CN102051100A - Lamellar ordered hybrid coating film and preparation method thereof - Google Patents
Lamellar ordered hybrid coating film and preparation method thereof Download PDFInfo
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- CN102051100A CN102051100A CN 201010523695 CN201010523695A CN102051100A CN 102051100 A CN102051100 A CN 102051100A CN 201010523695 CN201010523695 CN 201010523695 CN 201010523695 A CN201010523695 A CN 201010523695A CN 102051100 A CN102051100 A CN 102051100A
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- 238000002360 preparation method Methods 0.000 title claims description 25
- 238000000576 coating method Methods 0.000 title abstract description 40
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- 239000000839 emulsion Substances 0.000 claims abstract description 49
- 239000002105 nanoparticle Substances 0.000 claims abstract description 45
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 35
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000004528 spin coating Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 25
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- 239000005357 flat glass Substances 0.000 claims description 17
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- 239000011159 matrix material Substances 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
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- 238000002156 mixing Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 8
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- 241000282326 Felis catus Species 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000011505 plaster Substances 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 8
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- 241000276425 Xiphophorus maculatus Species 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
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- 230000000977 initiatory effect Effects 0.000 abstract 1
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- 238000010792 warming Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 6
- 238000009396 hybridization Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000002052 molecular layer Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 241000446313 Lamella Species 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241001083492 Trapa Species 0.000 description 2
- 235000014364 Trapa natans Nutrition 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 235000009165 saligot Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a lamellar ordered hybrid coating film. The lamellar ordered hybrid coating film with thickness ranging from 500 nm to 40 mum is formed by alternately piling inorganic nano-particle layers with thicknesses ranging from 10 nm to 200 nm and polymer layers with thicknesses ranging from 50 nm to 5 mum; each inorganic nano-particle layer adopts a montmorillonite layer or hydrotalcite layer; the polymer layer is prepared by a polymer emulsion coating film; and the polymer emulsion is prepared by adopting the following method: adding a monomer, surface-active agent and initiating agent into deionized water to carry out polymerization reaction for 5 to 8 hours under the temperature of 50 DEG C to 80 DEG C, then cooling to room temperature after completion of reaction, and then obtaining the polymer emulsion. The lamellar ordered hybrid coating film material is prepared by adopting the alternately spincoating or spraying method, the thicknesses of the polymer layers and the norganic nano-particle layers can be controlled through the process; and in addition, the surface-active agent capable of taking part in polymerization is selected, and the chemical binding between inorganic platy particles and polymer phase can be realized, so that the mechanical property, the heat resistance, the corrosion resistance and other properties of the material are enhanced.
Description
(1) technical field
The present invention relates to the orderly hydridization of a kind of stratiform and film and preparation method thereof, particularly a kind of polymer/inorganic nanometer particle layer is alternately piled up the orderly hydridization of forming of stratiform and is filmed and preparation method thereof.
(2) background technology
Along with the raising constantly that people require material protection in productive life, traditional polymeric coating material is many can not to meet the demands.Therefore, exploitation multifunction, wear-resisting, corrosion-resistant contour performance organic inorganic hybridization class coating material become a focus of coating research and industry.The organic inorganic hybridization class coating material is meant that inorganic nano-particle has the homodisperse heterogeneous material of Nano grade in polymer coating film, with the feature performance benefit of organic materials and inorganic materials.Because the inorganic particulate phase size is in the nanometer range, make hybrid coating show excellent optical transparence, resistance to elevated temperatures, wear-resisting, corrosion-resistant and special functional.At present, inorganic nano-particle commonly used comprises nano silicon, nano titanium oxide etc., and the method for preparation has sol-gel method, graft process and self-assembly method etc.Patent CN101649152 discloses a kind of environmentally-friendly organic inorganic hybridized paint and preparation method thereof, and this method is to form inorganic network structure by sol-gel method in organosilicon crylic acid latex.Resulting organic inorganic hybridization silicon-acrylic coatings has good mechanical property, has super-hydrophobicity simultaneously.Clay and hydrotalcite material have the nano material of laminated structure, behind organic modification, use and the polymer modification aspect widely, because its special laminated structure is often given material favorable mechanical performance, barrier property and high temperature resistant, flame retardant properties.The clay of non-modified and hydrotalcite have fabulous dispersing property in water, therefore, it can be dispersed in and prepare organic inorganic hybridized paint in the water-borne coatings, CN1715349A discloses the method that a kind of direct blend prepares polyurethane/hydrotalcite coating, the adding of hydrotalcite all is greatly improved the over-all propertieies such as hardness, shock-resistance and wear resistance of filming, and gives the ultraviolet shielded function of filming simultaneously.Document (chemical building material 2005,21 (1), 18-19) reported that employing emulsion intercalation legal system has the imvite modified acrylic ester emulsion hybridization coating of machine, the mechanical property of filming, water resistance, heat aging property and ultraviolet aging resistance performance all increase than pure acrylic acid ester emulsion film.
