CN108129691B - preparation method of micro-nano two-stage polymer composite microspheres for super-hydrophobicity - Google Patents
preparation method of micro-nano two-stage polymer composite microspheres for super-hydrophobicity Download PDFInfo
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Abstract
The invention discloses a preparation method of a micro-nano two-stage polymer composite microsphere for super-hydrophobicity, and belongs to the technical field of preparation of super-hydrophobic materials. According to the invention, a proper template, a proper monomer, a proper cross-linking agent and a proper etching agent are selected to prepare the polymer hollow microsphere, the corresponding monomer, an initiator and other reagents are adsorbed inside the hollow microsphere based on the excellent adsorption performance of the hollow microsphere, and the adsorbed monomer is polymerized by thermal initiation after being applied to a corresponding base material, so that an mastoid structure is generated on the surface of the microsphere, and thus the super-hydrophobic surface with the micro-nano two-stage polymer composite microsphere is prepared. The super-hydrophobic surface prepared by the invention can meet the requirements of special groups on water repellency and water resistance under specific conditions, and has good durability.
Description
Technical Field
The invention relates to a preparation method of a micro-nano two-stage polymer composite microsphere for super-hydrophobicity, belonging to the technical field of preparation of super-hydrophobic materials.
Background
the super-hydrophobic material is a functional material with a surface static water contact angle larger than 150 degrees and a water rolling angle smaller than 10 degrees, is widely applied to the fields of water repellency, stain resistance, fog resistance, snow resistance, self-cleaning, corrosion resistance, oxidation resistance and the like, and particularly has a higher application prospect in the research and development of super-hydrophobic and self-cleaning functional textiles. Natural superhydrophobic surfaces, such as the surfaces of certain plant leaves and petals, bird feathers, insect trunks, and reptile foot surfaces, are ubiquitous in nature, and their excellent superhydrophobic properties as well as special microstructures have attracted a great deal of attention from the academic community.
Since the discovery and the inspiration of the lotus leaf effect, the academia carries out extensive research on the excellent super-hydrophobic and self-cleaning performances of the lotus leaf surface and an exploratory bionic simulation attempt. The Barthlott, Neinhuis and the like deeply research the special self-cleaning function of the lotus leaf surface, and research results show that the super-hydrophobic phenomenon and the self-cleaning function are caused by the coexistence of micron-sized coarse papillae on the lotus leaf surface and surface wax. However, the Cheng et al research indicates that the intrinsic contact angle of the wax layer on the lotus leaf surface is only about 74 degrees, so that the micro-rough structure of the lotus leaf surface is mainly contributed to the super-hydrophobic property of the lotus leaf. Jiang et al found that there are nanostructures on the papilla of the micrometer structure on the lotus leaf surface through related testing means, and the hierarchical structure of the micrometer and nanometer structures is considered to be the root cause of the super-hydrophobicity on the lotus leaf surface. Therefore, based on the above research, it is considered that a surface with a superhydrophobic function should generally have a lower surface energy and a certain surface roughness, and if the two are combined, a superior superhydrophobic performance can be exhibited. At present, researches on super-hydrophobic materials by researchers are mainly divided into the following two aspects: firstly, the surface microstructure and chemical components of an organism with a super-hydrophobic function in some organisms in the nature are analyzed and researched, and then the super-hydrophobic surface is simulated in a bionic mode through a corresponding method. Secondly, the base material is subjected to surface treatment by using a low surface energy reagent so as to reduce the solid critical surface tension of the base material, so that the treated surface achieves a super-hydrophobic effect.
