Summary of the invention
Use hypovanadic oxide powder and hypovanadic oxide powder and the compound preparation film of other materials, method is simple, is convenient to large-scale operation, not only can be used for the energy-saving transformation of original glass port, and can be coated on the different substrates, enlarges the applicability of vanadium dioxide.But hypovanadic oxide powder is prepared into the vanadium dioxide slurries, when forming film and coating, requires hypovanadic oxide powder to have excellent dispersing property and chemical stability.
At this, the invention provides a kind of vanadium dioxide composite granule, comprise that chemical constitution is V
1-xM
xO
2Vanadium dioxide nano powder, the vanadium dioxide nano powder surface is connected to machine modification long chain molecule, wherein M is doped element, 0≤x≤0.5.
Vanadium dioxide composite granule of the present invention, organically-modified to the surface process of vanadium dioxide and Dope nano-power thereof.It is different from the hypovanadic oxide powder of general unmodified or inorganic parcel and modification, and the mode by organic modifiers makes the vanadium dioxide surface connect organically-modified long chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.Use vanadium dioxide composite granule stability provided by the invention and good dispersity, can prolonged preservation use, can be used as intelligent heat insulation powder and be applied to prepare intelligent energy-saving coating or coating, also can be used for the heat insulation occasions such as glass and exterior wall.It is different from general lagging material, and it can significantly intercept infrared light when transformation temperature is above, can highly see through and be lower than the transformation temperature infrared rays, and this variation is reversible, can realize that the intelligence of solar heat is regulated.
Preferably, in the vanadium dioxide composite granule of the present invention, the content of organically-modified long chain molecule is 0.1~50%.More preferably, organically-modified long chain molecule content is 1~10%.Organically-modified long chain molecule content is too small, then can't realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between the organic molecule, affects on the contrary dispersion effect.
Preferably, organically-modified long chain molecule chain length is at 0.1nm~100nm.
The present invention relates to the organic surface modifying of vanadium dioxide nano particle, can effectively improve the dispersiveness of vanadium dioxide and Dope nano-power thereof and the chemical stability of powder.
Organically-modified long chain molecule is for comprising the functionalized organic long-chains such as chain alkyl, polyacrylic acid group, polyvinyl alcohol group, epoxide group, chain alkyl amine groups, halogenation chain alkyl, carboxylated chain alkyl.
Vanadium dioxide composite granule of the present invention, by the grafting of organically-modified properties-correcting agent on the hypovanadic oxide powder surface, be wrapped in the hypovanadic oxide powder surface, thereby can change the surface property of vanadium dioxide, difference according to selected group, can increase the dispersing property of vanadium dioxide composite particles in different solvents, expand the purposes of vanadium dioxide particle in intelligent temperature control coating or coating.
Preferably, the vanadium dioxide nano powder in the vanadium dioxide composite granule of the present invention is Rutile Type, and phase transition temperature is adjustable at-20~70 ℃.The shared ratio of rutile phase hypovanadic oxide can be up to 80%, even can reach 100%.This vanadium dioxide nano powder has the first-order phase transition characteristic, but the induced environment temperature variation, and this variation of intelligent response realizes that the band selective to sunlight sees through or covers.Usually when envrionment temperature was lower than transformation temperature, the film or the coating that contain vanadium dioxide almost were fully penetrating to the visible light in the sunlight and mid-infrared light; When temperature surpassed the semi-conductor of vanadium dioxide-metal phase change temperature, vanadium dioxide underwent phase transition and is converted into the R phase, and this moment, material can to the blocking of mid-infrared light selectivity, reach the purpose of transparent (visible light sees through) thermal resistance.Semi-conductor-the metal phase change of vanadium dioxide is thermoinducible reversible change, and its temperature switch effect can be used to the ultrared break-make of centering and carries out intelligent control.
The doped element M of regulation can be or arbitrary combination in the elements such as near 21~30 transition element the vanadium in the periodic table of elements, tin and near element thereof and tungsten, molybdenum, ruthenium, niobium in the present invention.Wherein, near 21~30 transition element in the periodic table of elements vanadium comprise scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and described tin and near element thereof comprise indium, antimony, tin, gallium, germanium, lead and bismuth.Preferred doped element is tungsten, molybdenum, bismuth, tin, iron, zinc and titanium.