From present disclosed patent and document as can be known, the method of the organic inorganic hybridized paint of preparation polymer emulsion and laminar nano particle mainly comprises aqeous suspension and emulsion blending or the two kinds of approach of in-situ polymerization with the laminar nano particle, inorganic nano-particle exists with random form in the resultant hybridization coating, because the special laminated structure of laminar nano particle, if with its oriented in coating, the then obstruct of coating, wear-resisting, corrosion resistance nature will have raising by a larger margin.Based on this thought, the present invention utilizes the electrostatic interaction between latex particle and the layered inorganic nanoparticle, adopt the mode of layer assembly to realize the orientations of layered inorganic nanoparticle in coating, though patent CN101245151 discloses a kind of method for preparing hydrotalcite/polyalcohol composite self-supporting thin film by the static self-assembling technique, but it is by the electrostatic interaction between polymine, polyacrylic acid and the hydrotalcite, and prepared material is the hybrid film of self-supporting.
(3) summary of the invention
The purpose of this invention is to provide the orderly hydridization of a kind of stratiform films, and the preparation method who provides layered orderly hydridization to film, layered orderly hydridization is filmed and is meant that wherein lamella inorganic nano-particle is at class coating material camber ordered arrangement, the orderly hydridization of the stratiform that makes films and overcome the shortcoming of the prepared hybrid material laminate inorganic nano-particle random dispersion of traditional blend and situ aggregation method, effectively improved stratified nano materials to class coating material intercept, the functioning efficiency of performance such as corrosion-resistant.
The technical solution used in the present invention is:
The orderly hydridization of a kind of stratiform is filmed, the orderly hydridization of the described stratiform orderly hydridization of stratiform of alternately piling up 500nm～40um thickness of forming by the polymer layer of the inorganic nano-particle sublayer of 10～200nm thickness and 50nm～5um thickness of filming is filmed, described inorganic nano-particle sublayer is cheating engaging layer or hydrotalcite layer, described polymer layer is filmed by polymer emulsion and is prepared, described polymer emulsion makes by the following method: monomer, tensio-active agent, initiator adds in the deionized water, under 50～80 ℃ of temperature, carried out polyreaction 5～8 hours, reaction finishes postcooling to room temperature, make polymer emulsion, described monomer, tensio-active agent, initiator, the mass ratio of deionized water is 10～70: 0.5～3: 0.05～0.3: 100; Described monomer is one or more the mixing in butyl acrylate, vinylformic acid, methyl methacrylate, vinylbenzene, vinyl acetate, butyl methacrylate, Hydroxyethyl acrylate, methacrylic acid, the acrylamide; When described inorganic nano-particle sublayer was cheating engaging layer, described tensio-active agent was a cats product, and when described inorganic nano-particle sublayer was the hydrotalcite layer, described tensio-active agent was an anion surfactant; Described initiator is azo-bis-isobutyrate hydrochloride or ammonium persulphate.
The solid content of described polymer emulsion is generally 8～40wt%, is lower than theoretical solid content.
Comparatively concrete, described cats product is following one or more mixing: cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide or methylacryoyloxyethyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.
Described anion surfactant is following one or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or methacrylic hydroxyl sulfoacid sodium.
The orderly hydridization of stratiform of the present invention is filmed alternately to be piled up by inorganic nano-particle sublayer and polymer layer and is formed, and wherein the inorganic nano-particle sublayer can be electronegative montmorillonite layer, also can be positively charged hydrotalcite layer.Polymer layer is obtained through filming by polymer emulsion, the surface charge property of polymer emulsion latex particle is by the charged character decision of inorganic nano-particle sublayer institute, the surface charge of polymer emulsion latex particle must be electrically charged opposite with inorganic nano-particle sublayer institute, and the latex particle surface charge is by the water-wet side generation of employed tensio-active agent in the preparation polymer emulsion, that is to say, when the inorganic nano-particle sublayer is electronegative montmorillonite layer, the latex particle surface requirements is a positive charge, and the tensio-active agent when then preparing polymer emulsion uses cats product; When the inorganic nano-particle sublayer is the positively charged hydrotalcite lamella in surface, the latex particle surface requirements is a negative charge, and the tensio-active agent when then preparing polymer emulsion uses anion surfactant.
