CN103288364A - Preparation method of super-hydrophobic surface of glass - Google Patents
Preparation method of super-hydrophobic surface of glass Download PDFInfo
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- CN103288364A CN103288364A CN2012105521364A CN201210552136A CN103288364A CN 103288364 A CN103288364 A CN 103288364A CN 2012105521364 A CN2012105521364 A CN 2012105521364A CN 201210552136 A CN201210552136 A CN 201210552136A CN 103288364 A CN103288364 A CN 103288364A
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Abstract
The invention relates to the field of super-hydrophobic surfaces. In order to solve the problems of poor binding force between the existing super-hydrophobic SiO2 micro-nano double rough structural layer and a glass substrate and insufficient hydrophobicity, the invention provides a preparation method of the super-hydrophobic surface of glass. The method comprises the following steps of: firstly, preparing fluorosilicone modified acrylic ester emulsion; secondly, preparing modified SiO2 sol; and finally preparing the super-hydrophobic surface of glass. The preparation method is simple and low in cost; a hydrophobic coating has excellent hydrophobicity and has excellent binding force with the glass; and the coating can maintain super-hydrophobicity for a long time.
Description
Technical field
The present invention relates to the super hydrophobic surface field, particularly a kind of preparation method of glass super hydrophobic surface and application.
Background technology
Surface wettability is one of critical nature of solid surface.When referring to solid surface and water contact angle greater than 150 °, the surface has super-hydrophobicity.The professor W.Barthlott of Univ Bonn Germany and C.Neinhuis think that by the observation to the leaf surface microstructure the little mastoid process of micron order of uneven surface and the existence of surperficial wax make it have ultra-hydrophobicity.River thunder academicians etc. find also to have nanostructure on the mastoid process of lotus leaf surface micrometer structure on the basis of this research, have disclosed the lotus leaf effect reason, and these preparation and researchs that are found to be super hydrophobic surface provide developing direction.Because its unique surface property has important Research Significance in daily life and industrial circle.As make a super hydrophobic surface at glass surface, then can prevent contamination by dust by super hydrophobic surface, also can suppress microorganism adhering at glass surface, thereby can be used as the automatically cleaning material of glass surface.Popularizing with increasing of Highrise buildings of automobile makes that the glass with self-cleaning function is paid close attention to widely.Prepare super hydrophobic surface at glass surface, become the focus of research.
The preparation super hydrophobic surface mainly contains two kinds of approach: a kind of is to make up micro-nano pair of coarse structure on the hydrophobic material surface; Another kind is to obtain rough surface structure earlier, modifies the low surface energy material at uneven surface then.Low-surface-energy material is the basic substance that obtains super hydrophobic surface, and low-surface-energy material commonly used has fluorocarbon resin, fluorine silicon resin, silicone resin etc.Most importantly the thermoset polysiloxane system that has highly cross-linked structure in the silicone resin, because Si-O key bond energy height, big, the Si-O-Si main chain softness of bond angle, side-chain radical plays shielding effect to main chain, and the singularity of these chain structures is given the performance of the many excellences of organosilicon polymer.SiO
2As the simplest unit of silica segment in the silicone resin, have characteristics such as preparation technology is simple, production cost is low.
The method for preparing at present super hydrophobic surface mainly contains phase separation method, template, sol-gel method, etching method, photochemical method, chemical Vapor deposition process etc.Sol-gel method is preparation super hydrophobic surface modal method, adopts this method control surface structure preferably, effectively regulates and improves surfaceness, gives the super-hydrophobicity of filming.Sol-gel method reaction conditions gentleness, normal temperature and pressure gets final product, thereby is widely adopted.Yet, by the super-hydrophobicity SiO of Prepared by Sol Gel Method
2When using, poor with the cohesive force of glass baseplate, wear resistance is poor, and very easily wearing and tearing in the use causes hydrophobicity to reduce, so the application of glass super hydrophobic surface never has industrialization.
Chinese patent CN20120110100 discloses a kind of preparation method of glass super hydrophobic surface, and this method is by the SiO of electro-deposition techniques formation of deposits one deck rough porous
2Film is modified deposition surface with chain alkyl siloxanes hydrolyzed solution then.For improving SiO
2Thin-film hydrophobic is with porous SiO
2Film immerses chain alkyl siloxanes hydrolyzed solution, so that the long-chain hydrophobic grouping is deposited on film surface.But SiO
2Between film self and the matrix, to form the SiO of the two coarse structures of little sodium rice
2Link to each other with matrix, cause cohesive force and wear resistance poor, very easily wearing and tearing in the use causes hydrophobicity to reduce, and therefore causes hydrophobic surface short work-ing life, needs the repetition dip-coating to obtain super-hydrophobicity again.
Summary of the invention
For overcoming present super-hydrophobic SiO
2The two coarse structure layers of little sodium rice and substrate of glass cohesive force are poor, problems such as hydrophobicity deficiency, the present invention proposes a kind of preparation method of glass super hydrophobic surface, this method for preparing super-hydrophobic surface is simple, cost is low, hydrophobic coating not only has excellent hydrophobicity, and good bonding force between coating and the glass, can guarantee that coating keeps its super-hydrophobicity for a long time.
The present invention is achieved by the following technical solutions: a kind of preparation method of glass super hydrophobic surface, the preparation method of described glass super hydrophobic surface are following steps:
(1) prepare fluorinated silicone modified acrylic ester emulsion,
(2) preparation modification SiO
2Colloidal sol,
(3) preparation glass super hydrophobic surface.
