CN102086333A - Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof - Google Patents
Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic-inorganic composite coating in a chrysanthemum-shaped micro-nano structure and a preparation method thereof. The preparation method comprises the following steps of: preparing hybridized nano silicon dioxide with double bonds on a surface by using vinyl siloxane as a raw material with an emulsion polymerization method; then copolymerizing the hybridized nano silicon dioxide with a vinyl monomer, wherein the surface of the hybridized nano silicon dioxide is provided with double bonds so that the hybridized nano silicon dioxide can be directly polymerized, and a stable organic-inorganic composite emulsion can be prepared without carrying out modification on the silicon dioxide in a reaction process; and coating the composite emulsion on a glass slide, then drying the glass slide in an oven at a certain temperature so that the obtained composite coating is in a chrysanthemum-shaped micro-nano coarse structure and can be used for the field of hydrophobic coatings.
Description
Technical field
The invention belongs to chemical field, relate to a kind of about organic and inorganic compound coating and make each method with chrysanthemum shape micro-nano structure.
Background technology
The organic and inorganic compound coating is on the basis of good characteristics such as the film-forming properties that keeps organic materials, the transparency, flexibility, have advantages such as the high rigidity of inorganic nano-particle and thermotolerance again, nano hybridization structure formation is various, and can in sizable scope, regulate and control, can give compound coating with new function, therefore be subjected to people and more and more pay attention to.At present, the method that is used to prepare the organic and inorganic compound coating with micro-nano structure mainly comprises: sol-gel method, galvanic deposit or chemical deposition, plasma treatment, planography method etc.These methods generally are earlier with inorganic nano-particle and the direct blend of organic polymer or with polymkeric substance inorganic nano-particle simply to be coated (chemical reaction does not take place between inorganic nano-particle and the polymkeric substance), and then are prepared into the coating with micro-nano structure.But required electrochemical conditions that these preparation methods have and technology harshness, the needs that have use a large amount of organic solvents or apparatus expensive to be difficult to obtain industrialized application on the micro-nano structure structure of organic and inorganic compound coating.Therefore, seek that a kind of processing condition are simple, the organic and inorganic compound coating of safety non-toxic seems very important.
Chinese patent application numbers 200810232749.3 has proposed a kind of preparation method of porcelain insulator surface super-hydrophobic coating, prepare silicon dioxide gel by sol-gel method, and adding silane coupling agent, it is carried out modification handles, then the porcelain insulator after the surface treatment is immersed in silicon dioxide gel and the add-on type liquid silicon rubber colloidal sol and lift plated film, after heat treatment obtain having the transparent hydrophobic coating of micro/nano level coarse structure, but the coating preparation step is various, the processing condition complexity.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of excellent performance, safety non-toxic, technology and simply have organic and inorganic compound coating of chrysanthemum shape micro-nano structure and preparation method thereof, the polymer chemistry that will contain organic fluorine with the method for copolymerization is grafted on the hybridized nanometer silicon-dioxide, makes the manufactured coating material have only the excellent hydrophobicity energy.
Technical scheme: the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure of the present invention wt% is by weight percentage counted:
Hybridized nanometer silicon-dioxide 0.1-10 wt%
Nonfluorinated vinyl monomer 2-30 wt%
Fluorinated vinyl monomer 0.5-12wt%
Initiator 0.05-2wt%
Tensio-active agent 0.03-2wt%
Sodium bicarbonate 0.5-5wt%
Surplus is a deionized water.
The particle diameter of described hybridized nanometer silicon-dioxide is 100-500nm.
Described fluorinated vinyl monomer is the fluoroacrylate monomer.
Described nonfluorinated vinyl monomer is one or more in methacrylic ester, alkenyl aromatic compound or the acrylate monomer.
Described initiator is persulphate or water-soluble azo initiator.
Described tensio-active agent is one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the stearic acid.
