CN102086333B - 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
- Publication number
- CN102086333B CN102086333B CN 201010563630 CN201010563630A CN102086333B CN 102086333 B CN102086333 B CN 102086333B CN 201010563630 CN201010563630 CN 201010563630 CN 201010563630 A CN201010563630 A CN 201010563630A CN 102086333 B CN102086333 B CN 102086333B
- Authority
- CN
- China
- Prior art keywords
- organic
- vinyl monomer
- inorganic composite
- composite coating
- nano structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 with chrysanthemum shape micro-nano structure and make each method.
Background technology
The organic and inorganic compound coating is on the basis of the good characteristics such as the film-forming properties that keeps organic materials, the transparency, flexibility, have again the advantages such as the high rigidity of inorganic nano-particle and thermotolerance, nano hybridization structure formation is various, and can in sizable scope, regulate and control, can give compound coating with new function, therefore be subject to people and more and more pay attention to.At present, the method for the preparation of 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 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 occur between inorganic nano-particle and the polymkeric substance) first, and then are prepared into the coating with micro-nano structure.But the required electrochemical conditions that these preparation methods have and technique needs harsh, that have use a large amount of organic solvents or apparatus expensive to be difficult to obtain industrialized application at 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, 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 process is various, and processing condition are complicated.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of excellent performance, safety non-toxic, technique 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 only have excellent hydrophobic performance.
Technical scheme: the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure of the present invention by weight percentage wt% is 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 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) take vinylsiloxane as raw material, deionized water is solvent, Sodium dodecylbenzene sulfonate is 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) with step 1) in hybridized nanometer silicon-dioxide in deionized water, fully disperse, then with polymerization of vinyl monomer, vinyl monomer comprises fluorinated vinyl monomer and nonfluorinated vinyl monomer, the initiator of polymerization is thermal initiator or water-soluble azo initiator, the employing sodium bicarbonate is buffer reagent, about the pH value to 11 of regulation system; First 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, then slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor, 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, then be placed in the baking oven drying treatment under 40-60 ℃ temperature, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Described step 1) vinylsiloxane in can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
The present invention has prepared the hybridized nanometer silicon-dioxide of surface with two keys according to emulsion polymerization.Hybridized nanometer dioxy gasification silicon is take vinylsiloxane as raw material, the silicon-dioxide that is different from the preparation take tetraethoxy as raw material, the surface is not contained-the Si-OH key, but enrichment a large amount of-Si-CH=CH2 key, therefore hydridization silicon-dioxide has good hydrophobic lipophilicity, and since surface enrichment two key groups, preparation organic-need not silicon-dioxide is carried out surface treatment during the inorganic compounding emulsion, 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; then the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer slowly splash in the reactor; 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 with organic and inorganic compound coating of chrysanthemum shape micro-nano structure that the present invention proposes, 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, can simplify experimental procedure, can guarantee that again polymkeric substance is in the grafting amount of 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 large roughness, make coating have excellent hydrophobic performance, 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) take vinylsiloxane as raw material, deionized water is 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) with step 1) in hybridized nanometer silicon-dioxide in deionized water, fully disperse, then with polymerization of vinyl monomer, vinyl monomer comprises fluorinated vinyl monomer and nonfluorinated vinyl monomer, the initiator of polymerization is thermal initiator or water-soluble azo initiator, the employing sodium bicarbonate is buffer reagent, about the pH value to 11 of regulation system; First 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; then slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor; 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 deionized water.
3) with step 2) in the oyster white dispersion liquid be coated on the slide glass, then be placed in the baking oven drying treatment under certain temperature, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Among the present invention, described step 1) vinylsiloxane in can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
The surface of adopting among the present invention, described step 1) is with 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, such as methacrylic acid 17 fluorine esters in the last of the ten Heavenly stems, methacrylic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, 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, such 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, such 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, described step 3) the drying treatment temperature in is 40-60 ℃.
