CN114874675A - Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite - Google Patents
Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite Download PDFInfo
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Abstract
The invention discloses a preparation method of a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite, which comprises the steps of firstly synthesizing a PS-co-HFA (polystyrene-co-high frequency-methyl-methacrylate) low-surface-energy binder through free radical polymerization, then carrying out phase separation on the binder to prepare a low-surface-energy PS-co-HFA micro-particle dispersion liquid, finally coating low-surface-energy modified polyaniline/attapulgite nanoparticles on the surface of the binder to construct a ' core-shell ' structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micro-particle dispersion liquid, and spraying the core-shell ' structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micro-particle dispersion liquid on the surface of a substrate to prepare the durable super-hydrophobic micro-droplet self-cleaning coating based on the polyaniline/attapulgite. The coating prepared by the invention has excellent super-hydrophobic performance and durability for micro-droplets with the volume less than 1 mu L, effectively solves the problems of easy adhesion and poor durability of the micro-droplets in the practical application of the super-hydrophobic coating, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of an ultralyophobic coating, in particular to a preparation method of a durable ultralyophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite, and belongs to the technical field of preparation of ultralyophobic coatings.
Background
Ultralyophobic coatings are special surfaces with a high contact angle (CA > 150 °) and a low rolling angle for liquids such as water, oil, etc. Due to the unique wettability, the ultralyophobic coating has wide application prospect in the fields of corrosion prevention, icing prevention, self-cleaning and the like. To date, researchers have developed a number of methods for producing ultralyophobic coatings, such as: sol-gel methods, etching methods, self-assembly methods, vapor deposition methods, and the like. Although the ultralyophobic coating has wide application prospect in various fields, the durability is poor, and the practical application of the ultralyophobic coating is severely limited.
To date, researchers have developed various methods to increase the durability of ultralyophobic coatings, such as: build up of micro "armor" to protect the nanostructures, build up of self-similar structures, introduction of binders, and the like. Among these methods, the introduction of a binder to prepare a durable ultralyophobic coating is favored by researchers because of its advantages such as easy operation and large-area preparation. In patent CN108587447B, alkyl chain silane coupling agent is firstly adopted to carry out super-hydrophobic modification on nano-silica, then the nano-silica is dispersed into alkane solvent, polydimethylsiloxane is introduced as a binder, and finally the nano-silica is repeatedly coated on the surface of a substrate for many times to successfully prepare the durable transparent super-hydrophobic coating. In patent CN112175520A, low surface energy molecules are grafted on the surfaces of nanoparticles to modify the nanoparticles with low surface energy, then room temperature curing resin is introduced to mix to prepare uniform dispersion liquid, and the uniform dispersion liquid is coated on the surface of a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic coating. The coating shows good properties of transparency, super-hydrophobicity, durability, self-cleaning and the like.
Although great efforts have been made to improve the durability of the ultralyophobic coating by introducing a binder, the binder usually embeds low surface energy nanoparticles, which makes the surface energy of the ultralyophobic coating higher, and then causes microdroplets to be in a Wenzel state on the surface of the coating, so that the ultralyophobic coating loses its functionality, thereby severely limiting its practical application. According to the invention patent CN113308151A of the team, FEVE binder microspheres are synthesized through phase separation, and then low-surface-energy nanoparticles are wrapped on the surfaces of the microspheres, so that the problem of embedding of the low-surface-energy nanoparticles by introducing a binder is effectively solved, and the ultra-hydrophobic micro-droplet coating with excellent weather resistance is successfully prepared. However, the surface energy of this coating is still relatively high, resulting in ultralyophobic properties only for liquids greater than 1 μ L, while tiny droplets less than 1 μ L in volume tend to adhere. In addition, because the coating adopts the nano particles with low dielectric constant, the electrostatic action exists on the surface of the coating, and the micro liquid drops with the volume less than 1 mu L are also adhered to the surface of the coating. The problem of adhesion of the tiny droplets can lead to a gradual contamination of the coating, severely limiting the practical application of ultralyophobic coatings.
Disclosure of Invention
The invention aims to provide a preparation method of a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite, which can effectively solve the problems of the existing super-hydrophobic coating.
Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite
The invention relates to a preparation method of a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite, which comprises the following steps:
(1) synthesis of Poly (styrene-co-perfluorodecyl acrylate) copolymer (hereinafter referred to as PS-co-HFA) Low surface energy adhesive: and sequentially adding the styrene, the perfluorodecyl acrylate and the azodiisobutyronitrile initiator with the polymerization inhibitor removed into tetrahydrofuran, uniformly mixing, and then carrying out reflux reaction at 60-80 ℃ for 18-30 h under the protection of nitrogen to obtain a viscous state, thus synthesizing the PS-co-HFA low surface energy binder. The molar ratio of the styrene to the perfluorodecyl acrylate is 1: 1-1: 4, and the total mass fraction of the styrene to the perfluorodecyl acrylate in a binder synthesis system is 4.8-33%. The addition amount of the azodiisobutyronitrile initiator is 3% -9% of the total amount of the styrene and the perfluorodecyl acrylate.
(2) Preparation of PS-co-HFA Binder microparticle Dispersion: dissolving PS-co-HFA low surface energy binder in a benign solvent, and dropwise adding a poor solvent under stirring to cause phase separation to obtain the low surface energy PS-co-HFA binder micron particle dispersion liquid. The benign solvent is one of dichloromethane, trichloromethane, ethyl acetate and butyl acetate, and the mass fraction of the PS-co-HFA low-surface-energy binder in the benign solvent is 15-35%. The poor solvent is one of methanol, ethanol and isopropanol, and the ratio of the benign solvent to the poor solvent is 5: 1-1: 1.
(3) Preparation of low surface energy modified polyaniline/attapulgite nano particles
i. Preparing polyaniline/attapulgite nano particles: adding acid-activated attapulgite and aniline into a hydrochloric acid solution according to the mass ratio of 0.3: 1-2: 1, stirring and mixing uniformly at room temperature, then controlling the temperature of the mixed solution at 0-10 ℃ by using an ice water bath, slowly adding a hydrochloric acid solution containing ammonium persulfate, and stirring and polymerizing for 3-5 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution, stirring for 20-40 min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. The concentration of the hydrochloric acid solution is 0.5-1.5M, and the mass ratio of ammonium persulfate to aniline is 2: 1-2.5: 1.
ii, preparation of modified polyaniline/attapulgite nano particles with low surface energy
Dispersing polyaniline/attapulgite nanoparticles into absolute ethyl alcohol, adding ammonia water as a catalyst, stirring and ultrasonically dispersing uniformly, then adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and perfluorodecyl trimethoxy silane, reacting at room temperature for 2-8 h to prepare a low-surface-energy modified polyaniline/attapulgite nanoparticle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nanoparticles. The mass ratio of the perfluorodecyl trimethoxy silane to the polyaniline/attapulgite nanoparticles is 1: 1-2: 1, and the mass ratio of the gamma- (2, 3-glycidoxy) propyl trimethoxy silane to the perfluorodecyl trimethoxy silane is 1: 4-1: 2. The ammonia water has a conventional concentration (25-30%) and has a volume fraction of 10-20% in a reaction system.
(4) Preparing a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite: adding the low-surface-energy modified polyaniline/attapulgite nano particles prepared in the step (3) into the low-surface-energy poly (styrene-co-perfluorodecyl acrylate) copolymer binder micron particle dispersion liquid prepared in the step (2), stirring and uniformly dispersing by ultrasonic to prepare poly (styrene-co-perfluorodecyl acrylate) copolymer @ polyaniline/attapulgite nano particle micron particle dispersion liquid, spraying the poly (styrene-co-perfluorodecyl acrylate) copolymer @ polyaniline/attapulgite nano particle micron particle dispersion liquid onto the surface of a base material, and curing at room temperature to prepare the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite. The mass ratio of the low-surface-energy PS-co-HFA binder micron particle dispersion to the low-surface-energy modified polyaniline/attapulgite nanoparticles is 1: 1-2: 1. The base material is one of glass, magnesium alloy, aluminum alloy, ABS and PP.
Second, performance of the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite
(1) Ultra-hydrophobic droplet performance
The test shows that the contact angle of the coating to 1 mu L water drop is more than 158 degrees and the rolling angle is less than 2 degrees; the contact angle for a 0.5 mul drop is greater than 153.5 deg. and the roll off angle is less than 5.1 deg.. The coating prepared by the invention has excellent super-hydrophobic micro-droplet performance.
(2) Durability test
The contact angle of the coating to 1 mu L water drop after Taber rubbing for 200 times under the condition of loading 250g is larger than 156.3 degrees and the rolling angle is smaller than 3.8 degrees; the contact angle for a 0.5 mul drop is greater than 150.4 deg. and the roll off angle is less than 9.7 deg.. This result demonstrates the excellent mechanical stability of the coating.
