CN102051100B - 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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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
The raising constantly that Along with people's requires material protection in productive life, the conventional polymer coating material is many can not to meet the demands.Therefore, exploitation multifunction, high-performance organic inorganic hybridization class coating material such as wear-resisting, corrosion-resistant 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 material and inorganic material.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-gal process, 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 in Silicone acrylic emulsion, to form inorganic network structure through sol-gal process.Resulting organic inorganic hybridization silicon-acrylic coatings has good mechanical performance, has super-hydrophobicity simultaneously.Clay and hydrotalcite material have the nano material of lamellar structure; Behind organic modification; Use and the polymer modification aspect widely, because its special lamellar structure is often given material favorable mechanical performance, barrier property and high temperature resistant, fire resistance.The clay of non-modified and hydrotalcite have fabulous dispersive property in water; Therefore; Can it be dispersed in and prepare organic inorganic hybridized paint in the water paint; CN1715349A discloses the method that a kind of direct blend prepares polyurethane/hydrotalcite coating, and the adding of hydrotalcite all is greatly improved the combination properties such as hardness, resistance to impact and wearability 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 acid 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.
Can know from present disclosed patent and document; The method of the organic inorganic hybridized paint of preparation polymer emulsion and laminar nano particle mainly comprises water slurry and emulsion blending or 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 lamellar structure of laminar nano particle, if with its oriented in coating, the then obstruct of coating, wear-resisting, decay resistance 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 nano particle; Adopt the mode of layer assembly to realize the orientations of layered inorganic nano particle in coating; Though patent CN101245151 discloses and a kind ofly prepared the method for hydrotalcite/polyalcohol composite self-supporting thin film through the static self-assembling technique, it is through 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 lamella inorganic nano-particle high-sequential arrangement in class coating material wherein; 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 scheme that the present invention adopts 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 polymeric layer of the inorganic nano-particle sublayer of 10～200nm thickness and 50nm～5um thickness of filming is filmed; Said inorganic nano-particle sublayer is cheating engaging layer or hydrotalcite layer; Said polymeric layer is filmed by polymer emulsion and is prepared; Said polymer emulsion makes by following method: monomer, surfactant, initator add in the deionized water, under 50～80 ℃ of temperature, carry out polymerisation 5～8 hours, are cooled to room temperature after reaction finishes; Make polymer emulsion, the mass ratio of said monomer, surfactant, initator, deionized water is 10～70: 0.5～3: 0.05～0.3: 100; Said monomer is one or more the mixing in butyl acrylate, acrylic acid, methyl methacrylate, styrene, vinylacetate, butyl methacrylate, hydroxy-ethyl acrylate, methacrylic acid, the acrylamide; When said inorganic nano-particle sublayer was cheating engaging layer, said surfactant was a cationic surfactant, and when said inorganic nano-particle sublayer was the hydrotalcite layer, said surfactant was an anion surfactant; Said initator is azo-bis-isobutyrate hydrochloride or ammonium persulfate.
The solid content of said polymer emulsion is generally 8～40wt%, is lower than theoretical solid content.
Comparatively concrete; Said cationic surfactant is following one or more mixing: softex kw, octadecyl trimethylammonium bromide or methylacryoyloxyethyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, DTAC or stearyl dimethyl benzyl ammonium chloride.
Said anion surfactant is following one or more mixing: lauryl sodium sulfate, dodecyl sodium sulfate, neopelex or methacrylic hydroxyl sulfoacid sodium.
The orderly hydridization of stratiform according to the invention is filmed alternately to be piled up by inorganic nano-particle sublayer and polymeric layer and is formed, and wherein the inorganic nano-particle sublayer can be electronegative montmorillonite layer, also can be positively charged hydrotalcite layer.Polymeric 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 that is to say, when the inorganic nano-particle sublayer is electronegative montmorillonite layer by the water-wet side generation of employed surfactant in the preparation polymer emulsion; The latex particle surface requirements is a positive charge, and the surfactant when then preparing polymer emulsion uses cationic surfactant; When the inorganic nano-particle sublayer is the positively charged hydrotalcite lamella in surface, the latex particle surface requirements is a negative electrical charge, and the surfactant when then preparing polymer emulsion uses anion surfactant.
