CN105713597A - Composite thermochromic paste and preparing method thereof - Google Patents
Composite thermochromic paste and preparing method thereof Download PDFInfo
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- CN105713597A CN105713597A CN201610111203.7A CN201610111203A CN105713597A CN 105713597 A CN105713597 A CN 105713597A CN 201610111203 A CN201610111203 A CN 201610111203A CN 105713597 A CN105713597 A CN 105713597A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention relates to composite thermochromic paste and a preparing method thereof. The composite thermochromic paste comprises vanadium dioxide nanometer powder serving as an inorganic thermochromic material, a dentate conversion body serving as an organic thermochromic material, a polymer base material and a dispersion medium. The dentate conversion body comprises convertible metal ions, a low-absorbancy ligand capable of forming a low-absorbancy complex with the convertible metal ions, and a high-adsorbancy ligand capable for forming a low-adsorbancy ligand with the convertible metal ions. The composite thermochromic paste has the advantages that the thermochromic wave band range covers the whole solar radiation spectrum comprising visible light, and the paste has extremely high total solar radiation adjusting rate compared with a traditional vanadium dioxide thermochromic materials.
Description
Technical field
The invention belongs to high-performance inorganic-organic composite material technical field, apply particularly to thermochromic material and energy-conserving and environment-protective thereof.
Background technology
Global energy shortage problem is day by day serious, and excessive carbon emission causes environment to go from bad to worse, and energy-saving and emission-reduction have become the top priority of current various countries.According to estimates, in society's total energy consumption, building energy consumption accounts for more than 30%, and therefore, to advance building energy conservation be energy-saving and emission-reduction, one of the emphasis measure realizing sustainable development.
In building energy consumption, significant portion is used for air-conditioning, and windowpane is as building and the extraneous main thoroughfare carrying out heat exchange, becomes the main path that air conditioner energy source runs off.Therefore, use various types of Energy Saving Windows, energy consumption can be effectively reduced, reach the purpose of energy-conserving and environment-protective.
Existing market Energy Saving Windows main product is Low emissivity (Low-E) glass and heat-reflecting glass etc., and due to technology maturation, low price, heat-proof quality is good, is widely used in building energy conservation.But owing to above-mentioned Energy Saving Windows optical property can not because of seasonal variations and think that demand arbitrarily changes, it is difficult to adapt to the energy saving requirement in most of cold summer thermally district of China and the requirement that people are increasingly higher to living environment level of comfort.Then, the new energy-conserving product being referred to as " Intelligent energy-saving window " just arises at the historic moment.
What Intelligent energy-saving window use optical property was variable causes off-color material, utilizes the changes such as its transflector performance that various physical stimulations are produced, reaches the controllable adjustment purpose of indoor environment photo-thermal.Obviously, Intelligent energy-saving window is suitable for the demand of overwhelming majority area and Different climate condition, also makes indoor living environment that people is more suitable.
According to physical stimulation kind and Discoloration mechanism, there is an electrochromism, gas-discoloration, photochromic, the Intelligent energy-saving window of multiple kinds such as thermochromism.
In various types of Intelligent energy-saving windows, utilize the thermochromism Energy Saving Windows that the SEMICONDUCTOR-METAL reversible transition principle of vanadium dioxide near room temperature is developed, there is simple in construction, material usage is few, completely dispense with switch or artificial energy source controls just to accord with one's environment variations in temperature and realize the remarkable advantages such as automatic photo-thermal regulation and control, obtain in various countries and pay attention to and in succession research and develop.Wherein, using the temperature control intelligent power saving Filming Technology of nano vanadium dioxide to take the lead in obtaining in China breaking through, the hypovanadic oxide-based temperature control intelligent power saving pad pasting prepared is about to put on market.
But, as the main inventive person of above-mentioned technology, notice that above-mentioned vanadium dioxide temperature control Intelligent energy-saving window still exists following some deficiencies simultaneously:
(1) insolation infrared band having the higher amplitude of accommodation, but the visible light wave range accounting for insolation gross energy 50% is had adjustment effect hardly, its result reduces global solar radiation regulation rate；
(2) owing to not there is obvious adjustment effect at visible light wave range, this adjustment cannot be utilized to produce enough visible change, thus being helpless to client is carried out strong regulating effect demonstration, conducting promotion to of product is caused conclusive harmful effect；
(3) short-wave band visible ray is had strong absorption effect, cause thin film yellow color development.
There is no mature technology so far and fundamentally solve above-mentioned some problem.It is clear that the solution of the problems referred to above will imply that the tremendous breakthrough of hypovanadic oxide-based thermochromism Energy Saving Windows application technology.