1, fluorinated silicone modified acrylic ester emulsion is prepared from by following each component in the step (1), and concrete preparation process is as follows:
(a) weight part of described fluorinated silicone modified acrylic ester emulsion each component is:
(b) take by weighing above-mentioned each component by the each component umber, alkyl methacrylate, alkyl acrylate are mixed and made into the monomer I, vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II, as preferably, the mass ratio of monomer I and monomer II is 2 ~ 4:1;
(c) 55% ~ 75% water, 50% ~ 80% emulsifying agent, 60% ~ 85% initiator, pH regulator agent in the component are added in the reactor, stir and be warming up to 75 ~ 80 ℃ after 10 ~ 20 minutes, get 10% ~ 20% in the monomer I in 15 ~ 30 minutes adding reactors, dropwise the back insulation after 15 ~ 30 minutes, again 50% ~ 70% in the monomer I was added drop-wise in the reactor in 2.5 ~ 4 hours, dropwises the back insulation and obtain emulsion after 15 ~ 30 minutes;
(d) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir was added drop-wise in the emulsion that obtains in the step (c) in 0.5 ~ 1.5 hour continuously; Dropwise afterreaction 0.5 ~ 1 hour, and be warming up to 80 ~ 85 ℃ of insulations 1 ~ 2 hour again, be cooled to 40 ~ 50 ℃ then, filter discharging, obtain fluorinated silicone modified acrylate polymer emulsion.Per 20 ~ 40 minutes measured reaction system pH in the reaction process are regulated the pH value between 6.0 ~ 7.0, use the pH value of the material conditioned reaction system identical with pH regulator agent composition in this step.
The joining day that step (c), (d) limit material is for keeping thermal equilibrium and the reaction mass certain reaction speed in the reactor, and different weight of material can be by keeping the speed of response of material at the reactor of corresponding size.
In the described fluorinated silicone modified acrylic ester emulsion each component:
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three butoxy silanes, γ-methacryloxypropyl trimethoxy silane, the γ-methacryloxypropyl triethoxyl silane;
Described vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester are selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-3-hydroxy propyl ester;
Described fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are selected from vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, the vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid ten trifluoro octyl group ethyl esters, methacrylic acid ten trifluoro octyl group ethyl esters, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, methacrylic acid ten trifluoro monooctyl esters, dodecafluorhe-ptylacrylate, a kind of in the methacrylic acid ten difluoro heptyl esters;
Described initiator is selected from persulfuric acid salt system, as preferably, is selected from the mixture of one or more arbitrary proportions in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate;
Described emulsifying agent is anionic emulsifier and reactive emulsifier compound, reactive emulsifier is 1 ~ 4 times of anionic emulsifier quality, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl phenyl ether disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), the sodium lauryl sulphate (SDS); Reactive emulsifier is selected from 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt (AMPS-Na), 2-acrylamido-2-methyl-propyl sulfonic acid ammonium salt (AMPS-NH
4), the mixture of one or more arbitrary proportions in the 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium (HAPS), 2-acrylamido tetradecane sulfonate sodium (NaAMC14S), hydroxyethyl methacrylate propanesulfonic acid sodium (HPMAS);
Described pH regulator agent is selected from the mixture of one or more arbitrary proportions in sodium bicarbonate, saleratus, Sodium phosphate dibasic, the dipotassium hydrogen phosphate;
Described water is deionized water.
The present invention has prepared fluorinated silicone modified acrylic ester emulsion by the principle of particle design.With the organosilane monomer of low surface energy and fluorine-containing alkyl ester or the design of fluorine-containing alkyl methacrylate monomer at the particle shell, fluorine silicone content and distribution thereof are from micelle radius about 50 ~ 70% to surperficial progressive increases, can give full play to the hydrophobic interaction of fluorine silicon segment, use a spot of organosilicon, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate monomer can reach the good hydrophobic effect, water contact angle can reach 110 ~ 120 °.On the other hand, adopt the reinforced method of gradient, the organosilicon of adding and fluorochemical monomer and emulsion particle are whole phenomenon of phase separation can not to take place in conjunction with very tight, makes film coated surface have stable performance.
2, modification SiO in the step (2)
2Colloidal sol is prepared from by following each component, and concrete preparation process is as follows,
(a) described modification SiO
2The weight part of colloidal sol each component is:
(b) take by weighing above-mentioned each component by the each component umber, tetraalkyl orthosilicate is added drop-wise in the mixing solutions of water, basic catalyst and alcohol composition, at 50 ~ 70 ℃ of hydrolysis 1 ~ 6h, make hydrolyzed solution A;
(c) methyl trialkoxysilane is added drop-wise among the said hydrolyzed liquid A, continues hydrolysis 1 ~ 6h, make hydrolyzed solution B;
(d) chain alkyl trialkoxy silane or long chain fluorine-containing alkyltrialkoxysilaneand are joined among the hydrolyzed solution B, hydrolysis 1 ~ 6h is cooled to room temperature behind insulation 12 ~ 24h again, obtains modification SiO
2Colloidal sol.
Modification SiO
2Whole process system keeps whipped state in the colloidal sol preparation process.