Common methods for preparing the super-hydrophobic material generally include a template etching method, a sol-gel method, an electrostatic spinning method, a high-energy particle sputtering method, a chemical vapor deposition method, a self-assembly construction method and the like. The Jiangre project group of the Chinese academy of sciences takes porous alumina as a template, a polymer enters pores of the alumina by a template extrusion method, and a nanofiber array is obtained after the template is removed, so that nanofiber array membranes of polyacrylonitrile and polyvinyl alcohol are prepared, and the static contact angles of the membrane surface and water are respectively as high as 173.8 degrees and 171.2 degrees. Shirtcliffe et al, using a combined photolithography and electrochemical deposition process, produced a two-stage roughness hierarchical structure on the copper surface, with a static contact angle of the surface with water up to 160 ° after fluorination. Kanamori and the like take vinyltrimethoxysilane and vinylmethyldimethoxysilane as raw materials, and the silicon aerogel material with super hydrophobicity and self-cleaning is prepared by a sol-gel process, and has a porous microstructure formed by connecting nano particles, so that the static water contact angle of the porous material in practical application is higher than 150 degrees. Jiang et al prepared a polyaniline/polystyrene composite film with a lotus-leaf-like surface structure by a simple electrostatic spinning technique, the surface had stable superhydrophobic performance and conductive performance in a plurality of corrosive and oxidizing solutions, and research shows that the appearance of the material surface can be controlled by controlling the concentration of polystyrene in the solution, thereby further controlling the hydrophobic performance and the conductive performance. Gui et al prepared intercommunicated three-dimensional network structure superhydrophobic materials composed of carbon nanotubes by a chemical vapor deposition method, the materials had ultralow density and higher porosity, and exhibited good performance in self-cleaning applications. Ren and the like firstly treat an aluminum sheet in boiling water at high temperature for a period of time to form a rough surface, then coat polyethylene imine, and then adsorb a self-assembled stearic acid monomolecular layer through the chemical bond combination of carboxyl and amido to obtain the super-hydrophobic film with the static contact angle of 166 degrees with water.
Researchers at home and abroad obtain inspiration from the super-hydrophobic micro-coarse structure of organisms such as lotus leaves, geckos, water striders and the like, and then the micro-nano material with the super-hydrophobic function is prepared and is applied in correlation. However, the currently developed superhydrophobic material has many problems, such as poor durability, poor self-cleaning effect on some oil stains, an accurate and controlled method for constructing a micro-nano two-stage rough structure, which is yet to be developed, and a complex superhydrophobic application process.
disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a micro-nano two-stage polymer composite microsphere for super-hydrophobicity, which is characterized in that a proper template, a monomer, a cross-linking agent and an etching agent are selected to prepare a polymer hollow microsphere, the corresponding monomer, an initiator and other reagents can be adsorbed inside the hollow microsphere based on the excellent adsorbability of the polymer hollow microsphere, and the adsorbed monomer is polymerized by thermal initiation after being applied to a corresponding base material, so that a mastoid structure is generated on the surface of the microsphere, and the super-hydrophobic surface of the micro-nano two-stage polymer composite microsphere is prepared. The micro-nano two-stage polymer composite microsphere prepared by the invention can meet the super-hydrophobic requirement of a common base material, and has the advantages of good deposition effect and simple and convenient application process.
The invention provides a micro-nano two-stage polymer composite microsphere for super-hydrophobicity, which is prepared by firstly preparing a polymer hollow microsphere by a template etching method, and then adsorbing a monomer, an initiator and a cross-linking agent into the polymer hollow microsphere to initiate the monomer to polymerize to form a super-hydrophobic surface with the micro-nano two-stage polymer composite microsphere.
In one embodiment of the present invention, the monomer is a hard monomer or a fluorine-containing monomer.
In an embodiment of the present invention, the monomer is one or more selected from styrene, 3-chlorostyrene, 2-chlorostyrene, 4-fluorostyrene, 3-fluorostyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene, ethylstyrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, trifluoroethyl methacrylate, trifluoroacetyl triflate, 3-fluorophenyl acetate, dodecafluoroheptyl methacrylate, (perfluorohexyl) ethylene, and hexafluorobutyl methacrylate.
in one embodiment of the present invention, the crosslinking agent is acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, N-methylolacrylamide or diacetone acrylamide.
In one embodiment of the invention, the initiator is potassium persulfate, ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile, or azobisisobutylamidine hydrochloride.