Described polymer layer is filmed by polymer emulsion and is prepared, and described filming can adopt spin-coating or spraying method to film.
The preparation method that the present invention also provides layered orderly hydridization to film, described method may further comprise the steps:
(1) inorganic nano-particle is added in the deionized water, the back ultra-sonic dispersion (disperseing 10～30 minutes under the ultrasonic wave effect of 100～600W power usually) that stirs makes mass concentration and is the suspension of 0.1～5% inorganic nano-particle; Described inorganic nano-particle is polynite or hydrotalcite;
(2) monomer, tensio-active agent, initiator add in the deionized water, under 50～80 ℃ of temperature, carried out polyreaction 5～8 hours, reaction finishes postcooling to room temperature, make polymer emulsion, the mass ratio of described monomer, tensio-active agent, initiator, deionized water is 10～70: 0.5～3: 0.05～0.3: 100; Described monomer is one or more the mixing in butyl acrylate, vinylformic acid, methyl methacrylate, vinylbenzene, vinyl acetate, butyl methacrylate, Hydroxyethyl acrylate, methacrylic acid, the acrylamide; When described inorganic nano-particle was polynite, described tensio-active agent was a cats product, and when described inorganic nano-particle was hydrotalcite, described tensio-active agent was an anion surfactant; Described initiator is azo-bis-isobutyrate hydrochloride or ammonium persulphate;
(3) polymer emulsion for preparing of step (2) makes the first layer polymer layer that thickness is 50nm～5um thickness by spin-coating or spraying method at matrix, after the drying, the suspension of the inorganic nano-particle that step (1) is prepared makes the first layer inorganic nano-particle sublayer that thickness is 10～200nm thickness by spin-coating or spraying method on the first layer polymer layer, make the first layer hydridization after the drying and film; Described matrix is glass basis, metallic matrix, stone material matrix or plaster matrix;
(4) according to the method recirculation operation of step (3), the orderly hydridization of stratiform that makes thickness 500nm～40um is filmed.
Described inorganic nano-particle is polynite or hydrotalcite, and described polynite can be the inorganic polynite of any component, as common calcium base, sodium base, Sodium base, magnesium base montmorillonite etc., all is applicable to the present invention.Described hydrotalcite also can be the inorganic hydrotalcite of any component, as magnesium aluminum-hydrotalcite, zinc-aluminium hydrotalcite, iron aluminum hydrotalcite etc., all is applicable to the present invention.
In the described step (3), the method for spin-coating is for rotating speed being 500～2000 rev/mins whirler spin-coating 1～5 minute.
In the described step (3), described glass basis be with sheet glass in the mass ratio of the vitriol oil and 30wt% hydrogen peroxide is 70: 30 mixed solution, after soaking 15～30 minutes under 90～95 ℃ of temperature, clean through deionized water rinsing, drying obtains described glass basis.
In the described step (3), described drying is at room temperature placing 2～10 minutes.
In the described step (3), described metallic matrix is a stainless steel substrate, and described stainless steel substrate can obtain by stainless steel plate is carried out pre-treatment with the alkali liquid washing oil removing.
Advantage of the present invention is:
1) by inorganic laminated nanoparticle and latex particle surface with the interaction of out-phase electric charge, can realize organic and layer assembly inorganic materials, realize the orientations of inorganic sheet particle simultaneously.
2) can participate in the polymeric tensio-active agent by selecting for use, can realize that inorganic platy particle is connected with the chemistry of polymer phase, thereby improve the mechanics of material, performance such as heat-resisting, corrosion-resistant.
3) can regulate and control the arrangement pitches of the inorganic laminated nanoparticle of ordered arrangement by the solid content of regulation and control grain size of latex particle and emulsion, realize intercepting, the regulation and control of resistance toheat.
4) the orderly hydridization of stratiform provided by the invention is filmed and be can be applicable on the common various matrixes, improves heat-resisting, water-fast, the corrosion resistance nature of matrix surface.