Summary of the invention
Dentate conversion body thermochromism (LigandExchangeThermochromic is called for short LETC) material combines from different dentates by changing metal ion under different temperatures, form the coordination compound with different absorptance, thus producing thermo-chromic effects, in general, at low temperatures, metal ion is combined formation low absorption coefficient coordination compound with low absorption coefficient dentate, has higher transmitance；At high temperature, metal ion transfers to be combined formation high absorption coefficient coordination compound with high absorption coefficient dentate, has relatively low transmitance.This temperature control optical change is reversible, occurs mainly with visible light wave range particular range of wavelengths.
But, common LETC materials Thermochromic occurs over just wavelength band very narrow in the neighbouring i.e. full spectrum of insolation of visible ray, causes regulating power less than normal.More owing to being that the mid and far infrared wave band that human temperature hotness is most sensitive can not be regulated, it is impossible to carry out ensureing the adjustment of human body comfort.
It addition, LETC material is only capable of by the absorption of above-mentioned wavelength band light reaches adjustment purpose, material itself does not have reflection effect, and therefore regulating effect is affected.
The present inventor is based on the long-term R & D experience to thermochromic material, by repeatedly testing, find by constituting a kind of brand-new composite in conjunction with vanadium dioxide material with LETC material first, the thermo-chromic effects that can make new material contains the insolation full band range including visible ray and infrared band, regulating power and level of comfort have the progress of leap, has thus completed the present invention.
The present invention provides a kind of compound thermochromism slurry, including the vanadium dioxide nano powder as inorganic system thermochromic material, the dentate conversion body as organic system thermochromic material, polymeric substrate and disperse medium, described dentate conversion body comprises can change metal ion, can form the low absorbance ligand of low absorbance coordination compound with the described metal ion that changes and can form the high absorbance ligand of high absorbance coordination compound with the described metal ion that changes.
The compound thermochromism slurry of the present invention, is characterized in that thermochromism wavelength band contains the whole insolation spectrum including visible ray, thus has high global solar radiation regulation rate compared with tradition vanadium dioxide thermochromic material.Meanwhile, at the bigger mediating effect+6 of visible light wave range, being changed into visual significant change, effect plays and publicity popularization to product have decisive significance.Further, since add the visible ray absorption compared with long-wave band so that the intrinsic yellow color development of vanadium dioxide obtains bigger suppression.
It is preferred that described vanadium dioxide nano powder is doped or non-doped rutile phase hypovanadic oxide.
It is preferred that the particle diameter of described vanadium dioxide nano powder is 20～80nm.
Preferably, the described metal ion that changes is at least one in Fe (II), Co (II), Ni (II), Cu (II), described low absorbance ligand is at least one in dihydroxylic alcohols, trihydroxylic alcohol, polyhydric alcohol, preferred neopentyl glycol, trimethylolpropane, ethylene glycol, glycerol, 2-methyl isophthalic acid, at least one in ammediol；Described high absorbance ligand comprises can with the coordinating group that can change metal ion formation high absorbance coordination compound, it is preferable that tetrabutyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, choline chloride, triphenylphosphine, at least one in tetrathiacyclotetradecane.
It is preferred that the mol ratio of the changed metal ion in vanadium dioxide and dentate conversion body is 9:1～1:9, it is preferable that 2:1～1:6, more preferably 1:1～1:4.
It is preferred that described polymeric substrate is polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl acrylic acid methyl ester., polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly-2-ethyl-2-azoles quinoline, polyvinylpyrrolidone and containing at least one in the copolymer of above-mentioned polymers functionality.
It is preferred that described disperse medium is at least one in deionized water, ethanol, propanol, isopropanol, ethyl acetate, toluene, acetone, butanone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate.
It is preferred that in described compound thermochromism slurry, the concentration of vanadium dioxide nano powder is 0.1～2mol/L；The concentration of vanadium dioxide nano powder and polymeric substrate is than for 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1；The concentration that can change metal ion is 0.5～5mol/L.
On the other hand, the present invention also provides for the preparation method that any one compound thermochromism slurry above-mentioned is coated with, and comprises the following steps:
A. prepare vanadium dioxide nano powder and be scattered in disperse medium, obtaining dispersion liquid A；
B. adding soluble polymer in dispersion liquid A, stirring is completely dissolved to polymer, obtains dispersion liquid B；
C. adding dentate conversion body in dispersion liquid B, stirring, to being completely dissolved, obtains dispersion liquid C；
D. continuously stirred dispersion liquid C heating, the unnecessary disperse medium of evaporation section, obtains described compound thermochromism slurry.
It is preferred that vanadium dioxide concentration is 0.01～1mol/L in dispersion liquid A, it is preferable that 0.05～0.5mol/L, more preferably 0.1～0.2mol/L；In dispersion liquid B, the concentration of vanadium dioxide and polymer is than for 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1；In dispersion liquid C, the concentration of the changed metal ion of dentate conversion body is 0.01～5mol/L, 0.1～2mol/L, more preferably 0.5～1mol/L.
Another further aspect, the present invention also provides for a kind of compound thermochromic coatings, and it is prepared by any one compound thermochromism slurry above-mentioned.