In one embodiment of the invention, the polymer hollow microspheres are prepared by adding modified silica microspheres into absolute ethyl alcohol to prepare a modified silica microsphere ethanol dispersion with the mass ratio of 5-10%, adding 2.5-7.5% of a dispersing agent into the ethanol dispersion, dispersing the mixture at a high speed for 10-30 minutes at the temperature of 30 ℃, then adding 2.5-12.5% of a monomer, 1.5-5.25% of a cross-linking agent, 0.25-1% of an initiator and 2.5-25% of deionized water into the system, and continuing to disperse the mixture at a high speed for 1-3 hours under the same conditions; reducing the rotation speed to 300-500 r/min, raising the temperature of the dispersion system to 70-90 ℃, and reacting for 5-10 hours to obtain the silicon dioxide/polymer core-shell type microspheres; and adding 75-150% sodium hydroxide solution (0.5-2.0mol/L) to etch the silicon dioxide inner core in the core-shell microsphere for 2-6 hours, and finally obtaining the polymer hollow microsphere.
In one embodiment of the present invention, the particle size of the modified silica microsphere is between 300-3000 nm.
in one embodiment of the present invention, the monomer used in the polymeric hollow microspheres is one or more of styrene, 3-chlorostyrene, 2-chlorostyrene, 4-fluorostyrene, 3-fluorostyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene, ethylstyrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, trifluoroethyl methacrylate, trifluoroacetyl triflate, 3-fluorophenylacetate, dodecafluoroheptyl methacrylate, (perfluorohexyl) ethylene, hexafluorobutyl methacrylate.
in one embodiment of the present invention, the dispersant used in the polymeric hollow microspheres is sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, potassium oleate, sodium alkylnaphthalenesulfonate, polyvinylpyrrolidone, a polyoxyethylene alkylphenol condensate, a polyoxyethylene fatty alcohol condensate, a polyoxyethylene polyol ether fatty acid ester, or a polyoxyethylene ester of a fatty acid.
In one embodiment of the present invention, the cross-linking agent used in the polymeric hollow microspheres is acrylic acid, 1, 3-butadiene, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, N-methylolacrylamide or diacetone acrylamide.
in one embodiment of the invention, the initiator used in the polymeric hollow microspheres is potassium persulfate, ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile or azobisisobutylamidine hydrochloride.
the second purpose of the invention is to provide a preparation method of the composite microsphere, which comprises the following steps: (1) preparation of polymer hollow microspheres: adding modified silicon dioxide microspheres into absolute ethyl alcohol to prepare a modified silicon dioxide microsphere ethanol dispersion with the mass ratio of 5-10%, adding 2.5-7.5% of dispersing agent, dispersing for 10-30 minutes at a high speed (8000-; reducing the rotation speed to 300-500 r/min, raising the temperature of the dispersion system to 70-90 ℃, and reacting for 5-10 hours to obtain the silicon dioxide/polymer core-shell type microspheres; adding 75-150% sodium hydroxide solution (0.5-2.0mol/L) to etch the silicon dioxide inner core in the core-shell microsphere for 2-6 hours, and finally obtaining the polymer hollow microsphere;
(2) The preparation of the micro-nano two-stage polymer composite microsphere and the construction method of the super-hydrophobic surface thereof are as follows: adding 0.25-2.5% of selected monomer, 0.25-1.25% of cross-linking agent, 0.125-0.875% of initiator and 0.25-1.25% of polymer hollow microspheres into 37.5-112.5% of deionized water, stirring and adsorbing for 5-10 hours at room temperature, and performing centrifugal cleaning for a plurality of times after adsorption is finished; and then, applying the polymer microspheres adsorbing related substances to the surfaces of corresponding base materials to react for 2-8 hours in an oven at the temperature of 65-85 ℃, thereby preparing the super-hydrophobic surface with the micro-nano two-stage polymer composite microspheres.