Preparation method with organic and inorganic composite coating material of chrysanthemum shape micro-nano structure of the present invention comprises the steps:
1) with the vinylsiloxane is raw material, deionized water is a solvent, Sodium dodecylbenzene sulfonate is a tensio-active agent, under alkaline condition, press vinylsiloxane: deionized water: ammoniacal liquor: after the mass ratio of Sodium dodecylbenzene sulfonate=4-10:80-120:0.5-2.5:0.02-0.1 mixes, under 35-70 ° of C temperature, stir 5-30h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing;
2) the hybridized nanometer silicon-dioxide in the step 1) is fully disperseed in deionized water, then with polymerization of vinyl monomer, vinyl monomer comprises fluorinated vinyl monomer and nonfluorinated vinyl monomer, the polymeric initiator is thermal initiator or water-soluble azo initiator, the employing sodium bicarbonate is a buffer reagent, about the pH value to 11 of regulation system; Earlier deionized water and hybridized nanometer silicon-dioxide are stirred 0.5-5h under nitrogen protection during preparation, being warming up to 75 ℃ of adding sodium bicarbonates and initiator continues to stir O.5-5h, slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor then, stirring reaction 10-30h obtains the oyster white dispersion liquid;
3) with step 2) in the oyster white dispersion liquid be coated on the slide glass, be placed in the baking oven drying treatment under 40-60 ℃ temperature then, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Vinylsiloxane in the described step 1) can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
The present invention has prepared the surperficial hybridized nanometer silicon-dioxide that has two keys according to emulsion polymerization.Hybridized nanometer dioxy gasification silicon is raw material with the vinylsiloxane, be different from the tetraethoxy is the silicon-dioxide of feedstock production, the surface is not contained-the Si-OH key, but enrichment a large amount of-Si-CH=CH2 key, therefore hydridization silicon-dioxide has the good hydrophobic lipophilicity, and since surface enrichment two key groups, when preparation organic and inorganic composite emulsion, need not silicon-dioxide is carried out surface treatment, simplify experimental procedure.
The present invention is with above-mentioned hybridized nanometer silicon-dioxide; a certain amount of deionized water adds 250ml thermometer is housed; spherical condensation tube; in the four-hole boiling flask of agitator and nitrogen protection device; under nitrogen protection, stir O.5-5h; system temperature is increased to 75 ℃; add a certain amount of initiator and sodium bicarbonate; about the pH value to 11 of conditioned reaction system; continue to stir O.5-5h; the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer slowly splash in the reactor then; under nitrogen protection, react 5-30h; obtain the oyster white dispersion liquid, be SiO 2-polymer organic and inorganic composite emulsion.
The present invention is coated in above-mentioned composite emulsion on the slide glass, carries out drying treatment at baking oven under certain temperature, obtains having the organic and inorganic compound coating of chrysanthemum shape micro-nano structure.
Beneficial effect: a kind of preparation method that the present invention proposes with organic and inorganic compound coating of chrysanthemum shape micro-nano structure, have the following advantages: the hybridized nanometer silicon dioxide granule preparation process of employing is simple, the two key groups of surface enrichment, need not to carry out surface treatment, experimental procedure can be simplified, the grafting amount of polymkeric substance can be guaranteed again at silica sphere.Emulsion polymerization carries out in aqueous medium, do not contain any organic solvent, safety non-toxic, the preparation technology of organic and inorganic compound coating is simple, be easy to control, at a lower temperature the composite emulsion that is coated on the slide glass is carried out drying treatment, just can obtain stable performance, have the organic and inorganic compound coating of chrysanthemum shape micro-nano structure.The coating method of this coating can adopt drip be coated with, spin coating, spraying or crystal pulling method.
The organic and inorganic compound coating with chrysanthemum shape micro-nano structure of the present invention's preparation is formed by the composite particles deposition self-assembly of polymer overmold hybridized nanometer silicon-dioxide, wherein the polymkeric substance of fluorinated vinyl monomer polymerization generation has low table and free energy, and the chrysanthemum shape micro-nano structure that the self-assembly of composite particles deposition forms has big roughness, make coating have the excellent hydrophobicity energy, therefore can be used in the hydrophobic coating material that preparation has automatically cleaning, antipollution, anti-scribble performance.