(4) description of drawings
Film cross-sectional configuration pattern SEM figure of the orderly hydridization of the stratiform that Fig. 1 embodiment 1 makes
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
The sheet glass pre-treatment: sheet glass is in the mass ratio of the vitriol oil and hydrogen peroxide (mass percentage concentration 30%) is 70: 30 mixed solution, clean through deionized water rinsing after soaking 15 minutes under 90 ℃ of temperature, dry up and obtain pretreated sheet glass.
Embodiment 1
(sodium-based montmorillonite, Linan, Zhejiang Ward clay company) joins in the 100g water with the 0.1g polynite, stirs 1h under the room temperature, is the suspension that disperses to obtain in 10 minutes polynite under the ultrasonic wave of 100W at power then.
The 1.0g palmityl trimethyl ammonium chloride is dissolved in the 100g deionized water, be warming up to 70 ℃, add 18g vinylbenzene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 5h, system is cooled to room temperature obtains acrylic ester emulsion, solid content detects through weighting method and is 40wt%.
On pretreated sheet glass, it with the acrylic ester emulsion rotating speed 1500 rev/mins whirler spin coating 5 minutes, obtain the polymer layer of 250nm (AFM mensuration), dry 3 minutes, then on polymer layer, with montmorillonite suspension liquid is 1500 rev/mins of whirler spin coatings 5 minutes with rotating speed equally, form the inorganic layer of 10nm (AFM mensuration), room temperature condition was placed 3 minutes, finish the preparation that one deck hydridization is filmed, 10 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 2.6um (AFM mensuration).
With low-temperature brittle fracture in the class coating material liquid nitrogen, adopt scanning electronic microscope (SEM) to observe the structure and morphology of the cross section of filming, as shown in Figure 1.
As can be seen from the figure, being arranged in the class coating material of layered inorganic nanoparticle high-sequential forms the orderly hydridization of stratiform with polymer materials and films.
Comparative Examples 1
The 1.0g octadecyl trimethyl ammonium chloride is dissolved in the 100g deionized water, be warming up to 70 ℃, add 18g vinylbenzene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 5h, system is cooled to room temperature obtains acrylic ester emulsion, solid content is 40wt% after testing.
On pretreated sheet glass, acrylic ester emulsion is obtained the acrylate coatings that thickness is 2.6um (AFM mensuration) with the coating of blade coating spreader.
The orderly hydridization of prepared stratiform filmed and contrast acrylate coatings and adopt around the Resins, epoxy and be immersed in water, the 5%NaOH aqueous solution and 5%H respectively behind the edge sealing
2SO
4Carry out water tolerance and corrosion resistance measurement in the aqueous solution, the result is as shown in table 1, as seen, because the ordered arrangement of inorganic nano lamella structure, the water tolerance and the erosion resistance of the coating that has improved greatly.
Table 1
Embodiment 2
(calcium sodium-based montmorillonite, Linan, Zhejiang Ward clay company) joins in the 100g water with the 1.0g polynite, stirs 1h under the room temperature, disperses to obtain in 10 minutes the suspension of polynite then under the 200W ultrasonic wave.
The 1.0g Dodecyl trimethyl ammonium chloride is dissolved in the 100g deionized water, be warming up to 70 ℃, add 18g vinylbenzene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 5h, system is cooled to room temperature obtains acrylic ester emulsion, solid content detects through weighting method and is 40wt%.
On pretreated sheet glass, it with the acrylic ester emulsion rotating speed 500 rev/mins whirler spin coating 1 minute, obtain the polymer layer of 450nm (AFM mensuration), placed dry 5 minutes, then on polymer layer, with montmorillonite suspension liquid is 500 rev/mins of whirler spin coatings 1 minute with rotating speed equally, form the inorganic layer of 50nm (AFM mensuration), placed 3 minutes, finish the preparation that one deck hydridization is filmed, 20 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 10um (AFM mensuration).
Embodiment 3
(sodium-based montmorillonite, Linan, Zhejiang Ward clay company) joins in the 100g water with the 1.0g polynite, stirs 1h under the room temperature, disperses to obtain in 10 minutes the suspension of polynite then under the effect of 200W ultrasonic wave.
3.0g methylacryoyloxyethyl trimethylammonium bromide is dissolved in the 100g deionized water, be warming up to 80 ℃, add 3.0g methyl methacrylate, 3.0g vinylformic acid, 4.0g butyl acrylate mix monomer, 0.3g azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 8h, system is cooled to room temperature obtains acrylic ester emulsion, solid content detects through weighting method and is 8.0wt%.