The invention has the beneficial effects that the preparation method of the micro-nano two-stage polymer composite microsphere for super-hydrophobicity is provided, the polymer hollow microsphere is prepared firstly, corresponding monomers, an initiator and other reagents are adsorbed in the hollow microsphere based on the excellent adsorption performance of the polymer hollow microsphere, and the adsorbed monomers are polymerized by thermal initiation to generate a mastoid structure on the surface of the microsphere, so that the super-hydrophobic surface with the micro-nano two-stage polymer composite microsphere is prepared. The super-hydrophobic surface prepared based on the method can meet the requirements of water repellency and water resistance of special groups under specific conditions, and the structure of the super-hydrophobic surface has good durability, and can still retain higher hydrophobicity after being treated by heating, strong acid and strong alkali.
Drawings
FIG. 1 shows the surface morphology of a micro-nano dual-stage polymer composite microsphere.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention.
Example 1
Preparing polymethyl methacrylate-divinylbenzene- (perfluorohexyl) ethylene hollow microspheres:
3g of modified silica microspheres (particle size of 500nm) and 1g of sodium dodecylbenzenesulfonate were dissolved in 55mL of anhydrous ethanol, and the resulting solution was put into a three-necked flask equipped with a thermometer and a condenser and stirred at 1200 rpm for 30 minutes. 0.1g of ammonium persulfate is weighed and dissolved in 3g of methyl methacrylate, 0.9g of divinylbenzene and 4g of (perfluorohexyl) ethylene, 5mL of deionized water is added into the solution, the solution is slowly added into the liquid phase prepared at the previous stage after being uniformly mixed, and the stirring is continued for 2 hours under the condition of 1200 r/min. After stirring, the temperature is raised to 85 ℃ for reaction for 5 hours (the rotating speed is 400 rpm), and then 60mL of sodium hydroxide solution (2.0M) is added into the reaction system to etch the template for 2 hours. Finally, the polymethyl methacrylate-divinylbenzene- (perfluorohexyl) ethylene hollow microsphere is obtained.
Preparing polymethyl methacrylate-divinylbenzene- (perfluorohexyl) ethylene @ polystyrene-1, 3-butadiene micro-nano double-stage polymer composite microspheres on the surface of glass:
Weighing 0.2g of polymethyl methacrylate-divinylbenzene- (perfluorohexyl) ethylene hollow microspheres which are washed by centrifugation, adding the weighed materials into 40mL of deionized water, then adding 0.5g of styrene, 0.5g of 1, 3-butadiene and 0.15g of benzoyl peroxide into a liquid phase, and stirring and adsorbing for 8 hours at room temperature. After the adsorption is finished, the solution is centrifugally cleaned and placed on a glass plate to be heated to 75 ℃ for reaction for 3 hours. After the reaction is finished, preparing the polymethyl methacrylate-divinylbenzene- (perfluorohexyl) ethylene @ polystyrene-1, 3-butadiene micro-nano double-stage polymer composite microspheres on the surface of the glass.
the static contact angle of the prepared super-hydrophobic water surface to water is 151 degrees.
Example 2
Preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres:
2g of modified silica microspheres (particle size 300nm) and 1g of polyvinylpyrrolidone were dissolved in 40mL of anhydrous ethanol, and the resulting solution was put into a three-necked flask equipped with a thermometer and a condenser and stirred at 800 rpm for 10 minutes. Weighing 0.1g of AIBNP dissolved in 1g of styrene, 0.6g of divinylbenzene and 1g of trifluoroethyl methacrylate, adding 1mL of deionized water, uniformly mixing the liquids, slowly adding the liquids into the liquid phase prepared at the previous stage, and continuously stirring for 1 hour under the condition of 800 revolutions per minute. After stirring, the temperature is raised to 70 ℃ for 5 hours (the rotating speed is 300 r/min), and then 30mL of sodium hydroxide solution (0.5M) is added into the reaction system to etch the template for 2 hours. Finally, the polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres are obtained.
Preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of glass:
Weighing 0.1g of polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres (dispersant is removed by centrifugal cleaning) and adding the microspheres into 15mL of deionized water, then adding 0.5g of styrene, 0.1g of ethylene glycol dimethacrylate, 0.1g of trifluoroethyl methacrylate and 0.05g of AIBN into the liquid phase, and stirring (rotating speed 500 r/min) at room temperature for adsorption for 5 hours. After the adsorption is finished, the solution is centrifugally cleaned and placed on a glass plate to be heated to 65 ℃ for reaction for 2 hours. After the reaction is finished, preparing the polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of the glass.
The prepared super-hydrophobic water surface has a static contact angle of 155 degrees to water.
Example 3:
Preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres:
3g of modified silica microspheres (particle size: 700nm) and 2g of polyvinylpyrrolidone were dissolved in 45mL of anhydrous ethanol, and the resulting solution was put into a three-necked flask equipped with a thermometer and a condenser and stirred at 1200 rpm for 30 minutes. Weighing AIBN0.2g dissolved in 4g of styrene, 1.2g of divinylbenzene and 2g of trifluoroethyl methacrylate, adding 5mL of deionized water, uniformly mixing the liquids, slowly adding the liquids into the liquid phase prepared at the previous stage, and continuously stirring for 2 hours under the condition of 1200 revolutions per minute. After stirring, the temperature is raised to 80 ℃ for reaction for 6 hours (the rotating speed is 400 rpm), and then 50mL of sodium hydroxide solution (1M) is added into the reaction system to etch the template for 4 hours. Finally, the polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres are obtained.
preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of glass:
0.4g of polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres (dispersant is removed by centrifugal cleaning) are weighed and added into 30mL of deionized water, then 0.8g of styrene, 0.24g of ethylene glycol dimethacrylate, 0.24g of trifluoroethyl methacrylate and 0.1g of AIBN are added into the liquid phase, and the mixture is stirred (rotating speed is 600 revolutions per minute) at room temperature and adsorbed for 10 hours. After the adsorption is finished, the solution is centrifugally cleaned and placed on a glass plate to be heated to 80 ℃ for reaction for 6 hours. After the reaction is finished, preparing the polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of the glass.
The prepared super-hydrophobic water surface has a static contact angle of 163 degrees to water.
Example 4:
Preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres:
4g of modified silica microspheres (particle size of 3000nm) and 3g of polyvinylpyrrolidone were dissolved in 60mL of anhydrous ethanol, and the resulting solution was put into a three-necked flask equipped with a thermometer and a condenser and stirred at 1500 rpm for 30 minutes. Weighing 0.4g of AIBNP dissolved in 5g of styrene, 2.1g of divinylbenzene and 5g of trifluoroethyl methacrylate, adding 10mL of deionized water into the weighed materials, uniformly mixing the above liquids, slowly adding the liquids into the liquid phase prepared at the previous stage, and continuously stirring the mixture for 3 hours under the condition of 1500 revolutions per minute. After stirring, the temperature is raised to 90 ℃ for 10 hours (the rotating speed is 500 rpm), and then 60mL of sodium hydroxide solution (2M) is added into the reaction system to etch the template for 6 hours. Finally, the polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres are obtained.
preparing polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of glass:
Weighing 0.5g of polystyrene-divinylbenzene-trifluoroethyl methacrylate hollow microspheres (dispersant is removed by centrifugal cleaning) and adding the microspheres into 45mL of deionized water, then adding 1g of styrene, 0.5g of ethylene glycol dimethacrylate, 1g of trifluoroethyl methacrylate and 0.35g of AIBN into the liquid phase, and stirring (rotating speed of 800 r/min) at room temperature for adsorption for 10 hours. After the adsorption is finished, the solution is centrifugally cleaned and placed on a glass plate to be heated to 85 ℃ for reaction for 8 hours. After the reaction is finished, preparing the polystyrene-divinylbenzene-trifluoroethyl methacrylate @ polystyrene-ethylene glycol dimethacrylate-trifluoroethyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of the glass.
the prepared super-hydrophobic water surface has a static contact angle of 166 degrees to water.