Said polymeric layer is filmed by polymer emulsion and is prepared, and said 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 ultrasonic dispersion in back (usually under the ultrasonic wave effect of 100～600W power dispersion 10～30 minutes) that stirs makes mass concentration and is the suspension of 0.1～5% inorganic nano-particle; Said inorganic nano-particle is imvite or hydrotalcite;
(2) monomer, surfactant, initator add in the deionized water; Under 50～80 ℃ of temperature, carried out polymerisation 5～8 hours; After finishing, reaction is cooled to room temperature; Make polymer emulsion, the mass ratio of said monomer, surfactant, initator, deionized water is 10～70: 0.5～3: 0.05～0.3: 100; Said monomer is one or more the mixing in butyl acrylate, acrylic acid, methyl methacrylate, styrene, vinylacetate, butyl methacrylate, hydroxy-ethyl acrylate, methacrylic acid, the acrylamide; When said inorganic nano-particle was imvite, said surfactant was a cationic surfactant, and when said inorganic nano-particle was hydrotalcite, said surfactant was an anion surfactant; Said initator is azo-bis-isobutyrate hydrochloride or ammonium persulfate;
(3) polymer emulsion for preparing of step (2) makes the ground floor polymeric layer that thickness is 50nm～5um thickness through spin-coating or spraying method at matrix; After the drying; The suspension of the inorganic nano-particle that step (1) is prepared makes the ground floor inorganic nano-particle sublayer that thickness is 10～200nm thickness through spin-coating or spraying method on the ground floor polymeric layer, make ground floor hydridization after the drying and film; Said matrix is glass basis, metallic matrix, stone material matrix or plaster matrix;
(4) according to the method repetitive cycling operation of step (3), the orderly hydridization of stratiform that makes thickness 500nm～40um is filmed.
Said inorganic nano-particle is imvite or hydrotalcite, and said imvite can be the inorganic imvite of any component, like common calcium base, sodium base, Sodium base, magnesium base montmorillonite etc., all is applicable to the present invention.Said hydrotalcite also can be the inorganic hydrotalcite of any component, like magnalium hydrotalcite, zinc-aluminium hydrotalcite, iron aluminum hydrotalcite etc., all is applicable to the present invention.
In the said step (3), the method for spin-coating is 500～2000 rev/mins a whirler spin-coating 1～5 minute for using rotating speed.
In the said step (3); Said glass basis be with glass plate in the mass ratio of the concentrated sulfuric acid and 30wt% hydrogen peroxide solution is 70: 30 mixed liquor; After soaking 15～30 minutes under 90～95 ℃ of temperature, clean through deionized water rinsing, drying obtains described glass basis.
In the said step (3), said drying is at room temperature placing 2～10 minutes.
In the said step (3), said metallic matrix is a stainless steel substrate, and said stainless steel substrate can obtain through corrosion resistant plate is carried out preliminary treatment with the alkali liquid washing oil removing.
Advantage of the present invention is:
1) through inorganic laminated nano particle and latex particle surface with the interaction of out-phase electric charge, can realize organic and layer assembly inorganic material, realize the orientations of inorganic sheet particle simultaneously.
2), 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 through selecting the surfactant that to participate in polymerization for use.
3) solid content of grain size and the emulsion through the regulation and control latex particle can be regulated and control the arrangement pitches of the inorganic laminated nano particle of orderly arrangement, realizes intercepting, the regulation and control of heat resistance.
4) the orderly hydridization of stratiform provided by the invention is filmed and can be applicable on the common various matrixes, improves heat-resisting, water-fast, the decay resistance 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) specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
The glass plate preliminary treatment: glass plate is in the mass ratio of the concentrated sulfuric acid and hydrogen peroxide solution (mass percentage concentration 30%) is 70: 30 mixed liquor, clean through deionized water rinsing after soaking 15 minutes under 90 ℃ of temperature, dry up and obtain pretreated glass plate.
Embodiment 1
(sodium-based montmorillonite, Linan, Zhejiang Ward clay company) joins in the 100g water with the 0.1g imvite, stirs 1h under the room temperature, is the suspension that disperses to obtain in 10 minutes imvite under the ultrasonic wave of 100W at power then.