Described modification SiO
2In the colloidal sol each component:
Described tetraalkyl orthosilicate is selected from a kind of in methyl silicate, tetraethoxy, the butyl silicate;
Described alcohol is selected from a kind of in methyl alcohol, ethanol, the butanols, as preferably, and the alcohol that described alcohol is identical with moieties in the tetraalkyl orthosilicate;
Described methyl trialkoxysilane is selected from a kind of in methyltrimethoxy silane, Union carbide A-162, methyl three butoxy silanes, and as preferably, described methyl trialkoxysilane is identical with moieties in the alcohol;
Described chain alkyl trialkoxy silane or long chain fluorine-containing alkyltrialkoxysilaneand are selected from the octyl group Trimethoxy silane, the dodecyl Trimethoxy silane, ten trifluoro octyl group Trimethoxy silanes, the hexadecyl Trimethoxy silane, the octadecyl Trimethoxy silane, the perfluoro capryl Trimethoxy silane, 17 fluorine decyl Trimethoxy silanes, octyltri-ethoxysilane, the dodecyl triethoxyl silane, ten trifluoro octyltri-ethoxysilane, the hexadecyl triethoxyl silane, octadecyltriethoxy silane, the perfluoro capryl triethoxyl silane, in the 17 fluorine decyl triethoxyl silanes one or more;
Described basic catalyst is selected from a kind of in ammoniacal liquor, Tetramethylammonium hydroxide, the tetraethyl ammonium hydroxide;
Described water is deionized water.
Described preparation method's room temperature is commonly referred to as 25 ℃, and pressure is 101 kPas.
The fluorinated silicone modified acrylic ester emulsion of the present invention with improve and substrate of glass between cohesive force, and provide a kind of by forming SiO
2The two coarse structures of little sodium rice, introducing chain alkyl or long chain fluorine-containing alkyl are to improve its hydrophobic method.Fluorine silicone content and functional group thereof distribute from micelle radius 50 ~ 70% to surperficial progressive increase in the fluorinated silicone modified acrylic ester emulsion, mainly be distributed in shell and can give full play to the effect of fluorine silicon low-surface-energy segment, the emulsion film water contact angle can reach 110 ~ 120 °, and glass uses modification SiO after fluorinated silicone modified acrylic ester emulsion is filmed
2During colloidal sol, SiO
2Two coarse structures of little sodium rice that colloidal sol self forms and in chain alkyl or the acting in conjunction of long chain fluorine-containing alkyl of glass coating film surface grafting can further improve its surface hydrophobicity.The present invention adopts chain alkyl siloxanes or long chain fluorine-containing alkylsiloxane modification SiO
2, by sol-gel method at SiO
2Grafting methyl and chain alkyl or long chain fluorine-containing alkyl on the particle are at SiO
2After forming the two coarse structures of micro-nano on the particle, because chain alkyl or long chain fluorine-containing alkyl surface energy are low, can further improve the hydrophobicity of film coated surface, water contact angle can reach more than 155 °.
3, conventional spin-coating method or the dip-coating method that uses of present liquid film processed adopted in the preparation of glass super hydrophobic surface in the step (3).
The spin-coating method step is: will take out after fluorinated silicone modified acrylic ester emulsion 2 ~ 10 min of sheet glass spin coating in the spin coating instrument, self-vulcanizing 1 ~ 3 h is then with curing glass sheet spin coating modification SiO in the spin coating instrument
2Colloidal sol 2 ~ 5min treats to repeat spin coating 3 ~ 5 times after the surface drying, places 1 ~ 2h at last in 100 ~ 120 ℃ of baking ovens.
The dip-coating method step is: sheet glass is immersed in the fluorinated silicone modified acrylic ester emulsion take out after 2 ~ 10 min, self-vulcanizing 1 ~ 3 h immerses sheet glass modification SiO then
2Among 2 ~ 10min, repeat to lift 3 ~ 5 times in the colloidal sol, in 100 ~ 120 ℃ of baking ovens, place 1 ~ 2h.
The invention provides a kind of preparation method of glass super hydrophobic surface, film and substrate of glass cohesive force and chain alkyl siloxanes or the super-hydrophobic SiO of long chain fluorine-containing alkylsiloxane modification by preparing fluorinated silicone modified acrylic ester emulsion enhancing
2Colloidal sol improves hydrophobicity.Fluorinated silicone modified acrylic ester emulsion has been introduced organo-siloxane and fluorochemical monomer, F-Si hydrophobic group and functional group thereof that polymer emulsion is formed micelle distribute from micelle radius 50 ~ 70% to surperficial progressive increase, fluorine silicon segment and other set of monomers become content to increase gradually, have eliminated the difference of particle composition structure.On the other hand, when emulsion particle solidified, the F-Si hydrophobic segment mainly concentrated on the skin of particle, moves to film coated surface easily, can give full play to the effect of F-Si hydrophobic group, has improved the product price ratio.Modification SiO
2Colloidal sol is grafted on SiO by sol-gel method with chain alkyl or long chain fluorine-containing alkyl
2On the particle, can form the two coarse structures of micro-nano.The introducing of long chain fluorine-containing alkylsiloxane makes this coarse structure surface have lower surface energy, and hydrophobicity further strengthens.Preparation is during super hydrophobic surface, with fluorinated silicone modified acrylic ester emulsion as filmogen, with the hydrophobic SiO of long chain fluorine-containing alkylsiloxane modification
2Colloidal sol forms micro-nano structure in film coated surface, fluorine silicon low-surface-energy and the SiO of film coated surface
2The excellent super-hydrophobicity of filming has been given in the two coarse structure actings in conjunction of micro-nano.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention has prepared fluorinated silicone modified acrylic ester emulsion by the principle of particle design.With the organosilane monomer of low surface energy and fluorine-containing alkyl ester or the design of fluorine-containing alkyl methacrylate monomer at the particle shell, fluorine silicone content and distribution thereof are from micelle radius about 50 ~ 70% to surperficial progressive increases, can give full play to the hydrophobic interaction of fluorine silicon segment, use a spot of organosilicon, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate monomer can reach the good hydrophobic effect, water contact angle can reach 110 ~ 120 °.On the other hand, adopt the reinforced method of gradient, the organosilicon of adding and fluorochemical monomer and emulsion particle are whole phenomenon of phase separation can not to take place in conjunction with very tight, makes film coated surface have stable performance.