Another aspect, the present invention also provides for a kind of compound thermochromic thin film, and it is coated on matrix by any one compound thermochromism slurry above-mentioned and prepares.
Accompanying drawing explanation
Fig. 1 is the hypovanadic oxide-based composite film of embodiment 1 photo in kind under 20 DEG C (left sides) and 80 DEG C (right side)；
Fig. 2 is the hypovanadic oxide-based composite film of embodiment 1 absorption curve at 20 DEG C and 80 DEG C；
Fig. 3 is the hypovanadic oxide-based composite film of embodiment 3 photo in kind under 20 DEG C (left sides) and 80 DEG C (right side)；
Fig. 4 is the independent thin film of vanadium dioxide of comparative example 1 photo in kind under 20 DEG C (left sides) and 80 DEG C (right side).
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are merely to illustrate the present invention below in conjunction with accompanying drawing and following embodiment, and the unrestricted present invention.
The invention provides a kind of hypovanadic oxide-based thermochromic composite of high-performance, this composite contains inorganic system thermochromic material and organic system thermochromic material simultaneously, inorganic system thermochromic material is vanadium dioxide, and organic system thermochromic material is dentate conversion body.
In the present invention, dentate conversion body comprises can change metal ion, can form with it the low absorbance ligand of low absorbance coordination compound and can form with it high absorbance ligand both dentate materials of high absorbance coordination compound.Combine from different dentates by metal ion can be changed under different temperatures, form the coordination compound with different absorptance, thus producing thermo-chromic effects, at low temperatures, metal ion is combined formation low absorption coefficient coordination compound with low absorbance ligand, has higher transmitance；At high temperature, metal ion transfers to be combined formation high absorption coefficient coordination compound with high absorbance ligand, has relatively low transmitance.This temperature control optical change is reversible, occurs mainly with visible light wave range particular range of wavelengths.
The described metal ion that changes can be transition metal ions, it is preferred at least one in Fe (II), Co (II), Ni (II), Cu (II).Select at least one of which to combine from different dentates, specific absorption can be obtained at different-waveband as required.
The absorbability of light can be represented by dentate conversion body with absorbance.Described low absorbance refers at 400～1400nm wave-length coverage internal absorbance less than 0.2, and described high absorbance refers to that at 400～1400nm wave-length coverage internal absorbance be more than 0.8.
Low absorbance ligand includes but not limited at least one in dihydroxylic alcohols, trihydroxylic alcohol, polyhydric alcohol, it is preferable that neopentyl glycol, trimethylolpropane, ethylene glycol, glycerol, 2-methyl isophthalic acid, at least one in ammediol.High absorbance ligand comprises can with the coordinating group that can change metal ion formation high absorbance coordination compound, such as can contain at least one in N, P, S atom, and/or at least one in chloride, bromide, iodide, Pseudohalides, preferred tetrabutyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, choline chloride, triphenylphosphine, at least one in tetrathiacyclotetradecane.
In dentate conversion body, the mol ratio that can change metal ion and low absorbance ligand and high absorbance ligand can be (0.1～1): (1～10): (4～10).
It addition, dentate conversion body also can comprise polymer, using the bridge changed as ligand.Furthermore, it is to be understood that dentate conversion body not necessarily comprises polymer, there is solvent when existing, not need polymer, solvent and polymer and can replace mutually as ligand conversion bridge.Described polymer includes but not limited to polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl acrylic acid methyl ester., polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly-2-ethyl-2-azoles quinoline, polyvinylpyrrolidone and containing at least one in the copolymer of above-mentioned polymers functionality.
Vanadium dioxide in the present invention can be the vanadium dioxide of undoped, it is also possible to be the vanadium dioxide with doped chemical.Vanadium dioxide can be Rutile Type.Vanadium dioxide crystallization has reversible transition and the change of huge optical property at 68 DEG C.And by means such as element dopings, it is possible to transition temperature is accurately controlled near room temperature.Vanadium dioxide in the present invention includes the various key elements of traditional hypovanadic oxide-based thermochromism Energy Saving Windows such as doped vanadium dioxide.
The chemical composition of doped vanadium dioxide powder can be V1-xMxO2, in formula, 0 < x≤0.5.Doped chemical can be or combination in any in 21～30 transition elements near vanadium in the periodic table of elements, stannum and the element such as neighbouring element and tungsten, molybdenum, ruthenium, niobium, tantalum, magnesium thereof.Wherein, in the periodic table of elements, 21～30 transition elements near vanadium include scandium, titanium, chromium, manganese, ferrum, cobalt, nickel, copper and zinc, described stannum and neighbouring element thereof include indium, antimony, stannum, gallium, germanium, lead and bismuth, it is preferred that doped chemical is tungsten, molybdenum, bismuth, stannum, niobium, tantalum, magnesium, ferrum, zinc and titanium.Adopt above-mentioned doped chemical, it is possible to the size of controlled doping hypovanadic oxide powder and pattern, or also can regulate and control the phase transition temperature of vanadium dioxide simultaneously.