The 1.0g hexadecyltrimethylammonium chloride is dissolved in the 100g deionized water; Be warming up to 70 ℃; Add 18g styrene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA) keeps thermotonus 5h; System is cooled to room temperature obtains acrylic acid ester emulsion, solid content detects through weight method and is 40wt%.
On pretreated glass plate, it is 1500 rev/mins whirler spin coating 5 minutes that acrylic acid ester emulsion is used rotating speed, obtains the polymeric layer of 250nm (AFM mensuration); Dry 3 minutes; On polymeric layer, it is 1500 rev/mins of whirler spin coatings 5 minutes that montmorillonite suspension liquid is used rotating speed equally then, forms the inorganic layer of 10nm (AFM mensuration); Room temperature condition was placed 3 minutes; Accomplish 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 SEM (SEM) to observe the structure and morphology of the cross section of filming, shown in accompanying drawing 1.
As can be seen from the figure, being arranged in the class coating material of layered inorganic nano particle high-sequential forms the orderly hydridization of stratiform with polymeric material and films.
Comparative Examples 1
The 1.0g OTAC is dissolved in the 100g deionized water; Be warming up to 70 ℃; Add 18g styrene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA) keeps thermotonus 5h; System is cooled to room temperature obtains acrylic acid ester emulsion, solid content is 40wt% through detecting.
On pretreated glass plate, use the coating of blade coating spreader to obtain the acrylate coatings of thickness acrylic acid ester emulsion as 2.6um (AFM mensuration).
The orderly hydridization of prepared stratiform filmed and contrast acrylate coatings adopt around the epoxy resin and be immersed in water, the 5%NaOH aqueous solution and 5%H respectively behind the edge sealing
2SO
4Carry out resistance to water and corrosion resistance measurement in the aqueous solution, the result is as shown in table 1, and is visible, because the orderly arrangement of inorganic nano lamella structure, and the resistance to water and the corrosion 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 imvite, stirs 1h under the room temperature, and the 200W ultrasonic wave disperses to obtain in 10 minutes the suspension of imvite down then.
The 1.0g DTAC is dissolved in the 100g deionized water; Be warming up to 70 ℃; Add 18g styrene, 14g methyl methacrylate, 38g butyl acrylate mix monomer, 0.1g, azo-bis-isobutyrate hydrochloride (AIBA) keeps thermotonus 5h; System is cooled to room temperature obtains acrylic acid ester emulsion, solid content detects through weight method and is 40wt%.
On pretreated glass plate, it is 500 rev/mins whirler spin coating 1 minute that acrylic acid ester emulsion is used rotating speed, obtains the polymeric layer of 450nm (AFM mensuration); Placed dry 5 minutes; On polymeric layer, it is 500 rev/mins of whirler spin coatings 1 minute that montmorillonite suspension liquid is used rotating speed equally then, forms the inorganic layer of 50nm (AFM mensuration); Placed 3 minutes; Accomplish 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 imvite, stirs 1h under the room temperature, under the effect of 200W ultrasonic wave, disperses to obtain in 10 minutes the suspension of imvite then.
3.0g methylacryoyloxyethyl trimethylammonium bromide is dissolved in the 100g deionized water; Be warming up to 80 ℃; Add 3.0g methyl methacrylate, 3.0g acrylic 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 acid ester emulsion, solid content detects through weight method and is 8.0wt%.
On pretreated glass plate, be 1000 rev/mins whirler spin coating 3 minutes with acrylic acid ester emulsion through rotating speed, obtain the polymeric layer of 50nm (AFM mensuration); Placed 3 minutes; On polymeric layer, it is 1000 rev/mins of whirler spin coatings 3 minutes that montmorillonite suspension liquid is used rotating speed equally then, forms the inorganic layer of 12nm (AFM mensuration); Placed 4 minutes; Accomplish 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 imvite, stirs 1h under the room temperature, under the effect of 600W ultrasonic wave, disperses to obtain in 10 minutes the suspension of imvite then.