(2) the present invention adopts chain alkyl siloxanes or long chain fluorine-containing alkylsiloxane modification SiO
2, by sol-gel method at SiO
2Grafting methyl and chain alkyl or long chain fluorine-containing alkyl on the particle are at SiO
2After forming the two coarse structures of micro-nano on the particle, because chain alkyl or long chain fluorine-containing alkyl surface energy are low, can further improve the hydrophobicity of film coated surface, water contact angle can reach more than 155 °.
(3) method for preparing super-hydrophobic surface of the present invention is simple, and cost is low, and hydrophobic coating not only has excellent hydrophobicity, and good bonding force between coating and the glass, can guarantee that coating keeps its super-hydrophobicity for a long time.
Embodiment
Be described in further detail below in conjunction with the present invention of embodiment, raw materials used all commercially available among the embodiment, need to prove that embodiment does not constitute limiting the scope of the invention.
Embodiment 1:
(1), prepares fluorinated silicone modified acrylic ester emulsion;
(a) fluorinated silicone modified acrylic ester emulsion each component is as shown in table 1 below.Alkyl methacrylate, alkyl acrylate in the step component are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(b) 55%, 60% Potassium Persulphate, sodium bicarbonate with 55% water, SDS and AMPS-Na mixture quality in the step (a) adds in the reactor, stir and be warming up to 75 ℃ after 15 minutes, get the monomer I 10% in 15 minutes adding reactors, dropwise back insulation 15 minutes, again 50% of monomer I was added drop-wise in the reactor in 2.5 hours, dropwise back insulation 15 minutes, obtain emulsion;
(c) remaining emulsifying agent and initiator are dissolved in the residual ion water make mixing solutions, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir was added drop-wise in the emulsion that obtains in the above-mentioned steps in 0.5 hour continuously; Dropwise afterreaction and be warming up to 80 ℃ of insulations 1 hour after 1 hour again, be cooled to 40 ℃ then, filter discharging and get fluorinated silicone modified acrylate polymer emulsion.
Per 20 minutes measured reaction system pH in step (c) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
(2), preparation modification SiO
2Colloidal sol;
(a) 1 part of tetraethoxy is added drop-wise in the mixing solutions of 8 parts of deionized waters, 6 parts of ammoniacal liquor, 40 parts of ethanol compositions, 60 ℃ of hydrolysis 2h make hydrolyzed solution A;
(b) 1 part of Union carbide A-162 is added drop-wise among the hydrolyzed solution A, continues hydrolysis 2h, make hydrolyzed solution B.
(c) 1.5 parts of octyltri-ethoxysilane are joined among the hydrolyzed solution B, continue hydrolysis 2h, be cooled to room temperature behind the insulation 24h.Whole process system keeps stirring, and obtains modification SiO
2Colloidal sol.
(3), preparation glass super hydrophobic surface
Adopt the spin-coating method step to be: will take out after fluorinated silicone modified acrylic ester emulsion 5 min of sheet glass spin coating in the spin coating instrument, self-vulcanizing 1 h is then with curing glass sheet spin coating modification SiO in the spin coating instrument
2Colloidal sol 3 min treat to repeat spin coating 3 times after the surface drying, place 1 h at last in 100 ℃ of baking ovens.
In the fluorinated silicone modified acrylic ester emulsion preparation process, step (b) average particle size is about 65nm, and final median size is 105nm, narrow diameter distribution.Transmission electron microscope (TEM) analysis shows the latex particle size evenly, is the sphere of rule.Ultimate analysis shows that from 65nm to 105nm, particle fluorine silicone content increases gradually.Scanning electron microscope (SEM) analysis revealed emulsion has good film-forming properties, the fine and close no phenomenon of phase separation of film forming.The emulsion film water contact angle is 112 °.The modification SiO that makes
2Colloidal sol shows SiO through infrared analysis (FTIR)
2Particle is methyl and octyl group in the grafting.Filming of making carried out atomic force microscope (AFM) is analyzed and Static Water contact angle test (WCA) test, film coated surface has micro-nano pair coarse structures as a result, and water contact angle is 156 °, has super-hydrophobicity.