In the present invention, vanadium dioxide can be powder body, it is preferred to graininess, namely exists with the form of vanadium dioxide nano granule.The draw ratio of granule can be 1:1～10:1, it is preferred to 1:1～5:1, more preferably 1:1～2:1.Particle size is not more than 1 μm at least one dimension, it is preferable that be not more than 100nm at least one dimension, more preferably in three dimensions no more than 100nm, for instance 20～80nm.Described graininess can be subsphaeroidal, oval, snowflake shape, cube, sheet-shaped etc..
It addition, vanadium dioxide nano granule can also have external coating.This external coating is preferably transparent, it is possible to do not affect again the overall visible light permeability of vanadium dioxide granule while improving the stability of vanadium dioxide granule.As the material of external coating, include but not limited in carbon, silicon oxide, magnesium oxide and aluminium oxide more than one.The thickness range of external coating can be 2～20nm.
Vanadium dioxide and dentate conversion body can carry out compound as required in any proportion in principle, but great many of experiments shows, the preferred 9:1～1:9 of mol ratio, more preferably 2:1～1:6, it is most preferred that 1:1～1:4 of metal ion in vanadium dioxide and LETC material.
The present invention is by constituting a kind of brand-new composite in conjunction with vanadium dioxide material with LETC material, so that the thermo-chromic effects of new material covers the insolation full band range including visible ray and infrared band, regulating power and level of comfort have the progress of leap.
It is clear that by the adjustment effect to the visible light wave range accounting for insolation gross energy 50%, compared with tradition vanadium dioxide material, global solar radiation regulation rate obtains conclusive lifting.
Simultaneously as enough visible change that the obvious mediating effect+6 of visible light wave range produces, contribute to client is carried out strong effect demonstration, decisive impetus is played in the publicity popularization of product.Overcome vanadium dioxide range of accommodation and be mainly limited to infrared band, in the visible light wave range problem almost without visual obvious mediating effect+6.
Meanwhile, the absorption of LETC material visible-light specific wavelength, the intrinsic color development of vanadium dioxide is served useful mediation effect.
Meanwhile, insolation ultraviolet wavelength is had very strong barriering effect by vanadium dioxide, in the composite as natural ultraviolet absorber, can substantially increase the uvioresistant ability of LETC material.
The thermochromism scope of the composite of the present invention contains 300～2500nm insolation all band, and has obvious visual effect.Described thermochromism is reversible between 10 DEG C to 100 DEG C to be carried out.
The composite of the present invention can exist in a variety of forms, includes but not limited to slurry, coating, thin film etc..Wherein, the existence relation between inorganic system thermochromic material (vanadium dioxide) and organic system thermochromic material (dentate conversion body) can also have multiple, as long as both exist simultaneously.In one example, both can be present in slurry, coating, thin film with admixture.In another example, inorganic system thermochromic material and organic system thermochromic material exist with non-mixed state.This non-mixed state includes respectively being stratiform but interlayer contact, or does not respectively contact for stratiform and interlayer.Such as, the composite of the present invention can be a kind of laminated film by vanadium dioxide film and dentate conversion body pellicular cascade.In laminated film, both thin film can be respectively provided with one or more layers.Both thin film can be adjacent to stacking, it is also possible to separates with other nonwoven fabric from filaments between.Layered thing can be such as the glass etc. of PET (polyethylene terephthalate) thin film of flexibility, rigidity.
It addition, the composite of the present invention also can contain polymeric substrate.This polymeric substrate, on the one hand as the bridge of ligand conversion, can play dispersion, supporting role, for instance on the other hand in the film as film former in composite materials.In one example, vanadium dioxide (hypovanadic oxide powder of preferred nano-scale) and suitable LETC material compound in appropriate proportions, and it is dispersed among polymeric substrate, form the thermochromism compound film material with height temperature control optical adjustment properties.It addition, this polymeric substrate is preferably has intersolubility with the vanadium dioxide in composite and dentate conversion body, thus keeping slurry not produce precipitation, and keep the transparency of thin film.Exemplarily, described polymeric substrate is chosen as polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl acrylic acid methyl ester., polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly-2-ethyl-2-azoles quinoline, polyvinylpyrrolidone and containing at least one in the copolymer of above-mentioned polymers functionality.
In an embodiment, the composite of the present invention is a kind of compound thermochromism slurry, wherein comprises the vanadium dioxide nano powder as inorganic system thermochromic material, as the dentate conversion body of organic system thermochromic material, polymeric substrate and disperse medium.
Described disperse medium includes but not limited to as one or more in deionized water, ethanol, propanol, isopropanol, ethyl acetate, toluene, acetone, butanone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate, it is preferable that one or more in ethanol, isopropanol, acetone, gamma-butyrolacton.