Example 5:
Preparing polystyrene-ethylene glycol dimethacrylate hollow microspheres:
2g of modified silica microspheres (particle size: 600nm) and 2.5g of polyvinylpyrrolidone were dissolved in 50mL of anhydrous ethanol, and the resulting solution was put into a three-necked flask equipped with a thermometer and a condenser and stirred at 1000 rpm for 30 minutes. Weighing AIBN0.3g dissolved in 3.5g of styrene and 1.8g of ethylene glycol dimethacrylate, adding 8mL of deionized water, mixing the above liquids uniformly, slowly adding the mixture into the liquid phase prepared in the previous stage, and continuously stirring for 2 hours under the condition of 1200 rpm. After stirring, the temperature is raised to 70 ℃ for 10 hours (the rotating speed is 300 r/min), and then 40mL of sodium hydroxide solution (0.8M) is added into the reaction system to etch the template for 3 hours. Finally, the polystyrene-ethylene glycol dimethacrylate hollow microsphere is obtained.
Preparing polystyrene-ethylene glycol dimethacrylate @ polydimethylstyrene-hexafluorobutyl methacrylate micro-nano double-stage polymer composite microspheres on the surface of glass:
0.4g of polystyrene-ethylene glycol dimethacrylate hollow microspheres (which are centrifugally cleaned to remove the dispersant) are weighed and added into 20mL of deionized water, and then 0.6g of dimethyl styrene, 0.6g of hexafluorobutyl methacrylate and 0.15g of AIBN are added into the liquid phase, and the mixture is stirred and adsorbed for 8 hours at room temperature. After the adsorption is finished, the solution is centrifugally cleaned and placed on a glass plate to be heated to 85 ℃ for reaction for 3 hours. After the reaction is finished, the polystyrene-ethylene glycol dimethacrylate @ polydimethylstyrene-hexafluorobutyl methacrylate micro-nano double-stage polymer composite microspheres are prepared on the surface of the glass.
The static contact angle of the prepared super-hydrophobic water surface to water is 158 degrees.
The durability tests of the superhydrophobic materials prepared in examples 1-5 are shown in table 1.
TABLE 1 durability test of superhydrophobic materials
in Table 1, reference sample 1 is polystyrene-ethylene glycol dimethacrylate prepared by direct monomer polymerization; the control sample 2 is polystyrene-divinylbenzene-trifluoroethyl methacrylate prepared by direct monomer polymerization.
Comparative example 1:
the hollow microspheres and the polymer protrusions are constructed by using soft monomer butyl methacrylate as main raw materials, and other conditions are kept consistent with those of example 1. The comparison example is different from the above embodiment in that the polymer obtained by polymerizing the soft monomer has low hardness, cannot stably maintain the self-morphology and is not beneficial to forming a micro-nano double-stage structure, so that the static contact angle of the prepared super-hydrophobic surface to water is only 78 degrees.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The micro-nano double-stage polymer composite microsphere for super-hydrophobicity is characterized in that the composite microsphere is prepared by firstly preparing a polymer hollow microsphere through a template etching method, then adsorbing a monomer, an initiator and a cross-linking agent into the polymer hollow microsphere to initiate the monomer to polymerize to form a super-hydrophobic surface with the micro-nano double-stage polymer composite microsphere, wherein the monomer is styrene, 3-chlorostyrene, 2-chlorostyrene, 4-fluorostyrene, 3-fluorostyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene, ethylstyrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, trifluoroethyl methacrylate, trifluoroacetyl triflate, 3-fluorophenyl acetate, ethyl acetate, methyl acetate, ethyl acetate, trifluoroacetyl triflate, sodium benzoate, and ethyl acetate, One or more of dodecafluoroheptyl methacrylate, (perfluorohexyl) ethylene and hexafluorobutyl methacrylate;