Adopt above-mentioned doped element, can controlled doping hypovanadic oxide powder size and pattern, used doped element equally also can be regulated and control the phase transition temperature of vanadium dioxide.
In the present invention, doped vanadium dioxide powder is preferably particulate state, and the length-to-diameter ratio of particle is 1: 1~10: 1, is preferably 1: 1~5: 1, more preferably 1: 1~2: 1.Particle size is not more than 1um at least one dimension, preferably is not more than 100nm at least one dimension, more preferably all is not more than 100nm on three dimensions, most preferably all is not more than 70nm on three dimensions.Described particulate state can be such as subsphaeroidal, oval, snowflake shape, cube, sheet shape etc.
Hypovanadic oxide powder dispersed better with above-mentioned size and pattern.Dispersiveness through the composite granule after the modification also will be further enhanced.
The application also provides a kind of preparation method of vanadium dioxide composite granule, comprises that operation (1) is scattered in vanadium dioxide nano powder in the dispersion medium, gets mixture A; (2) in described mixture A, add dispersing auxiliary and the organic modifiers that is used to form hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to get mixture B; (3) mixture B drying is made organically-modified vanadium dioxide composite granule.
Hypovanadic oxide powder can be rutile phase hypovanadic oxide nanoparticle or doped rutile phase hypovanadic oxide nanoparticle.Can be the method preparation that provides according to publication 2010PA011267CN, also can be rutile phase hypovanadic oxide nanoparticle or the doped rutile phase hypovanadic oxide nanoparticle of other known method preparations.The powder granule gravel size decision is below 200nm.The pattern of powder can be particle, nanometer rod and flakes particle.If preparation doped rutile phase hypovanadic oxide nanoparticle, before doped element, can adopt alkaline reagents to process presoma (the tetravalent vanadium ion aqueous solution), can obtain the controlled hypovanadic oxide powder size of size and pattern (being not more than 1um at least one dimension) and pattern (particulate state, length-to-diameter ratio is not more than 10: 1), the hypovanadic oxide powder grain-size of preparation is little, uniform particle diameter, and stable crystal form, it is at water, good dispersity in the dispersion agent (for example polyvinylpyrrolidone), be easy to be coated on the matrixes such as glass, be suitable for preparing film and the coating of hypovanadic oxide powder.
The preparation method of vanadium dioxide composite granule provided by the invention, the dispersing auxiliary that adds in the operation (2) can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.
The organic modifiers that adds among the preparation method of vanadium dioxide composite granule provided by the invention, operation (2) can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent.Be preferably the silane coupling agent of pbz polymer long-chain.
Mode by coupling agent can make the vanadium dioxide surface connect the organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.
Used dispersion medium can be ethanol among the preparation method of vanadium dioxide composite granule provided by the invention, one or more in the inert solvents such as Virahol, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO) ethylene dichloride or acetone.
In inert media, carry out organically-modifiedly, can prevent the sex change of vanadium dioxide, improve the chemical stability of powder.
The preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.
In addition, the present invention also provides a kind of hypovanadic oxide powder slurry that comprises vanadium dioxide composite granule of the present invention.
Wherein, hypovanadic oxide powder slurry provided by the invention can possess, (1) vanadium dioxide composite granule, and it comprises that chemical constitution is V
1-xM
xO
2Vanadium dioxide nano powder, and described powder surface is connected to machine modification long chain molecule, wherein M is doped element, 0≤x≤0.5; And (2) dispersion medium.
In the hypovanadic oxide powder slurry of the present invention, vanadium dioxide composite granule weight ratio can be 1: 1~1: 1000.Preferably, the weight ratio of vanadium dioxide composite granule and dispersion medium is 1: 10~1: 100.Vanadium dioxide composite granule by the present invention's preparation can effectively disperse in 0~50% scope.If from the application point of smart coat, the scope of 1%-10% more preferably.Too high levels can affect the transmittance of coating, crosses the low intelligent effect of heat insulation that then is difficult to bring into play coating.
Can select in deionized water, ethanol, propyl alcohol, Virahol, ethyl acetate, toluene, the butanone one or more as the dispersion medium in the hypovanadic oxide powder slurry of the present invention again.
In addition, vanadium dioxide composite granule slurry of the present invention can also comprise dispersing auxiliary, this dispersing auxiliary can be to be selected from polyacrylate, polyacrylamide, polyphosphoric acid salt, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, one or more in modified polyurethane and the modified acroleic acid dispersion agent.
