and separating out the product to obtain the environment-friendly modified silicon dioxide for the water-repellent and oil-repellent coating.
8. Modified silica obtained by the preparation method according to claims 1 to 7.
9. Use of the modified silica according to claim 8 in a water-and oil-repellent coating.
10. The use according to claim 9, wherein the water-and oil-repellent coating is prepared by a process comprising the steps of: spraying an adhesive on the surface of the substrate, and drying to form an adhesive layer; and dispersing the modified silicon dioxide into a solvent to prepare a suspension, spraying the suspension on the surface of the adhesive layer, and drying to form the water-repellent and oil-repellent coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948515A (en) * | 2023-07-26 | 2023-10-27 | 苏州弘道新材料有限公司 | Anti-fouling coating liquid composition, preparation method and application |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080085742A (en) * | 2007-03-19 | 2008-09-24 | 다이니폰 인사츠 가부시키가이샤 | Anti-dazzling optical laminate |
| US20110195181A1 (en) * | 2008-08-11 | 2011-08-11 | Dic Corporation | Superhydrophobic powders, structure with superhydrophobic surface, and processes for producing these |
| WO2012064649A1 (en) * | 2010-11-10 | 2012-05-18 | 3M Innovative Properties Company | Optical device surface treatment process and smudge-resistant article produced thereby |
| CN103201331A (en) * | 2010-11-10 | 2013-07-10 | 3M创新有限公司 | Hydrophobic fluorinated coatings |
| JP6333454B1 (en) * | 2017-08-18 | 2018-05-30 | 株式会社フェクト | Method for forming water / oil repellent coating and water / oil repellent coating |
| JP2019014793A (en) * | 2017-07-05 | 2019-01-31 | 凸版印刷株式会社 | Water- and oil-repellent base material |
| CN110028412A (en) * | 2019-04-23 | 2019-07-19 | 南京信息工程大学 | A kind of perfluor replaces small molecule end group glycol and its preparation method and application |
| CN113136120A (en) * | 2020-01-20 | 2021-07-20 | 中国科学院化学研究所 | Transparent, water-impact-resistant and super-lyophobic coating and preparation method and application thereof |
| CN113249971A (en) * | 2021-05-06 | 2021-08-13 | 义乌市中力工贸有限公司 | Core-shell type short-chain fluorine-containing acrylate fabric water-repellent and oil-repellent finishing agent and preparation method and application thereof |
-
2022
- 2022-05-20 CN CN202210560902.5A patent/CN114854243B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080085742A (en) * | 2007-03-19 | 2008-09-24 | 다이니폰 인사츠 가부시키가이샤 | Anti-dazzling optical laminate |
| US20110195181A1 (en) * | 2008-08-11 | 2011-08-11 | Dic Corporation | Superhydrophobic powders, structure with superhydrophobic surface, and processes for producing these |
| WO2012064649A1 (en) * | 2010-11-10 | 2012-05-18 | 3M Innovative Properties Company | Optical device surface treatment process and smudge-resistant article produced thereby |
| CN103201331A (en) * | 2010-11-10 | 2013-07-10 | 3M创新有限公司 | Hydrophobic fluorinated coatings |
| JP2019014793A (en) * | 2017-07-05 | 2019-01-31 | 凸版印刷株式会社 | Water- and oil-repellent base material |
| JP6333454B1 (en) * | 2017-08-18 | 2018-05-30 | 株式会社フェクト | Method for forming water / oil repellent coating and water / oil repellent coating |
| CN110028412A (en) * | 2019-04-23 | 2019-07-19 | 南京信息工程大学 | A kind of perfluor replaces small molecule end group glycol and its preparation method and application |
| CN113136120A (en) * | 2020-01-20 | 2021-07-20 | 中国科学院化学研究所 | Transparent, water-impact-resistant and super-lyophobic coating and preparation method and application thereof |
| CN113249971A (en) * | 2021-05-06 | 2021-08-13 | 义乌市中力工贸有限公司 | Core-shell type short-chain fluorine-containing acrylate fabric water-repellent and oil-repellent finishing agent and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 朱杰;郑奎;王丽阁;王恩泽;: "超疏水涂膜的制备及其性能" * |
| 王静;孔庆刚;张龙;钱海燕;: "含氟低表面能修饰的超双疏涂层制备及其性能" * |
| 许莉丽;李晓光;倪星元;沈军;: "微结构与表面修饰对二氧化硅多孔薄膜疏水性能的影响" * |
| 马林娟;凌波;魏栖梧;周磊;: "二氧化硅改性后超疏水性质的粒径效应研究" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948515A (en) * | 2023-07-26 | 2023-10-27 | 苏州弘道新材料有限公司 | Anti-fouling coating liquid composition, preparation method and application |
| CN116948515B (en) * | 2023-07-26 | 2024-05-28 | 苏州弘道新材料有限公司 | Anti-fouling coating liquid composition, preparation method and application |
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