On pretreated sheet glass, 's 1000 rev/mins whirler spin coating 3 minutes with acrylic ester emulsion by rotating speed, obtain the polymer layer of 50nm (AFM mensuration), placed 3 minutes, then on polymer layer, with montmorillonite suspension liquid is 1000 rev/mins of whirler spin coatings 3 minutes with rotating speed equally, form the inorganic layer of 12nm (AFM mensuration), placed 4 minutes, finish the preparation that one deck hydridization is filmed, 8 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 500nm (AFM mensuration).
Embodiment 4
(sodium-based montmorillonite, Linan, Zhejiang Ward clay company) joins in the 100g water with the 5.0g polynite, stirs 1h under the room temperature, disperses to obtain in 10 minutes the suspension of polynite then under the effect of 600W ultrasonic wave.
2.0g octadecyl trimethylammonium bromide is dissolved in the 100g deionized water, be warming up to 70 ℃, add 4.0g methyl methacrylate, 6.0g Hydroxyethyl acrylate, 4.0g vinylbenzene, 4.0g vinylformic acid, 4.0g butyl acrylate mix monomer and 0.2g initiator azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 6h, system is cooled to room temperature obtains the cinnamic acrylic ester emulsion, solid content detects through weighting method and is 20wt%.
On pretreated sheet glass, with the whirler spin coating of cinnamic acrylic ester emulsion by 2000 rev/mins of rotating speeds 3 minutes, obtain the polymer layer of 80nm (AFM mensuration), placed 3 minutes, then on polymer layer, with montmorillonite suspension liquid is 2000 rev/mins of whirler spin coatings 3 minutes with rotating speed equally, form the inorganic nano layer of 45nm (AFM mensuration), placed 3 minutes, finish the preparation that one deck hydridization is filmed, 12 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 1.5um (AFM mensuration).
Embodiment 5
0.5g hydrotalcite (magnesium aluminum-hydrotalcite, Huzhou City water chestnut lake newly hope chemical industry company limited produce) is joined in the 100g water, stir 1h under the room temperature, under the effect of 200W ultrasonic wave, disperse to obtain in 10 minutes the suspension of hydrotalcite then.
The 0.5g sodium lauryl sulphate is dissolved in the 100g deionized water, be warming up to 50 ℃, add 6.0g methyl methacrylate, 6.0g vinyl acetate, 4.0g butyl methacrylate mix monomer, 0.2g ammonium persulphate, keep thermotonus 8h, system is cooled to room temperature obtains acrylic ester emulsion, solid content detects through weighting method and is 14.0wt%.
On pretreated sheet glass, 's 1500 rev/mins whirler spin coating 3 minutes with acrylic ester emulsion by rotating speed, obtain the polymer layer of 100nm (AFM mensuration), placed 3 minutes, then on polymer layer, with hydrotalcite suspension is 1000 rev/mins of whirler spin coatings 2 minutes with rotating speed equally, form the inorganic nano layer of 25nm (AFM mensuration), placed 4 minutes, finish the preparation that one deck hydridization is filmed, 12 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 1.5um (AFM mensuration).
Embodiment 6
The hydrotalcite suspension preparation is with embodiment 5.
The 1.0g Sodium dodecylbenzene sulfonate is dissolved in the 100g deionized water, be warming up to 70 ℃, add 5.0g methyl methacrylate, 6.0g Hydroxyethyl acrylate, 4.0g vinylbenzene 6.0g vinylformic acid, 6.0g butyl acrylate mix monomer and 0.2g initiator azo-bis-isobutyrate hydrochloride (AIBA), keep thermotonus 6h, system is cooled to room temperature obtains the cinnamic acrylic ester emulsion, solid content detects through weighting method and is 24.5wt%.
On pretreated sheet glass, with cinnamic acrylic ester emulsion rotating speed is 1000 rev/mins of whirler spin coatings 3 minutes, obtain the polymer layer of 200nm (AFM mensuration), placed 5 minutes, then on polymer layer, with hydrotalcite suspension is 500 rev/mins of whirler spin coatings 3 minutes with rotating speed equally, form the inorganic nano layer of 50nm (AFM mensuration), placed 3 minutes, finish the preparation that one deck hydridization is filmed, 12 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 3.0um (AFM mensuration).