Again, the present invention further also provides a kind of vanadium dioxide intelligent temperature control coating, is coated on flexible substrates after this coating is mixed by hypovanadic oxide powder slurry of the present invention, polymer emulsion and coatings additive(s) and forms.
The solid content of vanadium dioxide composite granule is 0.1~50% in the vanadium dioxide intelligent temperature control coating provided by the invention.Be preferably 2%-20%.Similarly, effective film forming in the scope of the solid content 0.1~50% of vanadium dioxide composite granule in the vanadium dioxide intelligent temperature control coating.From application point, the too high transmittance that can affect coating of solid content is crossed the low intelligent effect of heat insulation that then is difficult to bring into play coating.
Vanadium dioxide intelligent temperature control coating dry film thickness provided by the invention is 0.05~50um.Be preferably 0.5~10um;The coating of thermal control coating can be adopted the modes such as spraying, blade coating, brushing, showering or roller coat, for the higher occasion of some precision requirement, the general mode that adopts roller coat, coating thickness can be adjusted according to the order number of coating roll and the solid content of coating fluid, and adopting advanced roller coating technology minimum can be 0.05um with build.
In addition, the present invention also provides a kind of intelligent temperature control energy-conservation composite film-stuck, comprises from inside to outside release film layer, gel coating, vanadium dioxide intelligent temperature control coating of the present invention, base material and surface functional layer are installed.
In each layer of composite film-stuck, the thickness of release film and base material can be identical, for example is 2~250um.The thickness that gel coating and surface functional layer are installed also can be identical, for example is 0.05~50um.Gel coating and surface functional layer are installed all can be prepared by coating process, coating method comprises the in the industry coating method in common knowledge such as spraying, blade coating, brushing, showering or roller coat.
In each layer of composite film-stuck, gel coating is installed is formed on the one side that base material contains the intelligent temperature control layer; Described release film is compound on the base material by gel coating is installed.Surface functional layer is formed on the base material one side relative with the intelligent temperature control layer.
Surface functional layer can be the high hard coating of UV light-cured polyurethane, the high hard coating of UV light-cured acrylic, the high hard coating of UV photocuring organosilicon, also comprise some heat curing epoxy hardening resins, the high hard coating of urethane, the high hard coating of vinylformic acid and the high hard coating of organosilicon etc., also comprise some antifouling waterproof paints, anti-fingerprint coating and Antistatic Paint etc.Can adopt the modes such as spraying, blade coating, brushing, showering or roller coat that surface functional layer is formed at base material.
Vanadium dioxide composite granule of the present invention and the hypovanadic oxide powder slurry that comprises this powder, can be applicable to prepare intelligent energy-saving coating or coating, the coating transparency of preparation is high, low, the ageing-resistant ability of mist degree is strong, be mainly used in film, the flexible materialss such as cloth also can be used for the heat insulation occasions such as glass and exterior wall.
The energy-conservation composite film-stuck of intelligent temperature control of the present invention is multilayered structure, and surface functional layer provides high performance anti scuffing, wear-resisting or anti-soil, anti-fingerprint, the characteristic such as antistatic, can satisfy the required wear-resisting requirement of daily cleaning, keeps buildings for a long time as new; The intelligent temperature control coating is coated on the base material, have by adding special construction that vanadium dioxide and the Dope nano-power thereof of phase changing function are realized solar heat intelligent temperature control performance at a certain temperature, automatic variation according to envrionment temperature, regulate the transmitance of sunlight, can utilize the solar control temperature variation; It is adhesion and the installation capability that product is provided convenience that gel coating and release film layer are installed, and explosion prevention function.If at building doors and windows, this film of surface label last layer of vehicle glass and Industrial Metal container can be realized cold and hot two-ways regulation, and it is warming to reach winter, summer cold insulation effect, can be effectively save energy.
Embodiment
Below, with reference to accompanying drawing, and further specify the present invention in conjunction with subordinate's embodiment.
Among the preparation method of vanadium dioxide composite granule of the present invention, comprise, vanadium dioxide nano powder is scattered in the dispersion medium, get the operation of mixture A; In described mixture A, add dispersing auxiliary and be used to form the organic modifiers of hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to get the operation of mixture B; Mixture B drying is made the operation of organically-modified vanadium dioxide composite granule.