The super-hydrophobic micro-droplet performance of the coating is not obviously changed after the coating is soaked in 1M hydrochloric acid, 1M sodium hydroxide and 1M sodium chloride solution for 24 hours. This result demonstrates the excellent chemical stability of the coating.
After the coating is subjected to ultraviolet accelerated aging for 360 hours, the contact angle of the coating to 1 mu L of water drops is more than 155 degrees, and the rolling angle is less than 4.9 degrees; the contact angle for a 0.5 mul drop is greater than 150 ° and the sliding angle is less than 10 °. This result demonstrates the excellent environmental stability of the coating.
In summary, the present invention has the following advantages over the prior art:
(1) the influence of the introduction of the adhesive on the surface energy of the coating is weakened by synthesizing the fluorine-containing low-surface-energy adhesive through free radical polymerization; the modified low-surface-energy nano particles are wrapped on the surfaces of the adhesive micro particles to avoid the defect that the adhesive coats the low-surface-energy nano particles, and the two strategies are combined to minimize the influence of the introduction of the adhesive on the surface energy of the super lyophobic coating;
(2) according to the invention, the cheap natural clay mineral attapulgite is adopted as the nano particles, the polyaniline is modified to endow the nano particles with electric conductivity, and then the nano particles are modified with low surface energy to construct the super lyophobic coating with electric conductivity, so that the defect that micro droplets are adhered to the surface of the coating due to electrostatic action is effectively solved, the durable super lyophobic micro droplet self-cleaning coating is prepared, the problem that the coating is gradually polluted due to the adhesion problem of the coating to the micro droplets (less than or equal to 1 mu L) is effectively avoided, the production cost of the coating is greatly reduced, and the practical application significance of the super lyophobic coating is remarkable.
Detailed Description
The preparation and performance of the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite are further explained by the specific examples below.
Example 1
(1) 1g of styrene without polymerization inhibitor, 13g of perfluorodecyl acrylate, 0.48g of azobisisobutyronitrile and 150g of tetrahydrofuran are sequentially added into a 250mL round-bottom flask, nitrogen is introduced to remove oxygen for 30min, and the PS-co-HFA low surface energy adhesive is synthesized by reflux reaction at 70 ℃ for 24h under the protection of nitrogen.
(2) 2.5g of the synthesized PS-co-HFA low surface energy binder is dissolved in 7.5g of dichloromethane, and 3g of methanol is added dropwise under the condition of stirring at room temperature to cause phase separation, thus obtaining the PS-co-HFA low surface energy binder micron particle dispersion liquid.
(3) Firstly, adding 1.8g of acid-activated attapulgite and 0.9g of aniline into 100mL of hydrochloric acid solution (1M), stirring at room temperature for 10min, and performing ultrasonic treatment for 30 min; then, slowly adding 100mL of hydrochloric acid solution (1M) containing 2.2g of ammonium persulfate into the ice-water bath, and stirring for reacting for 4 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution (1M), stirring for 30min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. Then dispersing 10g of polyaniline/attapulgite nano particles into 440mL of absolute ethanol, adding 60mL of ammonia water, stirring for 30min and ultrasonically dispersing for 10min, then adding 6g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 18g of perfluorodecyl trimethoxy silane under the stirring condition at room temperature, reacting for 2h to prepare low-surface-energy modified polyaniline/attapulgite nano particle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nano particles.
(4) Adding 10g of low-surface-energy modified polyaniline/attapulgite nano particles into 13g of low-surface-energy PS-co-HFA binder micron particle dispersion liquid, stirring for 30min, performing ultrasonic treatment for 10min to obtain a core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle micron particle dispersion liquid, spraying the core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle micron particle dispersion liquid on the surface of glass at room temperature, and curing for 24h at room temperature to obtain the durable super-hydrophobic micro droplet self-cleaning coating based on polyaniline/attapulgite. The coating properties are shown in table 1:
TABLE 1 initial ultraphobic microdroplet properties and stability of the coating of example 1
Example 2
(1) 1g of styrene without polymerization inhibitor, 16g of perfluorodecyl acrylate, 0.45g of azobisisobutyronitrile and 125g of tetrahydrofuran are sequentially added into a 250mL round-bottom flask, nitrogen is introduced to remove oxygen for 30min, and the PS-co-HFA low surface energy adhesive is synthesized by reflux reaction at 70 ℃ for 24h under the protection of nitrogen.