2.0g octadecyl trimethylammonium bromide is dissolved in the 100g deionized water; Be warming up to 70 ℃; Add 4.0g methyl methacrylate, 6.0g hydroxy-ethyl acrylate, 4.0g styrene, 4.0g acrylic acid, 4.0g butyl acrylate mix monomer and 0.2g initator azo-bis-isobutyrate hydrochloride (AIBA) keep thermotonus 6h; System is cooled to room temperature obtains the cinnamic acrylic ester emulsion, solid content detects through weight method and is 20wt%.
On pretreated glass plate,, obtain the polymeric layer of 80nm (AFM mensuration) with the whirler spin coating of cinnamic acrylic ester emulsion through 2000 rev/mins of rotating speeds 3 minutes; Placed 3 minutes; On polymeric layer, it is 2000 rev/mins of whirler spin coatings 3 minutes that montmorillonite suspension liquid is used rotating speed equally then, forms the inorganic nano layer of 45nm (AFM mensuration); Placed 3 minutes; Accomplish 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 (magnalium hydrotalcite, Huzhou City water chestnut lake newly hope chemical industry Co., Ltd 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 lauryl sodium sulfate is dissolved in the 100g deionized water; Be warming up to 50 ℃; Add 6.0g methyl methacrylate, 6.0g vinylacetate, 4.0g butyl methacrylate mix monomer, 0.2g ammonium persulfate; Keep thermotonus 8h, system is cooled to room temperature obtains acrylic acid ester emulsion, solid content detects through weight method and is 14.0wt%.
On pretreated glass plate, be 1500 rev/mins whirler spin coating 3 minutes with acrylic acid ester emulsion through rotating speed, obtain the polymeric layer of 100nm (AFM mensuration); Placed 3 minutes; On polymeric layer, it is 1000 rev/mins of whirler spin coatings 2 minutes that hydrotalcite suspension is used rotating speed equally then, forms the inorganic nano layer of 25nm (AFM mensuration); Placed 4 minutes; Accomplish 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 neopelex is dissolved in the 100g deionized water; Be warming up to 70 ℃; Add 5.0g methyl methacrylate, 6.0g hydroxy-ethyl acrylate, 4.0g styrene 6.0g acrylic acid, 6.0g butyl acrylate mix monomer and 0.2g initator azo-bis-isobutyrate hydrochloride (AIBA); Keep thermotonus 6h, system is cooled to room temperature obtains the cinnamic acrylic ester emulsion, solid content detects through weight method and is 24.5wt%.
On pretreated glass plate, it is 1000 rev/mins of whirler spin coatings 3 minutes that the cinnamic acrylic ester emulsion is used rotating speed, obtains the polymeric layer of 200nm (AFM mensuration); Placed 5 minutes; On polymeric layer, it is 500 rev/mins of whirler spin coatings 3 minutes that hydrotalcite suspension is used rotating speed equally then, forms the inorganic nano layer of 50nm (AFM mensuration); Placed 3 minutes; Accomplish 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 Co., Ltd 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 hydroxy-ethyl acrylate, 4.0g styrene 4.0g acrylic 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% through detecting.
On pretreated glass plate; It is 2000 rev/mins whirler spin coating 3 minutes that the cinnamic acrylic ester emulsion is used rotating speed, obtains the polymeric layer of 80nm (AFM mensuration), places 3 minutes; It is 2000 rev/mins whirler spin coating 3 minutes that hydrotalcite suspension is used rotating speed equally; Form the inorganic nano layer of 30nm (AFM mensuration), placed 4 minutes, accomplish 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 acid ester emulsion preparation are with embodiment 1
With corrosion resistant plate aqueous slkali (oxygen sodium oxide molybdena 30g/L, sodium carbonate 30g/L, tertiary sodium phosphate 40g/L, OP-emulsifying agent 3mL/L) washing oil removing 15min under 80 ℃ of temperature.Through on the pretreated corrosion resistant plate, it is 1000 rev/mins whirler spin coating 5 minutes that acrylic acid ester emulsion is used rotating speed, obtains the polymeric layer of 350nm (AFM mensuration); Dry 3 minutes; On polymeric layer, it is 1000 rev/mins of whirler spin coatings 5 minutes that montmorillonite suspension liquid is used rotating speed equally then, forms the inorganic layer of 15nm (AFM mensuration); Room temperature condition was placed 3 minutes; Accomplish 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 acid ester emulsion preparation are with embodiment 1.
