CN105694615B - A kind of hypovanadic oxide-based thermochromic composite of high-performance - Google Patents
A kind of hypovanadic oxide-based thermochromic composite of high-performance Download PDFInfo
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- CN105694615B CN105694615B CN201610111868.8A CN201610111868A CN105694615B CN 105694615 B CN105694615 B CN 105694615B CN 201610111868 A CN201610111868 A CN 201610111868A CN 105694615 B CN105694615 B CN 105694615B
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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
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The present invention relates to a kind of hypovanadic oxide-based thermochromic composites of high-performance, the hypovanadic oxide-based thermochromic composite of high-performance includes: the vanadium dioxide as inorganic system's thermochromic material and the dentate conversion body as organic system thermochromic material, the dentate conversion body include can change metal ion, can with it is described change metal ion formed low absorbance complex low absorbance ligand and can be with the high absorbance ligand for changing metal ion and forming high absorbance complex.Hypovanadic oxide-based thermochromic composite of the invention its main feature is that thermochromism wavelength band covers the entire insolation spectrum including visible light, thus has high global solar radiation regulation rate compared with traditional vanadium dioxide thermochromic material.
Description
Technical field
The invention belongs to high-performance inorganic-organic composite material technical fields, in particular to thermochromic material and its section
It can environmental protection application.
Background technique
Global energy shortage problem is got worse, and excessive carbon emission causes environment worsening, and energy-saving and emission-reduction, which have become, works as
The top priority of preceding various countries.It is estimated that building energy consumption accounts for 30% or more in social total energy consumption, therefore, building energy conservation is promoted to be
One of energy-saving and emission-reduction, the emphasis measure for realizing sustainable development.
Significant portion is used for air-conditioning in building energy consumption, and windowpane carries out the main logical of heat exchange with extraneous as building
Road becomes the main path of air conditioner energy source loss.Therefore, using various types of Energy Saving Windows, it can be effectively reduced energy consumption, reached
Energy-saving and environment-friendly purpose.
Existing market Energy Saving Windows main product is Low emissivity (Low-E) glass and heat-reflecting glass etc., due to technology maturation,
Cheap, heat-proof quality is good, is widely used in building energy conservation.But since above-mentioned Energy Saving Windows optical property cannot be because of season
Change and think that demand arbitrarily changes, it is difficult to adapt to China's most of cold summers thermally the energy saving requirement in area and people to inhabitation ring
Border level of comfort increasingly higher demands.Then, the new energy-conserving product of referred to as " Intelligent energy-saving window " just comes into being.
The cause off-color material that Intelligent energy-saving window uses optical property can be changed, the transflection that various physical stimulations are generated using it
The variation such as performance is penetrated, the controllable adjustment purpose of indoor environment photo-thermal is reached.Obviously, Intelligent energy-saving window is suitable for most areas
With the demand of Different climate condition, also make indoor living environment more suitable to people.
According to physical stimulation type and Discoloration mechanism, there is electrochromism, gas-discoloration is photochromic, and thermochromism etc. is more
The Intelligent energy-saving window of a type.
It is former using the semiconductor-metal reversible transition of vanadium dioxide near room temperature in various types of Intelligent energy-saving windows
The thermochromism Energy Saving Windows developed are managed, have structure simple, material utilization amount is few, completely dispenses with switch or artificial energy source controls energy
Temperature change of according with one's environment and realize the remarkable advantages such as automatic photo-thermal regulation, obtained in various countries and pay attention to and research and develop in succession.Wherein, make
It has taken the lead in being broken through in China with the temperature control intelligent power saving Filming Technology of nano vanadium dioxide, the hypovanadic oxide-based temperature prepared
Control intelligent power saving pad pasting will be launched.
But the main inventive person as above-mentioned technology, while notice above-mentioned vanadium dioxide temperature control Intelligent energy-saving window according to
So there is following several deficiencies:
(1) to the insolation infrared band amplitude of accommodation with higher, but to the visible light wave range for accounting for insolation gross energy 50%
Hardly there is adjustment effect, result reduces global solar radiation regulation rate；
(2) due to not having apparent adjustment effect in visible light wave range, enough views can not be generated using this adjusting
Feel variation, to be helpless to carry out strong regulating effect demonstration to customer, to product conduct promotion to cause it is decisive
Adverse effect；
(3) there is strong sink effect to short-wave band visible light, leads to film yellow color development.
Mature technology there is no fundamentally to solve above-mentioned some problem so far.It is clear that the solution of the above problem will anticipate
Taste the tremendous breakthrough of hypovanadic oxide-based thermochromism Energy Saving Windows application technology.