(2) 2.5g of the synthesized low surface energy PS-co-HFA binder is dissolved in 8g of trichloromethane, and 3.5g of ethanol is added dropwise under the condition of stirring at room temperature to cause phase separation, thus obtaining the low surface energy PS-co-HFA binder micron particle dispersion liquid.
(3) Firstly, adding 0.9g of acid-activated attapulgite and 0.9g of aniline into 100mL of hydrochloric acid solution (1M), stirring at room temperature for 10min, and performing ultrasonic treatment for 30 min; then, slowly adding 100mL of hydrochloric acid solution (1M) containing 2.2g of ammonium persulfate into the ice-water bath, and stirring for reacting for 4 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution (1M), stirring for 30min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. Then dispersing 12g of polyaniline/attapulgite nano particles into 400mL of absolute ethyl alcohol, adding 100mL of ammonia water, stirring for 30min and ultrasonically dispersing for 10min, then adding 8g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 24g of perfluorodecyl trimethoxy silane under the stirring condition at room temperature, reacting for 2h to prepare low-surface-energy modified polyaniline/attapulgite nano particle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nano particles.
(4) Adding 7g of low-surface-energy modified polyaniline/attapulgite nano particles into 14g of low-surface-energy PS-co-HFA binder micron particle dispersion liquid, stirring for 30min, carrying out ultrasonic treatment for 10min to obtain a core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle micron particle dispersion liquid, spraying the core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle micron particle dispersion liquid on the surface of a magnesium alloy at room temperature, and curing for 24h at room temperature to obtain the durable super-hydrophobic micro droplet self-cleaning coating based on polyaniline/attapulgite. The coating properties are shown in table 2:
TABLE 2 initial ultraphobic microdroplet properties and stability of the coatings of example 2
Example 3
(1) 1g of styrene without polymerization inhibitor, 13g of perfluorodecyl acrylate, 0.48g of azobisisobutyronitrile and 150g of tetrahydrofuran are sequentially added into a 250mL round-bottom flask, nitrogen is introduced to remove oxygen for 30min, and the PS-co-HFA low surface energy adhesive is synthesized by reflux reaction at 70 ℃ for 24h under the protection of nitrogen.
(2) 2.5g of the synthesized PS-co-HFA low surface energy binder is dissolved in 7.5g of dichloromethane, and 3g of methanol is added dropwise under the condition of stirring at room temperature to cause phase separation, thus obtaining the PS-co-HFA low surface energy binder micron particle dispersion liquid.
(3) Firstly, adding 1.5g of acid-activated attapulgite and 0.9g of aniline into 100mL of hydrochloric acid solution (1M), stirring at room temperature for 10min, and performing ultrasonic treatment for 30 min; then, slowly adding 100mL of hydrochloric acid solution (1M) containing 2.2g of ammonium persulfate into the ice water bath, and stirring for reacting for 4 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution (1M), stirring for 30min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. And then dispersing 10g of polyaniline/attapulgite nanoparticles into 420mL of absolute ethanol, adding 80mL of ammonia water, stirring for 30min and ultrasonically dispersing for 10min, then adding 8g of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and 20g of perfluorodecyl triethoxysilane to react for 2h under the condition of stirring at room temperature to prepare low-surface-energy modified polyaniline/attapulgite nanoparticle suspension, and finally performing suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nanoparticles.
(4) Adding 7.8g of low-surface-energy modified polyaniline/attapulgite into 13g of low-surface-energy PS-co-HFA binder micron particle dispersion liquid, stirring for 30min and carrying out ultrasound treatment for 10min to obtain a core-shell structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micron particle dispersion liquid, spraying the core-shell structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micron particle dispersion liquid on the surface of an aluminum alloy at room temperature, and curing for 24h at room temperature to obtain the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite. The coating properties are shown in table 3:
TABLE 3 initial ultraphobic droplet properties and stability of the coatings of example 3
Example 4
(1) 1g of styrene without polymerization inhibitor, 16g of perfluorodecyl acrylate, 0.45g of azobisisobutyronitrile and 125g of tetrahydrofuran are sequentially added into a 250mL round-bottom flask, nitrogen is introduced to remove oxygen for 30min, and the PS-co-HFA low surface energy adhesive is synthesized by reflux reaction at 70 ℃ for 24h under the protection of nitrogen.