The preparation method of above-mentioned vanadium dioxide composite granule, particularly, dispersion medium elder generation's high-speed stirring dispersing and mixing and the ultra-sonic dispersion that can be with weight percent content 1~50% hypovanadic oxide powder and 50~99% get mixture, in mixture, add again afterwards dispersing auxiliary and organic modifiers, 0~200 ℃ of lower stirring of constant temperature, disperse by modes such as ultrasonic, sand milling or ball millings, again centrifugation, vacuum-drying obtains organically-modified vanadium dioxide composite granule under the certain temperature.
Wherein, with in vanadium dioxide nano powder and the operation that dispersion medium mixes, the weight ratio of vanadium dioxide nano powder and dispersion medium can be 1: 1~1: 20.Preferably, the weight ratio of vanadium dioxide nano powder and dispersion medium is 1: 1~1: 10.It more preferably is 1: 2~1: 5.When weight ratio was too small, then hypovanadic oxide powder was low with the organic modifiers contact probability, needed long jitter time and larger properties-correcting agent consumption; Weight ratio is excessive, then is unfavorable for the abundant dispersion of powder in dispersion medium and wetting, affects the modified effect in later stage.
In the above-mentioned vanadium dioxide nano powder surface organic modification, organic modifiers can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent, is preferably the silane coupling agent of pbz polymer long-chain.The amount that organic modifiers adds in the mixture can be 0.05~5 % by weight; Be preferably 0.1~2 % by weight.Organically-modified long chain molecule content is too small, then can't realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between the organic molecule, affects on the contrary dispersion effect.Mode by coupling agent can make the vanadium dioxide surface connect the organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.In addition, used dispersing auxiliary can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.Dispersing auxiliary is mainly used in reducing the surface tension of solution, and the raising solvent is wetting powder surface, thereby improves dispersion effect.The amount that dispersing auxiliary adds in the mixture can be 0.02~2 % by weight; Be preferably 0.05~1 % by weight.Few add-on can reach needed dispersion effect.Add the surface organic modification process that too much can affect on the contrary powder.
The preparation method of hypovanadic oxide powder slurry provided by the invention, particularly, can be with weight percent content 0.1~50% hypovanadic oxide powder add 40~99% the middle and high speed of dispersion medium stir carry out pre-dispersed, in mixture, add again afterwards dispersing auxiliary, the hypovanadic oxide powder slurry that high-speed stirring must mix.Can described slurry be mixed by dispersion methods such as ultrasonic, ball milling and/or sand millings in addition.
Among the present invention, no matter be in the preparation process of vanadium dioxide composite granule or in the preparation process of composite granule slurry, the rotating speed of high-speed stirring can be 1000~3000rad/min.Ultrasonic power can be 50~5000W, and frequency is 21KHz.In addition, drum's speed of rotation can be chosen as 10~2000rad/min.Again, the rotating speed of sand mill can be 10~2000rad/min.Grinding medium can be selected zirconia balls, and particle diameter is preferably the grinding medium of small particle size at 0.02mm~50mm.
Be coated on flexible substrates after intelligent temperature control coating of the present invention is mixed by hypovanadic oxide powder slurry of the present invention, polymer emulsion and coatings additive(s) and form.Particularly, desirable hypovanadic oxide powder slurry 10~60 % by weight of the present invention, the polymer emulsion that adds therein 20~80 % by weight, and then adding amounts to the coatings additive(s) of 0.01~5 % by weight, for example wetting aid, film coalescence aid, flow agent, defoamer and/or thickening material, high-speed stirring stirs appropriate time, must be used for forming the mixed solution (coating) of coating.When being coated flexible substrates, the coating that makes to select the modes such as spraying, blade coating, brushing, showering or roller coat.Described base material can be the plastics film of the materials such as polypropylene (PP), polyethylene (PE), polymeric amide (PA), polyvinyl chloride (PVC), polyethylene terephthalate (PET) and polymethylmethacrylate (PMMA), the fiber or the woven bag that are perhaps prepared by these materials.
Film coalescence aid in the coatings additive(s) can be in ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, propylene glycol monobutyl ether, glycol propyl ether, the dipropyl ether one or more.
Wetting aid in the coatings additive(s) can be in dodecyl sulfate, dodecane sulfonate, polyvinyl alcohol, polyvinylpyrrolidone, silicoorganic compound and the organofluorine compound one or more.