the polymer hollow microspheres are prepared by adding modified silicon dioxide microspheres into absolute ethyl alcohol to prepare a modified silicon dioxide microsphere ethanol dispersion with the mass ratio of 5-10%, adding 2.5-7.5% of dispersing agent into the ethanol dispersion, dispersing the mixture at a high speed for 10-30 minutes at the temperature of 30 ℃, then adding 2.5-12.5% of monomer, 1.5-5.25% of cross-linking agent, 0.25-1% of initiator and 2.5-25% of deionized water into the system, and continuing to disperse the mixture at a high speed for 1-3 hours under the same conditions; reducing the rotation speed to 300-500 r/min, raising the temperature of the dispersion system to 70-90 ℃, and reacting for 5-10 hours to obtain the silicon dioxide/polymer core-shell type microspheres; adding 75-150% sodium hydroxide solution with the concentration of 0.5-2.0mol/L to etch the silicon dioxide inner core in the core-shell microsphere for 2-6 hours, and finally obtaining the polymer hollow microsphere; the monomer used in the polymer hollow microsphere is one or more of styrene, 3-chlorostyrene, 2-chlorostyrene, 4-fluorostyrene, 3-fluorostyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene, ethylstyrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, trifluoroethyl methacrylate, trifluoroacetyl triflate, 3-fluorophenyl acetate, dodecafluoroheptyl methacrylate, (perfluorohexyl) ethylene and hexafluorobutyl methacrylate; the dispersing agent is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium oleate, sodium alkyl naphthalene sulfonate, polyvinylpyrrolidone, a polyoxyethylene alkyl phenol condensation compound, a polyoxyethylene fatty alcohol condensation compound, a polyoxyethylene polyol ether fatty acid ester or a polyoxyethylene ester of fatty acid; the cross-linking agent is acrylic acid, 1, 3-butadiene, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, N-methylol acrylamide or diacetone acrylamide; the initiator is potassium persulfate, ammonium persulfate, benzoyl peroxide, azodiisobutyronitrile or azodiisobutyl amidine hydrochloride.
2. The composite microspheres of claim 1, wherein the cross-linking agent is acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, N-methylolacrylamide or diacetone acrylamide.
3. the composite microsphere of claim 1, wherein the initiator is potassium persulfate, ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile or azobisisobutylamidine hydrochloride.
4. The composite microsphere according to claim 1, wherein the particle size of the modified silica microsphere is between 300 and 3000 nm.
5. The method for preparing the composite microspheres according to claim 1, wherein the method specifically comprises:
(1) Preparation of polymer hollow microspheres: adding modified silicon dioxide microspheres into absolute ethyl alcohol to prepare a modified silicon dioxide microsphere ethanol dispersion with the mass ratio of 5-10%, adding 2.5-7.5% of dispersing agent, dispersing for 10-30 minutes at the rotating speed of 8000-; reducing the rotation speed to 300-500 r/min, raising the temperature of the dispersion system to 70-90 ℃, and reacting for 5-10 hours to obtain the silicon dioxide/polymer core-shell type microspheres; adding 75-150% sodium hydroxide solution with the concentration of 0.5-2.0mol/L to etch the silicon dioxide inner core in the core-shell microsphere for 2-6 hours, and finally obtaining the polymer hollow microsphere;
(2) The preparation of the micro-nano two-stage polymer composite microsphere and the construction method of the super-hydrophobic surface thereof are as follows: adding 0.25-2.5% of selected monomer, 0.25-1.25% of cross-linking agent, 0.125-0.875% of initiator and 0.25-1.25% of polymer hollow microspheres into 37.5-112.5% of deionized water, stirring and adsorbing for 5-10 hours at room temperature, and performing centrifugal cleaning for a plurality of times after adsorption is finished; and then, applying the polymer microspheres adsorbing related substances to the surfaces of corresponding base materials to react for 2-8 hours in an oven at the temperature of 65-85 ℃, thereby preparing the super-hydrophobic surface with the micro-nano two-stage polymer composite microspheres.
6. Use of the composite microspheres of claim 1 in the textile field.
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