Acrylic acid ester emulsion is passed through high-pressure spray gun (jet size 0.3mm; Every some spray time 1s, gun slot is apart from glass plate 10cm) spraying one layer thickness is the polymeric layer of 4.8um (AFM mensuration) on pretreated glass plate, placed 10 minutes; Then on polymeric 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, placed equally 10 minutes, accomplish 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 dodecyl sodium sulfate is dissolved in the 100g deionized water; Be warming up to 50 ℃; Add 6.0g methyl methacrylate, 6.0g vinylacetate, 4.0g butyl methacrylate mix monomer, 0.2g ammonium persulfate; Keep thermotonus 8h, system is cooled to room temperature obtains acrylic acid ester emulsion, solid content detects through weight method and is 14.0wt%.
Acrylic acid ester emulsion is passed through high-pressure spray gun (jet size 0.3mm; Every some spray time 1s, gun slot is apart from glass plate 10cm) spraying one layer thickness is the polymeric layer of 3um (AFM mensuration) on pretreated glass plate, placed 8 minutes; Then on polymeric 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, accomplish the preparation of one deck hybrid coating; 8 circulations so repeatedly, obtaining thickness is the hydridization class coating material of 25um (AFM mensuration).
Claims (6)
1. 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 ultrasonic dispersion in back that stirs makes mass concentration and is the suspension of 0.1 ~ 5% inorganic nano-particle; Said inorganic nano-particle is imvite or hydrotalcite;
(2) monomer, surfactant, initator add in the deionized water; Under 50～80oC temperature, carried out polymerisation 5～8 hours; After finishing, reaction is cooled to room temperature; Make polymer emulsion, the mass ratio of said monomer, surfactant, initator, deionized water is 10～70: 0.5～3:0.05 ~ 0.3: 100; Said monomer is one or more the mixing in butyl acrylate, acrylic acid, methyl methacrylate, styrene, vinylacetate, butyl methacrylate, hydroxy-ethyl acrylate, methacrylic acid, the acrylamide; When said inorganic nano-particle was imvite, said surfactant was a cationic surfactant, and when said inorganic nano-particle was hydrotalcite, said surfactant was an anion surfactant; Said initator is azo-bis-isobutyrate hydrochloride or ammonium persulfate;
Said cationic surfactant is following one or more mixing: softex kw, octadecyl trimethylammonium bromide, methylacryoyloxyethyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, DTAC or stearyl dimethyl benzyl ammonium chloride;
Said anion surfactant is following one or more mixing: lauryl sodium sulfate, dodecyl sodium sulfate or neopelex;
(3) polymer emulsion for preparing of step (2) makes the ground floor polymeric layer that thickness is 50nm ~ 5 μ m thickness through spin-coating or spraying method on matrix; After the drying; The suspension of the inorganic nano-particle that step (1) is prepared makes the ground floor inorganic nano-particle sublayer that thickness is 10 ~ 200nm thickness through spin-coating or spraying method on the ground floor polymeric layer, make ground floor hydridization after the drying and film; Said matrix is glass basis, metallic matrix, stone material matrix or plaster matrix;
(4) according to the method repetitive cycling operation of step (3), the orderly hydridization of stratiform that makes thickness 500nm ~ 40 μ m is filmed.
2. the method for claim 1 is characterized in that in the said step (1), and said ultrasonic dispersion is under the ultrasonic wave effect of power 100 ~ 600W, to disperse 10 ~ 30 minutes.
3. the method for claim 1 is characterized in that in the said step (3), and the method for spin-coating is 500 ~ 2000 rev/mins a whirler spin-coating 1 ~ 5 minute for using rotating speed.
4. the method for claim 1; It is characterized in that in the said step (3); Said glass basis is to be in the mixed liquor of 70:30 with glass plate at the mass ratio of the hydrogen peroxide solution of the concentrated sulfuric acid and 30wt%; After soaking 15 ~ 30 minutes under 90 ~ 95 ℃ of temperature, clean through deionized water rinsing, drying obtains said glass basis.
5. the method for claim 1 is characterized in that in the said step (3), and said drying is at room temperature placing 2 ~ 10 minutes.
6. the method for claim 1 is characterized in that in the said step (3), said metallic matrix is a stainless steel substrate.
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