Embodiment 1:
(1) in the 250ml four-hole boiling flask, adds successively deionized water, vinyltriethoxysilane, ammoniacal liquor and Sodium dodecylbenzene sulfonate 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, then incite somebody to action the vinylbenzene that contains 2g of supersound process 10min, 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, then under 45 ℃, is placed on drying treatment in the baking oven, 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, then incite somebody to action the vinylbenzene that contains 3g of supersound process 10min, 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, then under 50 ℃, is placed on drying treatment in the baking oven, obtain having the compound coating (seeing Fig. 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 processed 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, then under 45 ℃, is placed on drying treatment in the baking oven, 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, then incite somebody to action the vinylbenzene that contains 2.5g of supersound process 20min, 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, then under 45 ℃, is placed on drying treatment in the baking oven, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
Claims (7)
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 deionized water,
Preparation method with organic and inorganic composite coating material of chrysanthemum shape micro-nano structure comprises the steps:
1) take vinylsiloxane as raw material, deionized water is solvent, Sodium dodecylbenzene sulfonate is 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) with step 1) in hybridized nanometer silicon-dioxide in deionized water, fully disperse, then with vinyl
Monomer polymerization, vinyl monomer comprise fluorinated vinyl monomer and nonfluorinated vinyl monomer, and the initiator of polymerization is thermal initiator, and the employing sodium bicarbonate is buffer reagent, about the pH value to 11 of regulation system; First deionized water and hybridized nanometer silicon-dioxide are stirred 0.5-5h under nitrogen protection during preparation, be warming up to 75 ℃ and add sodium bicarbonate and initiator continuation stirring 0.5-5h, then slowly splash into the tensio-active agent of supersound process 5-30min and the mixed solution of vinyl monomer in the reactor, 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, then be placed in the baking oven drying treatment under 40-60 ℃ temperature, obtain having the compound coating of chrysanthemum shape micro/nano level coarse structure.
2. according to the described organic and inorganic composite coating material with chrysanthemum shape micro-nano structure of claim l, it is characterized in that the particle diameter of described hybridized nanometer silicon-dioxide is 100-500nm.
3. the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure according to claim 1,
It is characterized in that described fluorinated vinyl monomer is the fluoroacrylate monomer.
4. according to the described organic and inorganic composite coating material with chrysanthemum shape micro-nano structure 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.
5. the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure according to claim 1,
It is characterized in that described initiator is persulphate or water-soluble azo initiator.
6. according to the described organic and inorganic composite coating material with chrysanthemum shape micro-nano structure of claim l, its
Be characterised in that described tensio-active agent is one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the stearic acid.
7. the organic and inorganic composite coating material with chrysanthemum shape micro-nano structure according to claim 1, it is characterized in that described step 1) in vinylsiloxane can adopt γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyltriacetoxy silane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010563630 CN102086333B (en) | 2010-11-29 | 2010-11-29 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010563630 CN102086333B (en) | 2010-11-29 | 2010-11-29 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102086333A CN102086333A (en) | 2011-06-08 |
| CN102086333B true CN102086333B (en) | 2013-04-03 |
Family
ID=44098340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010563630 Active CN102086333B (en) | 2010-11-29 | 2010-11-29 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102086333B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294851A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | Hydrophobic scratch-resistant coating on organic polymer surface and preparation method thereof |
| CN108250371B (en) * | 2016-12-28 | 2020-06-02 | 北京化工大学 | Bonding type polymer/silicon dioxide hybrid material and preparation method thereof |