Embodiment 7
1.0g hydrotalcite (zinc-aluminium hydrotalcite, Huzhou City water chestnut lake newly hope chemical industry company limited produce) is joined in the 100g water, stir 1h under the room temperature, under the effect of 500W ultrasonic wave, disperse to obtain in 10 minutes the suspension of hydrotalcite then.
2.0g methacrylic hydroxyl sulfoacid sodium is dissolved in the 100g deionized water, be warming up to 70 ℃, add 4.0g methyl methacrylate, 6.0g Hydroxyethyl acrylate, 4.0g vinylbenzene 4.0g vinylformic acid, 4.0g butyl acrylate mix monomer and 0.2g initiator ammonium persulfate, keep thermotonus 6h, system is cooled to room temperature obtains the cinnamic acrylic ester emulsion, solid content is 20wt% after testing.
On pretreated sheet glass, it with cinnamic acrylic ester emulsion rotating speed 2000 rev/mins whirler spin coating 3 minutes, obtain the polymer layer of 80nm (AFM mensuration), placed 3 minutes, be 2000 rev/mins whirler spin coating 3 minutes equally with rotating speed with hydrotalcite suspension, form the inorganic nano layer of 30nm (AFM mensuration), placed 4 minutes, finish the preparation that one deck hydridization is filmed, 12 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 1.3um (AFM mensuration).
Embodiment 8
Montmorillonite suspension liquid and acrylic ester emulsion preparation are with embodiment 1
With stainless steel plate alkaline solution (oxygen sodium oxide 30g/L, yellow soda ash 30g/L, tertiary sodium phosphate 40g/L, OP-emulsifying agent 3mL/L) washing oil removing 15min under 80 ℃ of temperature.On the pretreated stainless steel plate of process, it with the acrylic ester emulsion rotating speed 1000 rev/mins whirler spin coating 5 minutes, obtain the polymer layer of 350nm (AFM mensuration), dry 3 minutes, then on polymer layer, with montmorillonite suspension liquid is 1000 rev/mins of whirler spin coatings 5 minutes with rotating speed equally, form the inorganic layer of 15nm (AFM mensuration), room temperature condition was placed 3 minutes, finish the preparation that one deck hydridization is filmed, 10 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 3.8um (AFM mensuration).
Embodiment 9
Montmorillonite suspension liquid and acrylic ester emulsion preparation are with embodiment 1.
Acrylic ester emulsion is passed through high-pressure spray gun (jet size 0.3mm, every some spray time 1s, gun slot is apart from sheet glass 10cm) spraying one layer thickness is the polymer layer of 4.8um (AFM mensuration) on pretreated sheet glass, placed 10 minutes, then on polymer layer, adopt the method for spray gun spraying to spray the sheet inorganic nano material layer that a layer thickness is 200nm (an AFM mensuration) equally montmorillonite suspension liquid, the same placement 10 minutes, finish the preparation of one deck hybrid coating, 8 circulations so repeatedly, obtaining thickness is the orderly hydridization class coating material of stratiform of 40um (AFM mensuration).
Embodiment 10
The hydrotalcite suspension preparation is with embodiment 5.
The 0.5g sodium laurylsulfonate is dissolved in the 100g deionized water, be warming up to 50 ℃, add 6.0g methyl methacrylate, 6.0g vinyl acetate, 4.0g butyl methacrylate mix monomer, 0.2g ammonium persulphate, keep thermotonus 8h, system is cooled to room temperature obtains acrylic ester emulsion, solid content detects through weighting method and is 14.0wt%.
Acrylic ester emulsion is passed through high-pressure spray gun (jet size 0.3mm, every some spray time 1s, gun slot is apart from sheet glass 10cm) spraying one layer thickness is the polymer layer of 3um (AFM mensuration) on pretreated sheet glass, placed 8 minutes, then on polymer layer, adopt the method for spray gun spraying to spray the sheet inorganic nano material layer that a layer thickness is 120nm (an AFM mensuration) equally hydrotalcite suspension, placed 4 minutes, finish the preparation of one deck hybrid coating, 8 circulations so repeatedly, obtaining thickness is the hydridization class coating material of 25um (AFM mensuration).