In described slurry, the concentration of vanadium dioxide nano powder can be 0.1～2mol/L, it is preferred to 0.1～0.5mol/L.The concentration ratio of vanadium dioxide nano powder and polymeric substrate can be 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1.The concentration that can change metal ion can be 0.5～5mol/L, it is preferred to 0.5～2mol/L.The mol ratio of the changed metal ion in vanadium dioxide and dentate conversion body can be 9:1～1:9 as mentioned above, it is preferable that 2:1～1:6, more preferably 1:1～1:4.
Described slurry can also include dispersing aid, and this dispersing aid can be chosen from one or more in Polyethylene Glycol, oleic acid, triethyl group hexyl phosphoric acid, silane coupler, sodium lauryl sulphate, methyl anyl alcohol, fatty acid polyethylene glycol ester, polyacrylate, polyacrylamide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, modified polyurethane and modified acroleic acid dispersant.
Again, it is possible to add one or more in UV absorbent, light stabilizer, thermal stabilizer and plasticizer.
Hereinafter, exemplarily, the preparation method that above-mentioned slurry is described.
Prepare vanadium dioxide nano powder and be scattered in disperse medium, obtaining dispersion liquid A.Described vanadium dioxide nano powder can be through hydro-thermal method and prepares.It can be rutile phase hypovanadic oxide.In dispersion liquid A, vanadium dioxide concentration can be 0.01～1mol/L, it is preferable that 0.05～0.5mol/L, more preferably 0.1～0.2mol/L.It addition, dispersion liquid A can also add dispersing aid to promote the dispersion of vanadium dioxide nano powder.Dispersing mode can be ball milling etc..Rotational speed of ball-mill can be 500～1000r/min, and Ball-milling Time can be 1～3 hour.
Adding soluble polymer in dispersion liquid A, stirring is completely dissolved to polymer, obtains dispersion liquid B.In dispersion liquid B, the concentration of vanadium dioxide and polymer is than for 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1.Soluble polymer can be polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl acrylic acid methyl ester., Kynoar, polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly-2-ethyl-2-azoles quinoline, polyvinylpyrrolidone and containing at least one in the copolymer of above-mentioned polymers functionality.According to selected disperse medium, select to be dissolvable in water the phase emergencing copolymer of disperse medium, as the bridge that film former and ligand are changed.
Adding dentate conversion body in dispersion liquid B, stirring, to being completely dissolved, obtains dispersion liquid C, obtains described slurry.This dentate conversion body can be the mixture of convertible metal ion source, above-mentioned low absorbance ligand and above-mentioned high absorbance ligand.This three can add simultaneously, it is also possible to is added separately.As convertible metal ion source, can be corresponding slaine, for instance metal halide, metal nitrate, metal tetrafluoroborate, metal acetate salt, metal carbonate, metal perchlorate etc..In dispersion liquid C, dentate conversion body concentration can be 0.01～5mol/L, it is preferable that 0.1～2mol/L, more preferably 0.5～1mol/L.
According to the requirement to slurry concentration, it is also possible to continuously stirred dispersion liquid C heating, the unnecessary disperse medium of evaporation section again.
The compound thermochromism slurry of the present invention can be prepared as required becomes thermochromic coatings, and the thermochromic thin film such as various pad pasting or intermediate coat.Preparation method as thermochromic thin film, it is possible to be described slurry is coated on base material and is formed.Coating method can select the modes such as spraying, blade coating, brushing, showering or roller coat.Base material includes but not limited to the plastic sheeting of the material such as glass or polypropylene (PP), polyethylene (PE), polyamide (PA), polrvinyl chloride (PVC), polyethylene terephthalate (PET) and polymethyl methacrylate (PMMA).
Above-mentioned slurry, coating and thin film are applied to different types of transparent base, building and vehicle thermochromism Energy Saving Windows can be prepared.
Such as building or automobile energy-saving demand, the doping to vanadium dioxide can be passed through or select different LETC material fit, making that huge optical effect produced by thermochromism laminated film is reversible between 10 DEG C to 100 DEG C to be carried out.
The hypovanadic oxide-based thermochromic composite of high-performance of the present invention, is characterized in that thermochromism wavelength band contains whole insolation spectrum.Compared with tradition vanadium dioxide thermochromic material, the present invention has higher insolation and regulates efficiency.Simultaneously as have bigger mediating effect+6 at visible light wave range, thus creating obvious visible change, effect plays and publicity popularization to product have decisive significance.The present invention is with low cost, is suitable for high-volume commercial production, can be widely used for the energy-conservation field of Environment Protections such as Intelligent energy-saving window.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in hereafter example.
Embodiment 1
First prepare the vanadic anhydride solution 100ml containing 0.01mol/L, add 0.01g oxalic acid and stir into homogeneous solution.Above-mentioned solution is added in reactor and seals, react 24h in 240 DEG C.Take out after cooling, centrifugal, washing, dry obtain hypovanadic oxide powder.