(2) 2.5g of the synthesized PS-co-HFA low surface energy binder is dissolved in 8g of trichloromethane, and 3.5g of ethanol is added dropwise under the condition of stirring at room temperature to cause phase separation, thus obtaining the PS-co-HFA low surface energy binder micron particle dispersion liquid.
(3) Firstly, adding 0.6g of acid-activated attapulgite and 0.9g of aniline into 100mL of hydrochloric acid solution (1M), stirring at room temperature for 10min, and performing ultrasonic treatment for 30 min; then, slowly adding 100mL of hydrochloric acid solution (1M) containing 2.2g of ammonium persulfate into the ice-water bath, and stirring for reacting for 4 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution (1M), stirring for 30min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. Then dispersing 10g of polyaniline/attapulgite nano particles into 440mL of absolute ethanol, adding 60mL of ammonia water, stirring for 30min and ultrasonically dispersing for 10min, then adding 6g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 18g of perfluorodecyl trimethoxy silane under the stirring condition at room temperature, reacting for 2h to prepare low-surface-energy modified polyaniline/attapulgite nano particle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nano particles.
(4) Adding 7g of low-surface-energy modified polyaniline/attapulgite into 14g of low-surface-energy PS-co-HFA binder micron particle dispersion liquid, stirring for 30min and carrying out ultrasound treatment for 10min to obtain a core-shell structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micron particle dispersion liquid, spraying the core-shell structure PS-co-HFA @ polyaniline/attapulgite nanoparticle micron particle dispersion liquid on the surface of ABS at room temperature, and curing for 24h at room temperature to obtain the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite. The coating properties are shown in table 4:
TABLE 4 initial ultraphobic droplet properties and stability of the coatings of EXAMPLE 4
Example 5
(1) 1g of styrene without polymerization inhibitor, 20g of perfluorodecyl acrylate, 0.48g of azobisisobutyronitrile and 150g of tetrahydrofuran are sequentially added into a 250mL round-bottom flask, nitrogen is introduced to remove oxygen for 30min, and the PS-co-HFA low surface energy adhesive is synthesized by reflux reaction at 70 ℃ for 24h under the protection of nitrogen.
(2) 3g of the synthesized PS-co-HFA low-surface-energy binder is dissolved in 7g of ethyl acetate, and 4.5g of isopropanol is added dropwise under the condition of stirring at room temperature to cause phase separation, so as to prepare the PS-co-HFA binder micron particle dispersion liquid.
(3) Firstly, adding 0.3g of acid-activated attapulgite and 0.9g of aniline into 100mL of hydrochloric acid solution (1M), stirring at room temperature for 10min, and performing ultrasonic treatment for 30 min; then, slowly adding 100mL of hydrochloric acid solution (1M) containing 2.2g of ammonium persulfate into the ice-water bath, and stirring for reacting for 4 hours; and (3) after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution (1M), stirring for 30min, suction filtration, washing to neutrality and drying to obtain the polyaniline/attapulgite nano particles. Then dispersing 12g of polyaniline/attapulgite nano particles into 400mL of absolute ethyl alcohol, adding 100mL of ammonia water, stirring for 30min and ultrasonically dispersing for 10min, then adding 8g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 24g of perfluorodecyl trimethoxy silane under the stirring condition at room temperature, reacting for 2h to prepare low-surface-energy modified polyaniline/attapulgite nano particle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nano particles.