Embodiment
A kind of preparation method with organic and inorganic compound coating of chrysanthemum shape micro-nano structure that the present invention proposes comprises the steps:
1) with the vinylsiloxane is raw material, deionized water is a solvent, Sodium dodecylbenzene sulfonate is the table promoting agent, under alkaline condition, press vinylsiloxane: deionized water: ammoniacal liquor: after the mass ratio of Sodium dodecylbenzene sulfonate=4-10:80-120:0.5-2.5:0.02-0.1 mixes, under 35-70 ℃ of temperature, stir 5-30h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing three times;
2) the hybridized nanometer silicon-dioxide in the step 1) is fully disperseed in deionized water, then with polymerization of vinyl monomer, vinyl monomer comprises fluorinated vinyl monomer and nonfluorinated vinyl monomer, the polymeric initiator is thermal initiator or water-soluble azo initiator, the employing sodium bicarbonate is a buffer reagent, about the pH value to 11 of regulation system; Earlier O.5-5h deionized water and hydridization silicon-dioxide are stirred under nitrogen protection during preparation; be warming up to 75 ℃ and add sodium bicarbonate and initiator continuation stirring 0.5-5h; slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor then; stirring reaction 10-30h; obtain the oyster white dispersion liquid, this material is percentage by weight
Each component is counted with weight percent wt%:
Hybridized nanometer silicon-dioxide 0.1-10 wt%
Nonfluorinated vinyl monomer 2-30 wt%
Fluorinated vinyl monomer 0.5-12wt%
Initiator 0.05-2wt%
Tensio-active agent 0.03-2wt%
Sodium bicarbonate 0.5-5wt%
Surplus is a deionized water.
3) with step 2) in the oyster white dispersion liquid be coated on the slide glass, be placed in the baking oven drying treatment under certain temperature then, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Among the present invention, the vinylsiloxane in the described step 1) can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
Among the present invention, the surface of adopting in the described step 1) has the hybridized nanometer silicon-dioxide of two keys, and its particle diameter is 100-500nm.
Among the present invention, described step 2) the fluorinated vinyl monomer in is the fluoroacrylate monomer, as methacrylic acid 17 fluorine esters in the last of the ten Heavenly stems, methacrylic acid ten trifluoro monooctyl esters, methacrylic acid ten difluoro heptyl esters, methacrylic acid hexafluoro butyl ester, methylacrylic acid 2,2,2-fluorine ethyl ester etc.
Among the present invention, described step 2) the nonfluorinated vinyl monomer in is methacrylic ester, alkenyl aromatic compound, acrylate monomer, as methyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, vinylbenzene, alpha-methyl styrene, 4. vinyl toluene, 3,4-dimethyl styrene, ethyl propenoate, butyl acrylate, propyl acrylate etc.
Among the present invention, described step 2) initiator in is persulphate or water-soluble azo initiator, as Sodium Persulfate, Potassium Persulphate, ammonium persulphate, azo-bis-isobutyrate hydrochloride, azo two isobutyl propyl group amidine azoles quinoline hydrochlorides etc.
Among the present invention, described step 2) tensio-active agent in is one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, the stearic acid.
Among the present invention, the drying treatment temperature in the described step 3) is 40-60 ℃.