Defoamer in the coatings additive(s) can be in dimethyl silicone oil, ether ester compound, modified mineral oil, polyoxy ethyl glyceryl ether, small molecules metallorganics and the silicon modified organic polymer one or more.
Flow agent in the coatings additive(s) can be in butyl glycol ether, cellaburate, polyacrylate(s), silicone oil and the modified organic silicon compound one or more.
Thickening material in the coatings additive(s) can be cellulose thickener, polyethylene wax, aerosil, agent for polyacrylic acid thickening, or association type polyurethanes thickening material.
In addition, can also in coating, add 0.2~2% UV light absorber, use such as the UV light absorber that benzophenone and derivative, o-hydroxy-phenyl benzotriazole and derivative thereof, aromatic ester compound or hydroxy phenyl s-triazine and derivative thereof etc. all can be used as in the coating of the present invention.
Below, by embodiment the present invention is described in more details.
Should be understood that the above-mentioned embodiment that the present invention describes in detail, and following examples only are used for explanation the present invention and are not used in and limit the scope of the invention.The raw material that adopts, reagent can marketable material or traditional chemical transform mode are synthetic to be made by buying.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method and material similar to described content or that be equal to all can be applicable in the inventive method in addition.Other aspects of the present invention are because the disclosure of this paper is that appearance is intelligible to those skilled in the art.
Fig. 1 is that the hypovanadic oxide powder surface is without the transmission electron microscope picture of organically-modified hypovanadic oxide powder; Referring to Fig. 1 as can be known, without the pattern of organically-modified vanadium dioxide nano powder particle, diameter of particle 10~100nm does not wait, and is that agglomerating particles exists but comparatively loose between the particle.
Fig. 2 is that the hypovanadic oxide powder surface is through the transmission electron microscope picture of organically-modified vanadium dioxide composite granule; Referring to Fig. 2 as can be known, the pattern of the vanadium dioxide composite granule of process organic surface modifying, diameter of particle 10~100nm does not wait, and powder is because be coated with the machine group, and the more not organically-modified particle of particle diameter increases slightly, but presents dispersion state between the powder.
Fig. 3 is the high low temperature graphic representation of vanadium dioxide intelligent temperature control coating in the example of the present invention (embodiment 1); To have adopted hypovanadic oxide powder of the present invention and slurry thereof and the high low temperature graphic representation of the intelligent temperature control coating for preparing; Referring to Fig. 3 as can be known, the visual transmitance low temperature 53.3% of this embodiment floating coat, high temperature 51.8%, sun power transmitance low temperature 57%, high temperature 43.6%, 40 ℃ of the transformation temperatures of coating, high low-temperature solar energy is regulated efficient can reach 13.4%, the infrared integral adjustment rate 24.2% of high low temperature, high low temperature infrared light 1500nm transmitance difference can reach 36.8%.
Fig. 4 is the high low temperature curve (comparison example 6) that does not adopt the intelligent temperature control coating of modification vanadium dioxide preparation, its difference with the coating (Fig. 3) that adopts organically-modified vanadium dioxide preparation is, owing to do not adopt the modification hypovanadic oxide powder, its dispersiveness is bad, cause high temperature curve (red line) will be lower than low temperature curve (black line) at visible light part, and adopt the coating high-temp curve (red line) of modification hypovanadic oxide powder preparation will be higher than low temperature curve (black line) at visible light part.And visible light transmissivity, infrared performance of control will be lower than the coating (Fig. 3) that adopts the preparation of modification hypovanadic oxide powder.