| 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 |
| CN109880003B (en) * | 2019-03-19 | 2021-07-16 | 开翊新材料科技（上海）有限公司 | Absorbent 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 |
| CN115820058B (en) * | 2022-12-17 | 2023-09-29 | 沪宝新材料科技（上海）股份有限公司 | Noise-reducing water-based exterior wall paint and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690142A (en) * | 2004-04-19 | 2005-11-02 | 河南大学 | Process for preparing fluorine-containing nano SiO2 composite non-adhesive coating materials |
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
| CN101288832A (en) * | 2008-06-13 | 2008-10-22 | 哈尔滨工业大学 | Organic inorganic hybridization cation exchange membrane filled with nano granules and preparation method thereof |
| CN101372562A (en) * | 2008-10-09 | 2009-02-25 | 浙江工业大学 | UV photo-curing hydrophobic antifouling paint and preparation thereof |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
-
2010
- 2010-11-29 CN CN 201010563630 patent/CN102086333B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690142A (en) * | 2004-04-19 | 2005-11-02 | 河南大学 | Process for preparing fluorine-containing nano SiO2 composite non-adhesive coating materials |
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
| CN101288832A (en) * | 2008-06-13 | 2008-10-22 | 哈尔滨工业大学 | Organic inorganic hybridization cation exchange membrane filled with nano granules and preparation method thereof |
| CN101372562A (en) * | 2008-10-09 | 2009-02-25 | 浙江工业大学 | UV photo-curing hydrophobic antifouling paint and preparation thereof |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102086333A (en) | 2011-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102086333B (en) | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof | |
| CN102351983B (en) | Fluorine silicon acrylate copolymer, preparation process thereof and application thereof | |
| CN102731735B (en) | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method | |
| CN101649152B (en) | Environmentally-friendly organic inorganic hybridized paint and preparation method and application thereof | |
| CN103435742B (en) | Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application | |
| CN102585073B (en) | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof | |
| CN104558447B (en) | Inorganic nano composite anti-doodling resin and preparation method thereof | |
| CN103289031B (en) | High-transparency super-hydrophobicity coating material and application thereof | |
| CN102911308B (en) | Method for preparing fluorine contained polyacrylate/dual-sized nano SiO2 composite emulsion | |
| CN103724558B (en) | A kind of strawberry type structure inorganic/organic fluoride-containing microballoon and preparation method thereof and application | |
| CN105111875A (en) | Self-cleaning nano protective liquid used for glass and preparation method | |
| CN102093697A (en) | Lotus leaf surface-imitated super-hydrophobic film and preparation method thereof | |
| CN101899251B (en) | Paint for coating surface of sanitary ware made of composite materials and preparation method thereof | |
| CN105601799A (en) | Core/shell type organosilicone-modified acrylate emulsion and preparation method and application thereof | |
| CN102241937B (en) | POSS (polyhedral oligomeric silsesquioxane)-modified aqueous nano transparent heat-insulation coating and preparation method thereof | |
| CN103602193A (en) | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof | |
| CN101948561A (en) | Organic/inorganic silicon hybrid resin for coating and preparation method thereof | |
| CN103387645B (en) | Fluorinated copolymer Grafted Nano-scale TiO 2composite particles and preparation method thereof | |
| CN102391412A (en) | Organosilicon-modified acrylate core-shell emulsion capable of filming at room temperature and preparation method as well as application thereof | |
| CN103665280A (en) | Multifunctional fluorine-containing microsphere as well as preparation method and application thereof | |
| CN103627286A (en) | Water-based finishing coat for heavy-duty coating and preparation method of water-based finishing coat | |
| CN102558993B (en) | Nano-silica/silicone-acrylate composite icing-resistant coating, and preparation method and application thereof | |
| CN105348549B (en) | A kind of preparation method of ageing-resistant super-hydrophobic hybrid film | |
| CN106752606B (en) | A kind of aqueous fluorine silica acrylic acid coating and preparation method thereof | |
| CN113185134B (en) | Antireflection coating liquid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220412 Address after: No.8, Huangguan Road, high tech Zone, Anqing City, Anhui Province Patentee after: Anhui footprint New Material Technology Co.,Ltd. Address before: 213034 Jiangsu Changzhou New Zone hundred Zhangs Industrial Park Patentee before: JIANGSU FOOTMARK PAINT CO.,LTD. |
|
| TR01 | Transfer of patent right |