Summary of the invention
Dentate conversion body thermochromism (Ligand Exchange Thermochromic abbreviation LETC) material is not by
Metal ion can be changed in conjunction with different dentates under synthermal, the complex with different absorption coefficients is formed, to produce
Raw thermo-chromic effects, in general, at low temperature, metal ion forms low absorption coefficient in conjunction with low absorption coefficient dentate
Complex, transmitance with higher；At high temperature, metal ion transfers to form high-selenium corn in conjunction with high absorption coefficient dentate
Coefficient complex has lower transmitance.This temperature control optical change is reversible, and it is specific to occur mainly with visible light wave range
Wave-length coverage.
But to occur over just visible light very narrow i.e. in the full spectrum of insolation nearby for common LETC materials Thermochromic
Wavelength band causes regulating power less than normal.More due to being that the mid and far infrared wave band most sensitive to human body warm sensation cannot be adjusted
Section can not carry out the adjusting for guaranteeing human body comfort.
In addition, LETC material is only capable of reaching adjusting purpose by the absorption to above-mentioned wavelength band light, material itself is no
With reflection effect, therefore regulating effect is affected.
The present inventor is based on the long-term R & D experience to thermochromic material, and by testing repeatedly, discovery passes through knot for the first time
It closes vanadium dioxide material and LETC material constitutes a kind of completely new composite material, the thermo-chromic effects of new material can be made to cover
Insolation full band range including visible light and infrared band has the progress of leap on regulating power and level of comfort,
Thus the present invention is completed.
The present invention provides a kind of hypovanadic oxide-based thermochromic composite of high-performance, comprising: as it is inorganic be thermotropic change
The vanadium dioxide of color material and dentate conversion body as organic system thermochromic material, the dentate conversion body includes can
Transformation metal ion, can with it is described change metal ion formed low absorbance complex low absorbance ligand and can be with
The high absorbance ligand for changing metal ion and forming high absorbance complex.
Hypovanadic oxide-based thermochromic composite of the invention, its main feature is that thermochromism wavelength band covers including can
Entire insolation spectrum including light-exposed, thus adjusted compared with traditional vanadium dioxide thermochromic material with high global solar radiation
Rate.Meanwhile in the larger mediating effect+6 of visible light wave range, be changed into visual significant change, the effect of product is shown and
Publicity, which is promoted, has decisive significance.In addition, due to increasing absorption of the visible light compared with long-wave band, so that vanadium dioxide is intrinsic
Yellow color development has obtained larger inhibition.
Preferably, the vanadium dioxide is doping and/or undoped rutile phase hypovanadic oxide.
Preferably, the vanadium dioxide exists in the form of vanadium dioxide nano particle, it is preferable that the vanadium dioxide is received
The particle size range of rice grain is 20~80nm.
Preferably, the vanadium dioxide nano particle has external coating, the thickness range of the external coating is preferably 2
~20nm, the material of the external coating are preferably at least one of carbon, silica, magnesia and aluminium oxide.
Preferably, the metal ion that changes is at least one of Fe (II), Co (II), Ni (II), Cu (II).
Preferably, the low absorbance ligand be at least one of dihydric alcohol, trihydroxylic alcohol, polyalcohol, preferably new penta
Glycol, trimethylolpropane, ethylene glycol, glycerine, 2- methyl-1, at least one of 3-propanediol；The high absorbance is matched
Position body includes can be with the coordinating group that can change metal ion and formed high absorbance complex, preferably chloride, bromination
At least one of object, iodide, Pseudohalides, more preferable tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide,
Choline chloride, triphenylphosphine, at least one of tetrathiacyclotetradecane.
Preferably, the molar ratio for changing metal ion in vanadium dioxide and dentate conversion body is 9:1~1:9, it is excellent
Select 2:1~1:6, more preferable 1:1~1:4.
Preferably, further including polymeric substrate in the composite material, it is preferable that the polymeric substrate is polyacrylamide
Amine, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate,
Polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose,
In polyurethane, poly- 2- ethyl -2- oxazoline, polyvinylpyrrolidone and copolymer containing above-mentioned polymers functionality extremely
Few one kind.
Preferably, inorganic system's thermochromic material exists with organic system thermochromic material with admixture.
Preferably, inorganic system's thermochromic material and organic system thermochromic material exist with immiscible conjunction state, including each
For stratiform but interlayer contact, or respectively for stratiform and interlayer does not contact.
Preferably, the thermochromism of the composite material reversible progress between 10 DEG C to 100 DEG C.
Preferably, the composite material is deposited in the form of thermochromism slurry, thermochromic coatings or thermochromic thin film
?.