Embodiment 1:
(1) in the 250ml four-hole boiling flask, adds deionized water, vinyltriethoxysilane, ammoniacal liquor and Sodium dodecylbenzene sulfonate successively according to the mass ratio of 80:4:O.5:0.02,35.Stir 5h under the C temperature, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing three times;
(2) thermometer is being housed, spherical condensation tube, in the 250ml four-hole boiling flask of agitator and nitrogen protection device, add the hybridized nanometer silicon-dioxide of 0.3g and the deionized water of 65g, under nitrogen protection, stir 0.5h, be warming up to after 75 ℃, add O.03g ammonium persulphate and sodium bicarbonate O.24g, continue to stir 0.5h, to the vinylbenzene that contains 2g of supersound process 10min then, 0.6g methacrylic acid ten trifluoro monooctyl esters and the mixed solution of O.05g Sodium dodecylbenzene sulfonate slowly splash in the reactor, obtain milky composite emulsion behind the stirring reaction 10h;
(3) above-mentioned composite emulsion is coated on the slide glass, under 45 ℃, is placed on drying treatment in the baking oven then, obtain having the compound coating of chrysanthemumization shape micro/nano level coarse structure.
Embodiment 2:
(1) in 250rnl network interface flask, mass ratio according to 100:8:1.5:0.04 adds deionized water, vinyltriethoxysilane, ammoniacal liquor and Sodium dodecylbenzene sulfonate successively, under 50 ℃ of temperature, stir 10h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing three times;
(2) thermometer is being housed, spherical condensation tube, in the 250ml four-hole boiling flask of agitator and nitrogen protection device, add the hybridized nanometer silicon-dioxide of 0.5g and the deionized water of 65g, under nitrogen protection, stir 1h, be warming up to after 75 ℃, add the ammonium persulphate of 0.04g and the sodium bicarbonate of 0.24g, continue to stir 0.5h, to the vinylbenzene that contains 3g of supersound process 10min then, 0.6g methacrylic acid ten difluoro monooctyl esters and the mixed solution of O.05g Sodium dodecylbenzene sulfonate slowly splash in the reactor, obtain milky composite emulsion behind the stirring reaction 5h;
(3) above-mentioned composite emulsion is coated on the slide glass, under 50 ℃, is placed on drying treatment in the baking oven then, obtain having the compound coating (see figure 1) of chrysanthemum shape micro/nano level coarse structure.
Embodiment 3:
(1) in the 250ml four-hole boiling flask, mass ratio according to 120:10:2.5:0.08 adds deionized water, vinyltriethoxysilane, ammoniacal liquor and Sodium dodecylbenzene sulfonate successively, under 60 ℃ of temperature, stir 15h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing three times;
(2) thermometer is being housed, spherical condensation tube, in the 250m1 four-hole boiling flask of agitator and nitrogen protection device, add the hybridized nanometer silicon-dioxide of 0.3g and the deionized water of 80g, under nitrogen protection, stir 2h, be warming up to after 75 ℃, add the ammonium persulphate of 0.04g and the sodium bicarbonate of 0.24g, continue to stir O.5h, then oneself is handled the vinylbenzene that contains 2g of 15min through super Lu, 0.4.g methacrylic acid ten trifluoro monooctyl esters and the mixed solution of O.07g Sodium dodecylbenzene sulfonate slowly splash in the reactor, obtain milky composite emulsion behind the stirring reaction 24h;
(3) above-mentioned composite emulsion is coated on the slide glass, under 45 ℃, is placed on drying treatment in the baking oven then, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Embodiment 4:
1) in the 250ml four-hole boiling flask, mass ratio according to 100:8:1.5:0.04 adds deionized water, vinyltriethoxysilane, ammoniacal liquor and Sodium dodecylbenzene sulfonate successively, under 50 ℃ of temperature, stir 10h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing three times;
2) thermometer is being housed, spherical condensation tube, in the 250ml four-hole boiling flask of agitator and nitrogen protection device, add the hybridized nanometer silicon-dioxide of 0.3g and the deionized water of 70g, under nitrogen protection, stir 4h, be warming up to after 75 ℃, add the ammonium persulphate of 0.035g and the sodium bicarbonate of 0.24.g, continue to stir O.5h, to the vinylbenzene that contains 2.5g of supersound process 20min then, the mixed solution of methacrylic acid ten trifluoro monooctyl esters O.5g and Sodium dodecylbenzene sulfonate O.06g slowly splashes in the reactor, obtains milky composite emulsion behind the stirring reaction 24h;
(3) above-mentioned composite emulsion is coated on the slide glass, under 45 ℃, is placed on drying treatment in the baking oven then, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Claims (8)
1. organic and inorganic composite coating material with chrysanthemum shape micro-nano structure, it is characterized in that: wt% counts by weight percentage:
Hybridized nanometer silicon-dioxide 0.1-10 wt%
Nonfluorinated vinyl monomer 2-30 wt%
Fluorinated vinyl monomer 0.5-12wt%
Initiator 0.05-2wt%
Tensio-active agent 0.03-2wt%
Sodium bicarbonate 0.5-5wt%
Surplus is a deionized water.