Embodiment 1
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20~100nm), 20g
Ethanol (dispersion medium), 80g
Silane coupling agent (containing the polyvinyl alcohol group, organic modifiers), 1g
Polyvinylpyrrolidone (dispersing auxiliary), 0.05g;
High-speed stirring under 1500rad/min is disperseed 30min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 30min, again dispersing auxiliary and silane coupling agent are added wherein, 70 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide composite granule of organo-silicon coupling agent modification;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 4g
Deionized water, 95.5g
The modified acroleic acid dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 40%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 30%
Deionized water: 28%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
UV light absorber (hydroxy phenyl s-triazine derivative): 0.5%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 3.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 2
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (undopes particle diameter 20~100nm), 10g
Ethanol (dispersion medium), 90g
Silane coupling agent (containing the chain alkyl amine groups, organic modifiers), 1g
Polyvinyl alcohol (dispersing auxiliary), 0.05g
High-speed stirring under 1500rad/min is disperseed 30min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 30min, again dispersing auxiliary and stearic acid are added wherein, 60 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule of chain alkyl amine groups modification;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 5g
Deionized water, 94.5g
The polyacrylic acid dipersant, 0.05g
The organic modified nano powder is added the pre-dispersed 10min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 30min again, stir process 1h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 60%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 5%): 30%
Deionized water: 8.5%
Film coalescence aid (propylene glycol monobutyl ether): 0.25%
Wetting aid (polyvinyl alcohol): 0.1%
Flow agent (polyacrylate(s)): 0.15%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (association type polyurethanes thickening material): 0.35%
UV light absorber (o-hydroxy-phenyl benzotriazole derivatives): 0.4%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 2.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 3
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20~100nm), 15g
Virahol (dispersion medium), 85g
Silane coupling agent (containing epoxy functionalized group, organic modifiers), 1g
Organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution (dispersing auxiliary), 0.08g
High-speed stirring under 1000rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and silane coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule that the surface is connected to chain alkyl;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 1.5g
Deionized water, 98g
The modified poly ester dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 20min again, stir process 1h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (ACRYLIC EMULSION): 45%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 1.5%): 45%
Deionized water: 5%
Film coalescence aid (phenyl ether): 0.5%
Wetting aid (silicoorganic compound): 0.2%
Flow agent (modified organic silicon compound): 0.25%
Defoamer (small molecules metallorganics): 0.25%
Thickening material (association type polyurethanes thickening material): 0.8%
UV light absorber (o-hydroxy-phenyl benzotriazole derivatives): 0.5%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 2500rad/min stirs 3h, obtains vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of spraying, and coat-thickness is controlled at 6.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 4
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (doping molybdenum, particle diameter 20~100nm), 25g
Virahol (dispersion medium), 75g
Titanate coupling agent (containing epoxide group, organic modifiers), 1g
Polyvinyl alcohol (dispersing auxiliary), 0.15g
High-speed stirring under 1500rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and titanate coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 70 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano composite granule that the surface is connected to epoxide group;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 3g
Deionized water, 96.95g
The modified acroleic acid dispersion agent, 0.05g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 30min again, stir process 1h on homogenizer obtains vanadium dioxide and Dope nano-power slurry thereof;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (ACRYLIC EMULSION): 50%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 3%): 30%
Deionized water: 18.5%
Film coalescence aid (ethylene glycol monobutyl ether): 0.2
Wetting aid (silicoorganic compound): 0.05%
Flow agent (cellaburate): 0.2%
Defoamer (modified mineral oil): 0.35%
Thickening material (agent for polyacrylic acid thickening): 0.2%
UV light absorber (benzophenone derivates): 0.5%
Add ACRYLIC EMULSION and deionized water in the hypovanadic oxide powder slurry, add wetting aid again, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 2500rad/min stirs 2h, obtains vanadium dioxide intelligent temperature control coating; Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 2.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Embodiment 5
(1) surface organic modification of vanadium dioxide nano powder:
It is as follows to get each constituent mass:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20~100nm), 5g
Virahol (dispersion medium), 95g
Aluminate coupling agent (containing chain alkyl, organic modifiers), 0.7g
Polyvinylpyrrolidone (dispersing auxiliary), 0.04g
High-speed stirring under 1500rad/min is disperseed 20min with vanadium dioxide nano powder and dispersion medium first, and ultra-sonic dispersion 60min, again dispersing auxiliary and aluminate coupling agent are added wherein, 80 ℃ of lower 2h that stir of constant temperature on homogenizer, again centrifugation, 60 ℃ of lower vacuum-dryings obtain the vanadium dioxide nano powder that the surface is connected to chain alkyl;
(2) preparation of vanadium dioxide composite granule slurry:
It is as follows to get each constituent mass:
The vanadium dioxide composite granule that makes in the present embodiment (1), 4g
Ethyl acetate, 95.5g
The modified polyurethane dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(3) preparation vanadium dioxide intelligent temperature control coating
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 70%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 20%
Deionized water: 8.5%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of blade coating, and coat-thickness is controlled at 5.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Comparative example 6
(1) gets the vanadium dioxide nano powder of the non-modified of using in above-described embodiment 1 (1), 4g
Deionized water, 95.5g
The modified acroleic acid dispersion agent, 0.5g
The organic modified nano powder is added the pre-dispersed 5min of deionized water high-speed stirring, add dispersion agent ultra-sonic dispersion 60min again, stir process 2h on homogenizer obtains vanadium dioxide composite granule slurry;
The salient features of resulting vanadium dioxide composite granule and slurry thereof sees Table 1 in the present embodiment;
(2) get in this comparative example the slurry that makes in above-mentioned (1), each raw material is by following mass percent preparation:
Each raw material accounts for mass percent:
Polymer emulsion (polyaminoester emulsion): 40%
The hypovanadic oxide powder slurry that makes in the present embodiment (2) (solid content 4%): 30%
Deionized water: 28%
Film coalescence aid (propylene glycol monobutyl ether): 0.5%
Wetting aid (polyvinyl alcohol): 0.2%
Flow agent (polyacrylate(s)): 0.25%
Defoamer (modified organic silicon compound): 0.25%
Thickening material (cellulose thickener): 0.4%
UV light absorber (hydroxy phenyl s-triazine derivative): 0.5%
In the hypovanadic oxide powder slurry, add ACRYLIC EMULSION and deionized water, add again wetting aid, film coalescence aid, flow agent, defoamer, UV light absorber and thickening material high-speed stirring under 1500rad/min stirs 1h, obtains water-based vanadium dioxide intelligent temperature control coating.Resulting vanadium dioxide intelligent temperature control coating is applied on the PET with the mode of roller coat, and coat-thickness is controlled at 5.5 microns, and the intelligent temperature control coating fundamental property that obtains sees Table 2.
Referring to following table 1, from this table organically-modified vanadium dioxide composite granule and the slurry thereof that method provided by the invention obtains can be described, its particle diameter is significantly less than unmodified powder, and the BET specific surface area is greater than unmodified powder, and Stability of Slurry also will be significantly better than unmodified powdery pulp.Can find out by the surface organic modification process by 300 ℃ of weightless data, can connect at nano powder surface 5~10% organic long-chain, thereby greatly improve chemical stability and the dispersiveness of hypovanadic oxide powder.
Table 1:
Referring to following table 2, coating of the present invention has higher visible light transmissivity, complete shielding ultraviolet rays almost simultaneously, can carry out intelligence to the higher infrared rays of energy in the sunlight simultaneously and regulate (seeing through difference from high low temperature infrared rays can find out), the transparent light of appearance of coat (the coating mist degree is low) is ageing-resistant simultaneously, waterproof, sticking power is good, and abrasion resistance is strong; And not organically-modified VO2 slurry (contrast application example 6) is compared together, and the coating intelligent control rate that present method obtains is better, and visible light transmissivity is low, and mist degree is less.
Table 2 (coating property test):
Below, by embodiment energy-conservation composite film-stuck of intelligent temperature control of the present invention and preparation method thereof is described in detail.Should understand, below also can omit or use other alternative steps that can reach with texts about in the energy-conservation composite film-stuck preparation method of the intelligent temperature control of the present invention step certain, and each feature in each step neither be necessary or replaceable regularly and not, and just example ground explanation.
Embodiment 7
(1) chooses the PET release film, thickness 50um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 4) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 50um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 2.5um;
(3) preparation of surface functional layer.To contain the mode of light-cured acrylic cured coating by roller coat is applied on another surface of PET temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 80~100 ℃ of oven temperatures, UV lamp power 80~150W/cm, dry film coating thickness 1.5um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of acrylate pressure sensitive adhesive by roller coat is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, dry film coating thickness 5um.The one side that directly will be coated with acrylate pressure sensitive adhesive after the drying is compound by pressure roller with the release film of step (1) preparation, 50~60 ℃ of roller temperatures, 90~110 ℃ of oven temperatures.
Embodiment 8
(1) chooses the PET release film, thickness 25um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 100um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of the preparation release film of surface functional layer is similar with embodiment 7;
(4) preparation of the compound release film of the energy-conservation composite film-stuck of intelligent temperature control is similar with embodiment 7.
Embodiment 9
(1) chooses the PET release film, thickness 20um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 3) that will contain organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 25um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 4.5um;
(3) surface functional layer is selected antistatic coating, and the preparation of the preparation release film of coating is similar with embodiment 7;
(4) preparation of the compound release film of the energy-conservation composite film-stuck of intelligent temperature control is similar with embodiment 7.