Embodiment 2:
(1), prepares fluorinated silicone modified acrylic ester emulsion;
(a) fluorinated silicone modified acrylic ester emulsion component is as shown in table 2 below.Alkyl methacrylate, alkyl acrylate in the step component are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(b) with 65% water, LAS and AMPS-NH in the step (a)
465%, 70% ammonium persulphate of mixture quality, saleratus add in the reactor, stir and be warming up to 78 ℃ after 20 minutes, get the monomer I 20% in 20 minutes adding reactors, dropwise the back insulation after 20 minutes, again 60% of monomer I was added drop-wise in the reactor in 3.5 hours, dropwise back insulation 20 minutes, obtain emulsion;
(c) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir is in 1.5 hours, be added drop-wise to continuously in the emulsion that obtains in the step (c), dropwised afterreaction 1 hour, be warming up to 83 ℃ of insulations 1.5 hours again, be cooled to 45 ℃ then, filter discharging and get fluorinated silicone modified acrylate polymer emulsion.
Per 30 minutes measured reaction system pH in step (c) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
(2), preparation modifying super hydrophobicity SiO
2Colloidal sol;
(a) 6 parts of methyl silicates are added drop-wise in the mixing solutions of 15 parts of deionized waters, 15 parts of Tetramethylammonium hydroxide, 70 parts of methyl alcohol compositions, 70 ℃ of hydrolysis 1h make hydrolyzed solution A;
(b) 3 parts of methyltrimethoxy silanes are added drop-wise among the hydrolyzed solution A, hydrolysis 2h makes hydrolyzed solution B again.
(c) 4 parts of dodecyl Trimethoxy silanes are joined among the hydrolyzed solution B, hydrolysis 3h is cooled to room temperature behind the insulation 18h again, obtains modification SiO
2Colloidal sol, whole process system keep stirring.
(3), preparation glass super hydrophobic surface
Adopt dip-coating method that sheet glass is immersed in the fluorinated silicone modified acrylic ester emulsion and take out after 3 min, self-vulcanizing 3h immerses sheet glass modification SiO then
2Among the 10min, repeat to lift 5 times in the colloidal sol, in 110 ℃ of baking ovens, place 2h, namely get and have super-hydrophobic filming.
In the fluorinated silicone modified acrylic ester emulsion preparation process, step (2) average particle size is 62nm, and final median size is 110nm, narrow diameter distribution.Transmission electron microscope (TEM) analysis shows the latex particle size evenly, is the sphere of rule.Ultimate analysis shows that from 62nm to 110nm, particle fluorine silicone content increases gradually.Scanning electron microscope (SEM) analysis revealed emulsion has good film-forming properties, the fine and close no phenomenon of phase separation of film forming.The emulsion film water contact angle is 115 °
The modification SiO that makes
2Colloidal sol shows SiO through infrared analysis (FTIR)
2Particle is methyl and dodecyl in the grafting.Filming of making carried out atomic force microscope (AFM) is analyzed and Static Water contact angle test (WCA) test, film coated surface has micro-nano pair coarse structures as a result, and water contact angle is 159 °, has super-hydrophobicity.
Embodiment 3:
(1), prepares fluorinated silicone modified acrylic ester emulsion;
(a) fluorinated silicone modified acrylic ester emulsion component is as shown in table 3 below.Alkyl methacrylate, alkyl acrylate in the step component are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(b) 75%, 75% Sodium Persulfate, potassium primary phosphate with 55% water, DSB and HPMAS mixture quality in the step (a) adds in the reactor, stir and be warming up to 80 ℃ after 15 minutes, get the monomer I 15% in 30 minutes adding reactors, dropwise the back insulation after 30 minutes, again 60% of monomer I was added drop-wise in the reactor in 4 hours, dropwise back insulation 25 minutes, obtain emulsion;
(c) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir is in 1 hour, be added drop-wise to continuously in the emulsion that obtains in the step (c), dropwised afterreaction 1 hour, be warming up to 85 ℃ of insulations 2 hours again, be cooled to 50 ℃ then, filter discharging and get fluorinated silicone modified acrylate polymer emulsion.
Per 30 minutes measured reaction system pH in step (c) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
(2), preparation modifying super hydrophobicity SiO
2Colloidal sol;
(a) 10 parts of tetraethoxys are added drop-wise in the mixing solutions of 10 parts of deionized waters, 15 parts of tetraethyl ammonium hydroxides, 80 parts of ethanol compositions, 70 ℃ of hydrolysis 1h make hydrolyzed solution A;
(b) 5 parts of Union carbide A-162s are added drop-wise among the hydrolyzed solution A, hydrolysis 3h makes hydrolyzed solution B again.
(c) 2 parts of octadecyltriethoxy silane are joined among the hydrolyzed solution B, hydrolysis 6h is cooled to room temperature behind the insulation 18h again, obtains modification SiO
2Colloidal sol, whole process system keep stirring.
(3), preparation glass super hydrophobic surface
Adopt the spin-coating method step to be: will take out after fluorinated silicone modified acrylic ester emulsion 8 min of sheet glass spin coating in the spin coating instrument, self-vulcanizing 2.5 h are then with curing glass sheet spin coating modification SiO in the spin coating instrument
2Colloidal sol 4 min treat to repeat spin coating 4 times after the surface drying, place 1.5 h at last in 120 ℃ of baking ovens.
In the fluorinated silicone modified acrylic ester emulsion preparation process, step (b) average particle size is 60nm, and final median size is 114nm, narrow diameter distribution.Transmission electron microscope (TEM) analysis shows the latex particle size evenly, is the sphere of rule.Ultimate analysis shows that from 60nm to 114nm, particle fluorine silicone content increases gradually.Scanning electron microscope (SEM) analysis revealed emulsion has good film-forming properties, the fine and close no phenomenon of phase separation of film forming.The emulsion film water contact angle is 114 ° of modification SiO that make
2Colloidal sol shows SiO through infrared analysis (FTIR)
2Particle is methyl and octadecyl in the grafting.Filming of making carried out atomic force microscope (AFM) is analyzed and Static Water contact angle test (WCA) test, film coated surface has micro-nano pair coarse structures as a result, and water contact angle is 160 °, has super-hydrophobicity.