Taking and stir in the prepared vanadium dioxide nano powder of the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone addition 100g ethanol and after ultrasonic disperse 30min, dispersion liquid be transferred to ball grinder, when 900r/min, ball milling 1h obtains vanadium dioxide alcohol dispersion liquid；10g polyvinyl butyral resin adds above-mentioned dispersion liquid, and stirring is to dissolving；Continuously add 6.5g nickelous perchlorate, 6g neopentyl glycol and 24g tetrabutyl ammonium bromide, stir to being completely dissolved and mix homogeneously；Continuously stirred above-mentioned dispersion liquid 30min at 90 DEG C, namely obtains vanadium dioxide and the compound thermochromism slurry of dentate conversion body.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
Under low temperature (20 DEG C) and high temperature (80 DEG C) state, determine the spectrophotometric transmittance spectrum of described thermochromism glass with the spectrophotometer (Hitachi U-3010) with heating adnexa, calculate the visible light transmitance (T obtaining glass further according to formulalum: 380-780nm) and different-waveband under solar energy transmitance (Tsol, 260-380nm, 380-780nm, 780-2600nm), its computing formula is as follows:
Wherein, T (λ) represents the transmitance of af at wavelength lambda, φlum(λ) for the relative spectral luminous efficiency of human eye, φsol(λ) for the solar radiation curve of spectrum.
Test result of calculation are as shown in Table 1.Visible, with common vanadium dioxide thermochromism glassy phase ratio, the glass of the present invention has high visible light transmissivity；Further, even if under the premise up to the visible light transmissivity of 68.32%, variations in temperature the sunlight regulation rate produced is more than 18%.Meanwhile, from the superficial to the deep, color is also become blackish green (word in Fig. 1, figure is the background arranged to show the transparency of thin film) from yellowish-brown to plexiglass tint.That is, the visible change that dimming process is adjoint is apparent.Fig. 2 illustrates compound thermochromism slurry institute made membrane absorption curve at 20 DEG C and 80 DEG C, it can be seen that thin film at high temperature absorbs and is remarkably reinforced, and occurs in that characteristic absorption peak near 750nm and 1300nm wavelength, corresponds respectively to LETC and VO2。
Table 1
Embodiment 2
First preparing the vanadium oxysulfate solution 100ml containing 0.01mol/L, add the water hydrazine that 5g mass fraction is 10%, then using sodium hydroxide titration is 7 formation suspensions to pH, is again scattered in 100mL water and stirs into homogeneous solution by precipitation filtration washing.Above-mentioned solution is added in reactor and seals, react 24h in 260 DEG C.Taking-up after cooling, adds 0.1g glucose, capping still in a kettle., reacts 8h then at 180 DEG C and be cooled to room temperature, is centrifuged, washs, dries the hypovanadic oxide powder obtaining carbon cladding.
Taking and stir in the prepared carbon cladding vanadium dioxide nano powder of the above-mentioned hydro-thermal of 1g and 0.5g polyvinylpyrrolidone addition 100g acetone and after ultrasonic disperse 30min, dispersion liquid be transferred to ball grinder, when 900r/min, ball milling 1h obtains vanadium dioxide acetone dispersion liquor；10g polymethyl methacrylate adds above-mentioned dispersion liquid, and stirring is to dissolving；Continuously add 15g nickelous perchlorate, 12g trimethylolpropane and 52g tetrabutyl ammonium bromide, stir to being completely dissolved and mix homogeneously；Continuously stirred above-mentioned dispersion liquid 30min at 90 DEG C, namely obtains vanadium dioxide and the compound thermochromism slurry of dentate conversion body.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 2.Visible, the glass of the present invention is under the visible light transmissivity premise more than 50%, and its sunlight regulation rate reaches 24.59%.Owing to regulation rate improves, color change becomes apparent from.
Table 2
Embodiment 3
First prepare the vanadic anhydride solution 100ml containing 0.01mol/L, addition 0.005g Tungstic anhydride. and the water hydrazine that 0.5g mass fraction is 10%, stir into homogeneous solution.Above-mentioned solution is added in reactor and seals, react 24h in 260 DEG C.Take out after cooling, centrifugal, washing, dry obtain hypovanadic oxide powder.
Taking and stir in the prepared vanadium dioxide nano powder of the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone addition 100g acetone and after ultrasonic disperse 30min, dispersion liquid be transferred to ball grinder, when 900r/min, ball milling 1h obtains vanadium dioxide acetone dispersion liquor；10g polymethyl methacrylate adds above-mentioned dispersion liquid, and stirring is to dissolving；Continuously add 4g cobaltous bromide, 5g trimethylolpropane and 24g tetrabutyl ammonium bromide, stir to being completely dissolved and mix homogeneously；Continuously stirred above-mentioned dispersion liquid 30min at 90 DEG C, namely obtains vanadium dioxide and the compound thermochromism slurry of dentate conversion body.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 3.Visible, with common vanadium dioxide thermochromism glassy phase ratio, the glass of the present invention has high visible light transmissivity；Further, even if under the premise up to the visible light transmissivity of 66.12%, variations in temperature the sunlight regulation rate produced is more than 18%.Meanwhile, from the superficial to the deep, color is also become bottle green (word in Fig. 3, figure is the background arranged to show the transparency of thin film) from yellowish-brown to plexiglass tint.That is, the visible change that dimming process is adjoint is apparent.