Claims (9)
1. the orderly hydridization of stratiform is filmed, it is characterized in that the orderly hydridization of the described stratiform orderly hydridization of stratiform of alternately piling up 500nm ~ 40um thickness of forming by the polymer layer of the inorganic nano-particle sublayer of 10 ~ 200nm thickness and 50nm ~ 5um thickness of filming films, described inorganic nano-particle sublayer is cheating engaging layer or hydrotalcite layer, described polymer layer is filmed by polymer emulsion and is prepared, described polymer emulsion makes by the following method: monomer, tensio-active agent, initiator add in the deionized water, 50～80
oCarried out polyreaction under the C temperature 5～8 hours, reaction finishes postcooling to room temperature, makes polymer emulsion, and the mass ratio of described monomer, tensio-active agent, initiator, deionized water is 10～70:0.5～3:0.05 ~ 0.3:100; Described monomer is one or more the mixing in butyl acrylate, vinylformic acid, methyl methacrylate, vinylbenzene, vinyl acetate, butyl methacrylate, Hydroxyethyl acrylate, methacrylic acid, the acrylamide; When described inorganic nano-particle sublayer was cheating engaging layer, described tensio-active agent was a cats product, and when described inorganic nano-particle sublayer was the hydrotalcite layer, described tensio-active agent was an anion surfactant; Described initiator is azo-bis-isobutyrate hydrochloride or ammonium persulphate.
2. the orderly hydridization of stratiform as claimed in claim 1 is filmed, it is characterized in that described cats product is following one or more mixing: cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, methylacryoyloxyethyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.
3. the orderly hydridization of stratiform as claimed in claim 1 is filmed, and it is characterized in that described anion surfactant is following one or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or methacrylic hydroxyl sulfoacid sodium.
4. preparation method that the orderly hydridization of stratiform is filmed is characterized in that described method may further comprise the steps:
(1) inorganic nano-particle is added in the deionized water, the back ultra-sonic dispersion that stirs makes mass concentration and is the suspension of 0.1 ~ 5% inorganic nano-particle; Described inorganic nano-particle is polynite or hydrotalcite;
(2) monomer, tensio-active agent, initiator add in the deionized water, 50～80
oCarried out polyreaction under the C temperature 5～8 hours, reaction finishes postcooling to room temperature, makes polymer emulsion, and the mass ratio of described monomer, tensio-active agent, initiator, deionized water is 10～70:0.5～3:0.05 ~ 0.3:100; Described monomer is one or more the mixing in butyl acrylate, vinylformic acid, methyl methacrylate, vinylbenzene, vinyl acetate, butyl methacrylate, Hydroxyethyl acrylate, methacrylic acid, the acrylamide; When described inorganic nano-particle was polynite, described tensio-active agent was a cats product, and when described inorganic nano-particle was hydrotalcite, described tensio-active agent was an anion surfactant; Described initiator is azo-bis-isobutyrate hydrochloride or ammonium persulphate;
(3) polymer emulsion for preparing of step (2) makes the first layer polymer layer that thickness is 50nm ~ 5um thickness by spin-coating or spraying method on matrix, after the drying, the suspension of the inorganic nano-particle that step (1) is prepared makes the first layer inorganic nano-particle sublayer that thickness is 10 ~ 200nm thickness by spin-coating or spraying method on the first layer polymer layer, make the first layer hydridization after the drying and film; Described matrix is glass basis, metallic matrix, stone material matrix or plaster matrix;
(4) according to the method recirculation operation of step (3), the orderly hydridization of stratiform that makes thickness 500nm ~ 40um is filmed.
5. method as claimed in claim 4 is characterized in that in the described step (1), and described ultra-sonic dispersion is to disperse 10 ~ 30 minutes under the ultrasonic wave effect of power 100 ~ 600W.
6. method as claimed in claim 4 is characterized in that in the described step (3), and the method for spin-coating is for rotating speed being 500 ~ 2000 rev/mins whirler spin-coating 1 ~ 5 minute.
7. method as claimed in claim 4, it is characterized in that in the described step (3), described glass basis is to be in the mixed solution of 70:30 with sheet glass at the mass ratio of the hydrogen peroxide of the vitriol oil and 30wt%, after soaking 15 ~ 30 minutes under 90 ~ 95 ℃ of temperature, clean through deionized water rinsing, drying obtains described glass basis.
8. method as claimed in claim 4 is characterized in that in the described step (3) that described drying is at room temperature placing 2 ~ 10 minutes.
9. method as claimed in claim 4 is characterized in that in the described step (3), described metallic matrix is a stainless steel substrate.
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