Embodiment 4:
(1), prepares fluorinated silicone modified acrylic ester emulsion;
(a) fluorinated silicone modified acrylic ester emulsion component is as shown in table 4 below.Alkyl methacrylate, alkyl acrylate in the step component are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(b) 85%, 80% Sodium Persulfate, SODIUM PHOSPHATE, MONOBASIC with 75% water, SDS and HAPS mixture quality in the step (a) adds in the reactor, stir and be warming up to 75 ℃ after 20 minutes, get the monomer I 15% in 15 minutes adding reactors, dropwise the back insulation after 20 minutes, again 65% of monomer I was added drop-wise in the reactor in 2.5 hours, dropwise back insulation 30 minutes, obtain emulsion;
(c) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir is in 1.5 hours, be added drop-wise to continuously in the emulsion that obtains in the above-mentioned steps, dropwised afterreaction 0.5 hour, be warming up to 80 ℃ of insulations 1.5 hours again, be cooled to 40 ℃ then, filter discharging and get fluorinated silicone modified acrylate polymer emulsion.
Per 40 minutes measured reaction system pH in step (c) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
(2), preparation modifying super hydrophobicity SiO
2Colloidal sol;
(a) 10 parts of butyl silicates are added drop-wise in the mixing solutions of 20 parts of deionized waters, 15 parts of ammoniacal liquor, 80 parts of butanols compositions, 50 ℃ of hydrolysis 4h make hydrolyzed solution A;
(b) 5 parts of methyl three butoxy silanes are added drop-wise among the hydrolyzed solution A, hydrolysis 4h makes hydrolyzed solution B again.
(c) 4 part of 17 fluorine decyl Trimethoxy silane joined among the hydrolyzed solution B, hydrolysis 4h is cooled to room temperature behind the insulation 24h, obtains modification SiO
2Colloidal sol.Whole process system keeps stirring.
(3), preparation glass super hydrophobic surface
Adopt dip-coating method that sheet glass is immersed in the fluorinated silicone modified acrylic ester emulsion and take out after 8 min, self-vulcanizing 2.5h immerses sheet glass modification SiO then
2Among the 8min, repeat to lift 4 times in the colloidal sol, in 120 ℃ of baking ovens, place 1.5h, namely get and have super-hydrophobic filming.
In the fluorinated silicone modified acrylic ester emulsion preparation process, step (b) average particle size is 68nm, and final median size is 118nm, narrow diameter distribution.Transmission electron microscope (TEM) analysis shows the latex particle size evenly, is the sphere of rule.Ultimate analysis shows that from 68nm to 118nm, particle fluorine silicone content increases gradually.Scanning electron microscope (SEM) analysis revealed emulsion has good film-forming properties, the fine and close no phenomenon of phase separation of film forming.The emulsion film water contact angle is 110 ° of modification SiO that make
2Colloidal sol shows SiO through infrared analysis (FTIR)
2Particle is methyl and 17 fluorine decyls in the grafting.Filming of making carried out atomic force microscope (AFM) is analyzed and Static Water contact angle test (WCA) test, film coated surface has micro-nano pair coarse structures as a result, and water contact angle is 158 °, has super-hydrophobicity.
Embodiment 5:
(1), prepares fluorinated silicone modified acrylic ester emulsion;
(a) fluorinated silicone modified acrylic ester emulsion component is as shown in table 5 below.Alkyl methacrylate, alkyl acrylate in the step component are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(b) with 60% water, SDS and AMPS-NH in the step (a)
470%, 65% Potassium Persulphate of mixture quality, sodium bicarbonate add in the reactor, stir and be warming up to 77 ℃ after 15 minutes, get the monomer I 15% in 25 minutes adding reactors, dropwise the back insulation after 25 minutes, again 60% of monomer I was added drop-wise in the reactor in 3 hours, dropwise back insulation 25 minutes, obtain emulsion;
(c) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir is in 1.5 hours, be added drop-wise to continuously in the emulsion that obtains in the step (c), dropwised afterreaction 1 hour, be warming up to 82 ℃ of insulations 1 hour again, be cooled to 45 ℃ then, filter discharging and get fluorinated silicone modified acrylate polymer emulsion.
Per 30 minutes measured reaction system pH in step (c) reaction process are used sodium bicarbonate conditioned reaction system pH to 6.5 when the pH value is outside 6.0 ~ 7.0 intervals.
(2), preparation modifying super hydrophobicity SiO
2Colloidal sol;
(a) 5 parts of tetraethoxys are added drop-wise in the mixing solutions of 20 parts of deionized waters, 10 parts of tetraethyl ammonium hydroxides, 50 parts of ethanol compositions, 65 ℃ of hydrolysis 3h make hydrolyzed solution A;
(b) 2 parts of methyltrimethoxy silanes are added drop-wise among the hydrolyzed solution A, hydrolysis 3h makes hydrolyzed solution B again.
(c) 3 parts of dodecyl Trimethoxy silanes are joined among the hydrolyzed solution B, hydrolysis 3h is cooled to room temperature behind the insulation 18h again, obtains modification SiO
2Colloidal sol, whole process system keep stirring.