Table 3
Embodiment 4
First preparing the vanadium oxysulfate solution 100ml containing 0.01mol/L, add the water hydrazine that 5g mass fraction is 10%, then using sodium hydroxide titration is 7 formation suspensions to pH, is again scattered in 100mL water and stirs into homogeneous solution by precipitation filtration washing.Above-mentioned solution is added in reactor and seals, react 24h in 260 DEG C.Take out after cooling, reactant liquor is joined in 100mL dehydrated alcohol, add 10mL deionized water, 5mL ammonia stirs, it is added dropwise over 2.5mL tetraethyl orthosilicate subsequently, stirs 5h under room temperature, filter, washing, dry, annealing obtains the hypovanadic oxide powder of silicon oxide cladding.
Take in the prepared silicon oxide cladding vanadium dioxide nano powder of the above-mentioned hydro-thermal of 1g and 0.5g polyvinylpyrrolidone addition 100g ethanol and stir and after ultrasonic disperse 30min, dispersion liquid is transferred to ball grinder, and when 900r/min, ball milling 1h obtains vanadium dioxide alcohol dispersion liquid；10g polyvinyl butyral resin adds above-mentioned dispersion liquid, and stirring is to dissolving；Continuously add 9g cobaltous bromide, 14g neopentyl glycol and 52g tetrabutyl ammonium bromide, stir to being completely dissolved and mix homogeneously；Continuously stirred above-mentioned dispersion liquid 30min at 90 DEG C, namely obtains vanadium dioxide and the compound thermochromism slurry of dentate conversion body.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 4.Visible, the glass of the present invention is under the visible light transmissivity premise more than 50%, and its sunlight regulation rate reaches 21.91%.Owing to regulation rate improves, color change becomes apparent from.
Table 4
Comparative example 1
First prepare the vanadic anhydride solution 100ml containing 0.01mol/L, add 0.01g oxalic acid and stir into homogeneous solution.Above-mentioned solution is added in reactor and seals, react 24h in 240 DEG C.Taking out after cooling, centrifugal drying obtains hypovanadic oxide powder.Taking and stir in the prepared vanadium dioxide nano powder of the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone addition 100g ethanol and after ultrasonic disperse 30min, dispersion liquid be transferred to ball grinder, when 900r/min, ball milling 1h obtains the alcohol dispersion liquid of vanadium dioxide；9g polyvinyl butyral resin adds above-mentioned dispersion liquid, and stirring is to dissolving；At 90 DEG C, continuously stirred above-mentioned dispersion liquid 30min, namely obtains vanadium dioxide thermochromism slurry.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 5.Visible, under only using the vanadium dioxide premise as thermochromic material, the visible light transmissivity suitable for obtaining embodiment 1, its sunlight regulation rate only has before and after the half of embodiment 1.Meanwhile, from fig. 4, it can be seen that light modulation time glass do not produce visual tone variations.
Table 5
Comparative example 2
First prepare the vanadic anhydride solution 100ml containing 0.01mol/L, addition 0.005g Tungstic anhydride. and the water hydrazine that 0.5g mass fraction is 10%, stir into homogeneous solution.Above-mentioned solution is added in reactor and seals, react 24h in 260 DEG C.Take out after cooling, centrifugal, washing, dry and obtain hypovanadic oxide powder.Taking and stir in the prepared vanadium dioxide nano powder of the above-mentioned hydro-thermal of 1g and 0.5g polyvinylpyrrolidone addition 100g ethanol and after ultrasonic disperse 30min, dispersion liquid be transferred to ball grinder, when 900r/min, ball milling 1h obtains the alcohol dispersion liquid of vanadium dioxide；9g polyvinyl butyral resin adds above-mentioned dispersion liquid, and stirring is to dissolving；At 90 DEG C, continuously stirred above-mentioned dispersion liquid 30min, namely obtains vanadium dioxide thermochromism slurry.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, it is thus achieved that hypovanadic oxide-based thermochromism glass.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 6.Visible, under only using the vanadium dioxide premise as thermochromic material, as increased vanadium dioxide solid content, its sunlight regulation rate also increases up to 12.23% to some extent, but, its visible light transmissivity quickly falls to only about 40%.Additionally, do not observe obvious tone variations during light modulation.