2. according to the described organic and inorganic composite coating material of claim l, it is characterized in that the particle diameter of described hybridized nanometer silicon-dioxide is 100-500nm with chrysanthemum shape micro-nano structure.
3. the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure according to claim 1 is characterized in that described fluorinated vinyl monomer is the fluoroacrylate monomer.
4. according to the described organic and inorganic composite coating material of claim l, it is characterized in that described nonfluorinated vinyl monomer is one or more in methacrylic ester, alkenyl aromatic compound or the acrylate monomer with chrysanthemum shape micro-nano structure.
5. the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure according to claim 1 is characterized in that described initiator is persulphate or water-soluble azo initiator.
6. according to the described organic and inorganic composite coating material of claim l, it is characterized in that described tensio-active agent is one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the stearic acid with chrysanthemum shape micro-nano structure.
7. the preparation method with organic and inorganic composite coating material of chrysanthemum shape micro-nano structure according to claim 1 is characterized in that this method comprises the steps:
1) with the vinylsiloxane is raw material, deionized water is a solvent, Sodium dodecylbenzene sulfonate is a tensio-active agent, under alkaline condition, press vinylsiloxane: deionized water: ammoniacal liquor: after the mass ratio of Sodium dodecylbenzene sulfonate=4-10:80-120:O.5-2.5:0.02-0.1 mixes, under 35-70 ℃ of temperature, stir 5-30h, obtain the hybridized nanometer silicon-dioxide of the two keys of surface band behind the centrifuge washing;
2) the hybridized nanometer silicon-dioxide in the step 1) is fully disperseed in deionized water, then with polymerization of vinyl monomer, vinyl monomer comprises fluorinated vinyl monomer and nonfluorinated vinyl monomer, the polymeric initiator is thermal initiator or water-soluble azo initiator, the employing sodium bicarbonate is a buffer reagent, about the pH value to 11 of regulation system; Earlier deionized water and hybridized nanometer silicon-dioxide are stirred 0.5-5h under nitrogen protection during preparation, be warming up to 75C and add sodium bicarbonate and initiator continuation stirring 0.5-5h, slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor then, stirring reaction 10-30h obtains the oyster white dispersion liquid;
3) with step 2) in the oyster white dispersion liquid be coated on the slide glass, be placed in the baking oven drying treatment under 40-60 ℃ temperature then, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
8. the preparation method with organic and inorganic composite coating material of chrysanthemum shape micro-nano structure according to claim 7, it is characterized in that the vinylsiloxane in the described step 1) can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
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| CN102294851A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | Hydrophobic scratch-resistant coating on organic polymer surface and preparation method thereof |
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| CN108395799A (en) * | 2018-03-26 | 2018-08-14 | 福建瑞森新材料股份有限公司 | Novel fluoropolymers anti-pollution flashover coating and preparation method |
| CN109880003A (en) * | 2019-03-19 | 2019-06-14 | 开翊新材料科技（上海）有限公司 | A kind of absorbability porous substrate surface treating agent and preparation method thereof |
| CN114195960A (en) * | 2021-12-09 | 2022-03-18 | 盐城工学院 | Synthetic method of water-repellent fluorine-containing polyacrylate/silicon dioxide composite material |
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