(3), preparation glass super hydrophobic surface
Adopt dip-coating method that sheet glass is immersed in the fluorinated silicone modified acrylic ester emulsion and take out after 5 min, self-vulcanizing 2h immerses sheet glass modification SiO then
2Among the 6min, repeat to lift 4 times in the colloidal sol, in 115 ℃ of baking ovens, place 2h, namely get and have super-hydrophobic filming.
In the fluorinated silicone modified acrylic ester emulsion preparation process, step (2) average particle size is 66nm, and final median size is 117nm, narrow diameter distribution.Transmission electron microscope (TEM) analysis shows the latex particle size evenly, is the sphere of rule.Ultimate analysis shows that from 66nm to 117nm, particle fluorine silicone content increases gradually.Scanning electron microscope (SEM) analysis revealed emulsion has good film-forming properties, the fine and close no phenomenon of phase separation of film forming.The emulsion film water contact angle is 114 °
The modification SiO that makes
2Colloidal sol shows SiO through infrared analysis (FTIR)
2Particle is methyl and dodecyl in the grafting.Filming of making carried out atomic force microscope (AFM) is analyzed and Static Water contact angle test (WCA) test, film coated surface has micro-nano pair coarse structures as a result, and water contact angle is 157 °, has super-hydrophobicity.
Claims (9)
1. the preparation method of a glass super hydrophobic surface is characterized in that, the preparation method of described glass super hydrophobic surface is following steps:
(1) prepare fluorinated silicone modified acrylic ester emulsion,
(2) preparation modification SiO
2Colloidal sol,
(3) preparation glass super hydrophobic surface.
2. the preparation method of a kind of glass super hydrophobic surface according to claim 1 is characterized in that, fluorinated silicone modified acrylic ester emulsion is prepared from by following each component in the step (1), and concrete steps are as follows:
(a) weight part of described fluorinated silicone modified acrylic ester emulsion each component is:
(b) take by weighing above-mentioned each component by the each component umber, alkyl methacrylate, alkyl acrylate are mixed and made into the monomer I, and vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester, organo-siloxane, fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are mixed and made into the monomer II;
(c) 55% ~ 75% water, 50% ~ 80% emulsifying agent, 60% ~ 85% initiator, pH regulator agent in the component are added in the reactor, stir and be warming up to 75 ~ 80 ℃ after 10 ~ 20 minutes, get 10% ~ 20% in the monomer I in 15 ~ 30 minutes adding reactors, dropwise the back insulation after 15 ~ 30 minutes, again 50% ~ 70% in the monomer I was added drop-wise in the reactor in 2.5 ~ 4 hours, dropwises the back insulation and obtain emulsion after 15 ~ 30 minutes;
(d) remaining emulsifying agent and initiator are dissolved in make mixing solutions in the surplus water, the mixing solutions that the monomer II is dropped in the monomer I and mixture and remaining water, emulsifying agent and the initiator of above-mentioned monomer I and monomer II are made when continuing to stir was added drop-wise in the emulsion that obtains in the step (c) in 0.5 ~ 1.5 hour continuously; Dropwise afterreaction 0.5 ~ 1 hour, and be warming up to 80 ~ 85 ℃ of insulations 1 ~ 2 hour again, be cooled to 40 ~ 50 ℃ then, filter discharging, obtain fluorinated silicone modified acrylate polymer emulsion.
3. the preparation method of a kind of glass super hydrophobic surface according to claim 2 is characterized in that, in the described fluorinated silicone modified acrylic ester emulsion each component:
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the Isooctyl acrylate monomer;
Described organo-siloxane is selected from the mixture of one or more arbitrary proportions in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three butoxy silanes, γ-methacryloxypropyl trimethoxy silane, the γ-methacryloxypropyl triethoxyl silane;
Described vinylformic acid hydroxyalkyl acrylate or methacrylic acid hydroxyl alkyl ester are selected from the mixture of one or more arbitrary proportions in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-3-hydroxy propyl ester;
Described fluorine-containing alkyl ester or fluorine-containing alkyl methacrylate are selected from vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, the vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid ten trifluoro octyl group ethyl esters, methacrylic acid ten trifluoro octyl group ethyl esters, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, methacrylic acid ten trifluoro monooctyl esters, dodecafluorhe-ptylacrylate, a kind of in the methacrylic acid ten difluoro heptyl esters;
Described initiator is selected from persulfuric acid salt system;
Described emulsifying agent is anionic emulsifier and reactive emulsifier compound, reactive emulsifier is 1 ~ 4 times of anionic emulsifier quality, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl phenyl ether disodium sulfonate, Sodium dodecylbenzene sulfonate, the sodium lauryl sulphate; Reactive emulsifier is selected from the mixture of one or more arbitrary proportions in 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt, 2-acrylamido-2-methyl-propyl sulfonic acid ammonium salt, 1-allyloxy-2-hydroxypropyl azochlorosulfonate acid sodium, 2-acrylamido tetradecane sulfonate sodium, the hydroxyethyl methacrylate propanesulfonic acid sodium;
Described pH regulator agent is selected from the mixture of one or more arbitrary proportions in sodium bicarbonate, saleratus, Sodium phosphate dibasic, the dipotassium hydrogen phosphate;
Described water is deionized water.