Table 6
Comparative example 3
10g polymethyl methacrylate adding 100g acetone stirring to dissolving, be then added sequentially 15g nickelous perchlorate, 14g neopentyl glycol and 52g tetrabutyl ammonium bromide, stirring obtains dispersion liquid to dissolving.Adopt spin-coating method by dispersion in commercially available surface of ordinary glass, it is thus achieved that the only thermochromism glass of pbz polymer base.
With embodiment 1 same method, the performance of glass having been evaluated, its result is as shown in table 7.Visible, when being used alone LETC thermochromic material, though coated glass has higher visible light transmissivity and an obvious temperature control visible change, but the temperature control amplitude of accommodation within the scope of insolation infrared band is very faint is only 2.75%, does not have good infrared regulating effect.Meanwhile, this glass entirety infrared transmittivity is too high, does not have good infrared barrier effect in summer.
Table 7
The present invention is by constituting a kind of brand-new composite in conjunction with vanadium dioxide material with LETC material, so that the thermo-chromic effects of new material covers the insolation full band range including visible ray and infrared band, regulating power and level of comfort have the progress of leap, can be widely used for the energy-conservation field of Environment Protections such as Intelligent energy-saving window.
Claims (11)
1. a compound thermochromism slurry, it is characterized in that, including the vanadium dioxide nano powder as inorganic system thermochromic material, the dentate conversion body as organic system thermochromic material, polymeric substrate and disperse medium, described dentate conversion body comprises can change metal ion, can form the low absorbance ligand of low absorbance coordination compound with the described metal ion that changes and can form the high absorbance ligand of high absorbance coordination compound with the described metal ion that changes.
2. compound thermochromism slurry according to claim 1, it is characterised in that described vanadium dioxide nano powder is doped or non-doped rutile phase hypovanadic oxide.
3. compound thermochromism slurry according to claim 1 and 2, it is characterised in that the particle diameter of described vanadium dioxide nano powder is 20～80nm.
4. compound thermochromism slurry according to any one of claim 1 to 3, it is characterized in that, the described metal ion that changes is at least one in Fe (II), Co (II), Ni (II), Cu (II), described low absorbance ligand is at least one in dihydroxylic alcohols, trihydroxylic alcohol, polyhydric alcohol, preferred neopentyl glycol, trimethylolpropane, ethylene glycol, glycerol, 2-methyl isophthalic acid, at least one in ammediol；Described high absorbance ligand comprises can with the coordinating group that can change metal ion formation high absorbance coordination compound, it is preferable that at least one in tetrabutyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, choline chloride, triphenylphosphine, tetrathiacyclotetradecane.
5. compound thermochromism slurry according to any one of claim 1 to 4, it is characterised in that the mol ratio of the changed metal ion in vanadium dioxide and dentate conversion body is 9:1～1:9, it is preferable that 2:1～1:6, more preferably 1:1～1:4.
6. compound thermochromism slurry according to any one of claim 1 to 5, it is characterized in that, described polymeric substrate is polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral resin, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl acrylic acid methyl ester., polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly-2-ethyl-2-azoles quinoline, polyvinylpyrrolidone and containing at least one in the copolymer of above-mentioned polymers functionality.
7. compound thermochromism slurry according to any one of claim 1 to 6, it is characterized in that, described disperse medium is at least one in deionized water, ethanol, propanol, isopropanol, ethyl acetate, toluene, acetone, butanone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate.
8. compound thermochromism slurry according to any one of claim 1 to 7, it is characterised in that in described compound thermochromism slurry, the concentration of vanadium dioxide nano powder is 0.1～2mol/L；The concentration of vanadium dioxide nano powder and polymeric substrate is than for 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1；The concentration that can change metal ion is 0.5～5mol/L.
9. the preparation method of the compound thermochromism slurry according to any one of a claim 1 to 8, it is characterised in that comprise the following steps:
A. prepare vanadium dioxide nano powder and be scattered in disperse medium, obtaining dispersion liquid A；
B. adding soluble polymer in dispersion liquid A, stirring is completely dissolved to polymer, obtains dispersion liquid B；
C. adding dentate conversion body in dispersion liquid B, stirring, to being completely dissolved, obtains dispersion liquid C；
D. continuously stirred dispersion liquid C heating, the unnecessary disperse medium of evaporation section, obtains described compound thermochromism slurry.
10. preparation method according to claim 9, it is characterised in that in dispersion liquid A, vanadium dioxide concentration is 0.01～1mol/L, it is preferable that 0.05～0.5mol/L, more preferably 0.1～0.2mol/L；In dispersion liquid B, the concentration of vanadium dioxide and polymer is than for 1:9～9:1, it is preferable that 1:9～5:1, more preferably 1:5～1:1；In dispersion liquid C, the concentration of the changed metal ion of dentate conversion body is 0.01～5mol/L, 0.1～2mol/L, more preferably 0.5～1mol/L.
11. a compound thermochromic thin film, it is characterised in that the compound thermochromism slurry according to any one of claim 1 to 8 is coated on matrix and prepares.
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