(4) Adding 11.6g of low-surface-energy modified polyaniline/attapulgite nano particles into 14.5g of low-surface-energy PS-co-HFA binder micron particle dispersion liquid, stirring for 30min and carrying out ultrasound treatment for 10min to obtain a core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle dispersion liquid, spraying the core-shell structure PS-co-HFA @ polyaniline/attapulgite nano particle dispersion liquid on the surface of a magnesium alloy at room temperature, and curing for 24h at room temperature to obtain the durable super-hydrophobic micro droplet self-cleaning coating based on polyaniline/attapulgite. The coating properties are shown in table 5:
TABLE 5 initial ultraphobic droplet properties and stability of the coatings of example 5
Claims (10)
1. A preparation method of a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite comprises the following process steps:
(1) synthesis of Poly (styrene-co-perfluorodecyl acrylate) copolymer Low surface energy Binder: sequentially adding styrene, perfluorodecyl acrylate and azodiisobutyronitrile initiator with the polymerization inhibitor removed into tetrahydrofuran, uniformly mixing, and then carrying out reflux reaction at 60-80 ℃ for 18-30 h under the protection of nitrogen to obtain a viscous state, namely synthesizing the poly (styrene-co-perfluorodecyl acrylate) copolymer low surface energy binder;
(2) preparation of poly (styrene-co-perfluorodecyl acrylate) copolymer binder microparticle dispersion: dissolving the synthesized poly (styrene-co-perfluorodecyl acrylate) copolymer low-surface-energy binder in a benign solvent, dropwise adding a poor solvent under the stirring condition to cause phase separation, and preparing a low-surface-energy poly (styrene-co-perfluorodecyl acrylate) copolymer binder micron particle dispersion liquid;
(3) preparation of low surface energy modified polyaniline/attapulgite nano particles
i. Preparation of polyaniline/attapulgite nano particles
Adding acid-activated attapulgite and aniline into a hydrochloric acid solution according to the mass ratio of 0.3: 1-2: 1, stirring and mixing uniformly at room temperature, then controlling the temperature of the mixed solution at 0-10 ℃ by using an ice water bath, slowly adding a hydrochloric acid solution containing ammonium persulfate, and stirring and polymerizing for 3-5 hours; after suction filtration and washing, dispersing the filter cake into an excessive ammonia water solution, stirring for 20-40 min, then suction filtration, washing to neutrality and drying to obtain polyaniline/attapulgite nanoparticles;
ii, preparation of modified polyaniline/attapulgite nano particles with low surface energy
Dispersing polyaniline/attapulgite nanoparticles into absolute ethyl alcohol, adding ammonia water as a catalyst, stirring and ultrasonically dispersing uniformly, then adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and perfluorodecyl trimethoxy silane, reacting at room temperature for 2-8 h to prepare a low-surface-energy modified polyaniline/attapulgite nanoparticle suspension, and finally carrying out suction filtration, drying and crushing on the suspension to prepare the low-surface-energy modified polyaniline/attapulgite nanoparticles;
(4) preparing a durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite: adding the low-surface-energy modified polyaniline/attapulgite nano particles prepared in the step (3) into the low-surface-energy poly (styrene-co-perfluorodecyl acrylate) copolymer binder micron particle dispersion liquid prepared in the step (2), stirring and uniformly dispersing by ultrasonic to prepare poly (styrene-co-perfluorodecyl acrylate) copolymer @ polyaniline/attapulgite nano particle micron particle dispersion liquid, spraying the poly (styrene-co-perfluorodecyl acrylate) copolymer @ polyaniline/attapulgite nano particle micron particle dispersion liquid onto the surface of a base material, and curing at room temperature to prepare the durable super-hydrophobic micro-droplet self-cleaning coating based on polyaniline/attapulgite.
2. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating of claim 1, wherein the preparation method comprises the following steps: in the step (1), the molar ratio of the styrene to the perfluorodecyl acrylate is 1: 1-1: 4, and the total mass fraction of the styrene and the perfluorodecyl acrylate in a binder synthesis system is 4.8-33%.
3. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the addition amount of the azodiisobutyronitrile initiator is 3% -9% of the total amount of the styrene and the perfluorodecyl acrylate.
4. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (2), the benign solvent is one of dichloromethane, trichloromethane, ethyl acetate and butyl acetate, and the mass fraction of the poly (styrene-co-perfluorodecyl acrylate) copolymer low-surface-energy binder in the benign solvent is 15-35%.
5. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (2), the poor solvent is one of methanol, ethanol and isopropanol, and the ratio of the benign solvent to the poor solvent is 5: 1-1: 1.
6. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3) i, the concentration of the hydrochloric acid solution is 0.5-1.5M, and the mass ratio of ammonium persulfate to aniline is 2: 1-2.5: 1.
7. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3) ii, the mass ratio of the perfluorodecyl trimethoxy silane to the polyaniline/attapulgite nanoparticles is 1: 1-2: 1, and the mass ratio of the gamma- (2, 3-glycidoxy) propyl trimethoxy silane to the perfluorodecyl trimethoxy silane is 1: 4-1: 2.
8. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3) ii, the volume fraction of the ammonia water in the reaction system is 10-20%.
9. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (4), the mass ratio of the low-surface-energy poly (styrene-co-perfluorodecyl acrylate) copolymer binder micron particle dispersion liquid to the low-surface-energy modified polyaniline/attapulgite nanoparticles is 1: 1-2: 1.
10. The preparation method of the polyaniline/attapulgite-based durable super-hydrophobic micro-droplet self-cleaning coating as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (4), the base material is one of glass, magnesium alloy, aluminum alloy, ABS and PP.
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