4. the preparation method of a kind of glass super hydrophobic surface according to claim 2, it is characterized in that, the mass ratio of the middle monomer I of step (b) and monomer II is 2 ~ 4:1 in the fluorinated silicone modified acrylic ester emulsion preparation process, per 20 ~ 40 minutes measured reaction system pH in step (d) reaction process, regulate the pH value between 6.0 ~ 7.0, use the pH value of the material conditioned reaction system identical with pH regulator agent composition in this step.
5. the preparation method of a kind of glass super hydrophobic surface according to claim 1 is characterized in that, modification SiO in the step (2)
2Colloidal sol is prepared from by following each component, and the concrete steps of preparation are as follows,
(a) described modification SiO
2The weight part of colloidal sol each component is:
(b) take by weighing above-mentioned each component by the each component umber, tetraalkyl orthosilicate is added drop-wise in the mixing solutions of water, basic catalyst and alcohol composition, at 50 ~ 70 ℃ of hydrolysis 1 ~ 6h, make hydrolyzed solution A;
(c) methyl trialkoxysilane is added drop-wise among the said hydrolyzed liquid A, hydrolysis 1 ~ 6h makes hydrolyzed solution B again;
(d) chain alkyl trialkoxy silane or long chain fluorine-containing alkyltrialkoxysilaneand are joined among the hydrolyzed solution B, hydrolysis 1 ~ 6h is cooled to room temperature behind insulation 12 ~ 24h again, obtains modification SiO
2Colloidal sol.Room temperature is 25 ℃.
6. the preparation method of a kind of glass super hydrophobic surface according to claim 4 is characterized in that, described modification SiO
2In the colloidal sol each component:
Described tetraalkyl orthosilicate is selected from a kind of in methyl silicate, tetraethoxy, the butyl silicate;
Described alcohol is selected from a kind of in methyl alcohol, ethanol, the butanols;
Described methyl trialkoxysilane is selected from a kind of in methyltrimethoxy silane, Union carbide A-162, methyl three butoxy silanes;
Described chain alkyl trialkoxy silane or long chain fluorine-containing alkyltrialkoxysilaneand are selected from the octyl group Trimethoxy silane, the dodecyl Trimethoxy silane, ten trifluoro octyl group Trimethoxy silanes, the hexadecyl Trimethoxy silane, the octadecyl Trimethoxy silane, the perfluoro capryl Trimethoxy silane, 17 fluorine decyl Trimethoxy silanes, octyltri-ethoxysilane, the dodecyl triethoxyl silane, ten trifluoro octyltri-ethoxysilane, the hexadecyl triethoxyl silane, octadecyltriethoxy silane, the perfluoro capryl triethoxyl silane, in the 17 fluorine decyl triethoxyl silanes one or more;
Described basic catalyst is selected from a kind of in ammoniacal liquor, Tetramethylammonium hydroxide, the tetraethyl ammonium hydroxide;
Described water is deionized water.
7. according to the preparation method of claim 5 or 6 described a kind of glass super hydrophobic surfaces, it is characterized in that described modification SiO
2In the colloidal sol each component: the alcohol that described alcohol is identical with moieties in the tetraalkyl orthosilicate, described methyl trialkoxysilane is identical with moieties in the alcohol.
8. the preparation method of a kind of glass super hydrophobic surface according to claim 5 is characterized in that, described modification SiO
2Whole process system keeps stirring in the colloidal sol preparation process.
9. the preparation method of a kind of glass super hydrophobic surface according to claim 1 is characterized in that, spin-coating method or dip-coating method are adopted in the preparation of glass super hydrophobic surface in the step (3).
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| CN110590179A (en) * | 2019-09-20 | 2019-12-20 | 浙江师范大学 | Preparation method of anti-reflection self-cleaning photovoltaic glass with optical double-conversion characteristic |
| CN110606670A (en) * | 2019-09-20 | 2019-12-24 | 浙江师范大学 | Preparation method of broad-spectrum anti-reflection super-hydrophobic photovoltaic glass |
| CN111019473A (en) * | 2019-12-24 | 2020-04-17 | 齐鲁工业大学 | Preparation of coatings with excellent mechanical and chemical stability |
| CN111233342A (en) * | 2020-01-15 | 2020-06-05 | 华南师范大学 | Hydrophobic substrate, preparation method thereof, electronic screen and electronic device |
| CN111234642A (en) * | 2020-03-09 | 2020-06-05 | 中电保力（北京）科技有限公司 | Bi-component super-hydrophobic coating |
| CN111234642B (en) * | 2020-03-09 | 2021-04-06 | 中电保力（北京）科技有限公司 | Bi-component super-hydrophobic coating |
| CN111410886A (en) * | 2020-03-31 | 2020-07-14 | 中电保力（北京）科技有限公司 | Double-component super-hydrophobic coating |
| CN113698839A (en) * | 2021-08-30 | 2021-11-26 | 浙江理工大学 | Environment-friendly organic super-hydrophobic composite coating without VOC (volatile organic compound) emission and preparation method thereof |
| CN113698839B (en) * | 2021-08-30 | 2023-02-28 | 浙江理工大学 | Environment-friendly organic super-hydrophobic composite coating without VOC (volatile organic compound) emission and preparation method thereof |
| CN115491094A (en) * | 2022-10-26 | 2022-12-20 | 浙江鱼童新材料股份有限公司 | Normal-temperature curing fluorocarbon coating and preparation method thereof |
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