Embodiment 10
(1) chooses the PP release film, thickness 20um;
The preparation of (2) intelligent temperature control coating.The coating (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PP base material by the mode that sprays, base material thickness 50um, surface covered 35m/min, the rolling of process oven drying obtains containing the PP temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer.To contain the mode of photocuring organosilicon cured coating by spraying is applied on another surface of PP temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 90~120 ℃ of oven temperatures, UV lamp power 80~150W/cm, dry film coating thickness 2um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of organic silica gel by spraying is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, roller dry film coating thickness 10um.The one side that will be coated with afterwards acrylate pressure sensitive adhesive is compound by pressure roller with the release film of step (1) preparation, 50~60 ℃ of roller temperatures, 90~110 ℃ of oven temperatures.
Embodiment 11
(1) chooses the PVC release film, thickness 15um;
The preparation of (2) intelligent temperature control coating.The slurry (being made by above-described embodiment 1) that will contain organically-modified vanadium dioxide composite granule is applied on the PVC base material by the mode of blade coating, base material thickness 80um, surface covered 35m/min, the rolling of process oven drying obtains containing the PVC temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer.To contain the mode of thermofixation vinylformic acid cured coating by blade coating is applied on another surface of PVC temperature control film that step (2) contains the intelligent temperature control coating, surface covered 30m/min, after passing through again the baking oven preheating and drying, solidify through the UV lamp, rolling obtains that one side contains the intelligent temperature control coating, one side contains the PET temperature control film of surface functional layer, 90~120 ℃ of oven temperatures, UV lamp power 80~150W/cm, dry film coating thickness 2um;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of organic silica gel by blade coating is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, roller dry film coating thickness 10um.The one side that directly will be coated with acrylate pressure sensitive adhesive after the drying is compound by pressure roller with the release film of step (1) preparation, 50~60 ℃ of roller temperatures, 90~110 ℃ of oven temperatures.
Embodiment 12
(1) chooses the PET release film, thickness 25um;
The preparation of (2) intelligent temperature control coating.The slurry (being made by above-described embodiment 1) that will contain 3% organically-modified vanadium dioxide composite granule is applied on the PET base material by the mode of roller coat, base material thickness 80um, surface covered 35m/min, the rolling of process oven drying obtains containing the PET temperature control film of intelligent temperature control coating again, 90~120 ℃ of oven temperatures, dry film coating thickness 3.5um;
(3) preparation of surface functional layer is similar with embodiment 10;
(4) the energy-conservation composite film-stuck of intelligent temperature control is compound.The mode of acrylate pressure sensitive adhesive by roller coat is applied on the one side that contains the intelligent temperature control coating of PET temperature control laminated film of step (3) preparation, surface covered 30m/min, pass through oven drying again after, dry film coating thickness 5um.The one side that will be coated with afterwards acrylate pressure sensitive adhesive is compound by pressure roller with the release film of step (1) preparation, 50~60 ℃ of roller temperatures, 90~110 ℃ of oven temperatures.
Following table 3 is salient features and the performance test of the prepared intelligent temperature control composite film-stuck of embodiment 7-12:
Table 3 explanation, the energy-conservation composite film-stuck of intelligent temperature control of the present invention has higher visible light transmissivity, complete shielding ultraviolet rays almost simultaneously, can carry out intelligence to the higher infrared rays of energy in the sunlight simultaneously and regulate (seeing through difference from high low temperature infrared rays can find out), the transparent light of appearance of coat (the coating mist degree is low) is ageing-resistant simultaneously, waterproof, sticking power is good, and abrasion resistance is strong.
Industrial applicability: the preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.Vanadium dioxide composite granule of the present invention can be applicable to prepare the energy-conservation composite film-stuck of intelligent power saving coating, coating or intelligent temperature control, the coating of preparation or pad pasting transparency are high, low, the ageing-resistant ability of mist degree is strong, be mainly used in film, the flexible materialss such as cloth also can be used for the heat insulation occasions such as glass and exterior wall.Also can be widely used in energy-saving and emission-reduction equipment, for example energy-conservation film, energy-saving coatings, sun power temperature control unit; Or energy information equipment, for example, micro photo electric switch device, thermistor, battery material and optical information storage spare.