Detailed description of the invention
Fig. 1 is in kind photo of the hypovanadic oxide-based composite film of embodiment 1 under 20 DEG C (left sides) and 80 DEG C (right side)；
Fig. 2 is absorption curve of the hypovanadic oxide-based composite film of embodiment 1 at 20 DEG C and 80 DEG C；
Fig. 3 is in kind photo of the hypovanadic oxide-based composite film of embodiment 3 under 20 DEG C (left sides) and 80 DEG C (right side)；
Fig. 4 is in kind photo of the independent film of vanadium dioxide of comparative example 1 under 20 DEG C (left sides) and 80 DEG C (right side).
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
The present invention provides a kind of hypovanadic oxide-based thermochromic composite of high-performance, the composite material contain simultaneously whether there is or not
Machine system thermochromic material and organic system thermochromic material, inorganic system's thermochromic material are vanadium dioxide, and organic system is thermotropic
Off-color material is dentate conversion body.
In the present invention, dentate conversion body includes that can change metal ion, can form the low of low absorbance complex therewith
Absorbance ligand and can be formed therewith high absorbance complex high absorbance ligand both coordination sills.By not
Metal ion can be changed in conjunction with different dentates under synthermal, the complex with different absorption coefficients is formed, to produce
Raw thermo-chromic effects, at low temperature, metal ion forms low absorption coefficient complex in conjunction with low absorbance ligand, has
Higher transmitance；At high temperature, metal ion transfers to form high absorption coefficient complex in conjunction with high absorbance ligand, tool
There is lower transmitance.This temperature control optical change is reversible, and occurs mainly with visible light wave range particular range of wavelengths.
The metal ion that changes can be transition metal ions, preferably Fe (II), Co (II), Ni (II), Cu (II)
At least one of.It selects wherein at least one in conjunction with different dentates, can be obtained as needed in different-waveband specific
Absorption.
Dentate conversion body can indicate the absorbability of light with absorbance.The low absorbance refers to 400~
Less than 0.2, the high absorbance refers to is 1400nm wave-length coverage internal absorbance in 400~1400nm wave-length coverage internal absorbance
0.8 or more.
Low absorbance ligand includes but is not limited at least one of dihydric alcohol, trihydroxylic alcohol, polyalcohol, and preferably new penta 2
Alcohol, trimethylolpropane, ethylene glycol, glycerine, 2- methyl-1, at least one of 3-propanediol.High absorbance ligand packet
It, such as can be containing N, P, in S atom containing can be with the coordinating group that can change metal ion and formed high absorbance complex
At least one, and/or be selected from least one of chloride, bromide, iodide, Pseudohalides, preferably tetrabutyl phosphonium bromide
Ammonium, tetrabutylammonium chloride, tetrabutylammonium iodide, choline chloride, triphenylphosphine, at least one of tetrathiacyclotetradecane.
In dentate conversion body, mole of metal ion Yu low absorbance ligand and high absorbance ligand can be changed
Than that can be (0.1~1): (1~10): (4~10).
In addition, also may include polymer in dentate conversion body, using the bridge converted as ligand.Furthermore, it is to be understood that
Not necessarily include polymer in dentate conversion body, has and do not need polymer in the presence of solvent, solvent and polymer can be mutual
Mutually replace and converts bridge as ligand.The polymer include but is not limited to polyacrylamide, poly hydroxy ethyl acrylate,
Polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl third
E pioic acid methyl ester, polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly- 2- ethyl -2- oxazole
At least one of quinoline, polyvinylpyrrolidone and copolymer containing above-mentioned polymers functionality.
Vanadium dioxide in the present invention can be undoped vanadium dioxide, be also possible to the titanium dioxide with doped chemical
Vanadium.Vanadium dioxide can be Rutile Type.There is reversible transition and huge optical property to change at 68 DEG C for vanadium dioxide crystallization.
And by means such as element dopings, transition temperature can be accurately controlled near room temperature.Vanadium dioxide in the present invention includes
The various elements of the hypovanadic oxide-based thermochromism Energy Saving Windows of the tradition 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 element
In 21~30 transition elements, tin and its elements such as neighbouring element and tungsten, molybdenum, ruthenium, niobium, tantalum, magnesium in periodic table near vanadium
One or any combination.Wherein, 21~30 transition elements in the periodic table of elements near vanadium include scandium, titanium, chromium, manganese, iron,
Cobalt, nickel, copper and zinc, the tin and its neighbouring element include indium, antimony, tin, gallium, germanium, lead and bismuth, and preferred doped chemical is
Tungsten, molybdenum, bismuth, tin, niobium, tantalum, magnesium, iron, zinc and titanium.Using above-mentioned doped chemical, the ruler of doped vanadium dioxide powder can control
Very little and pattern, while can also regulate and control the phase transition temperature of vanadium dioxide.
In the present invention, vanadium dioxide can be powder, preferably graininess, i.e., is deposited in the form of vanadium dioxide nano particle
?.The draw ratio of particle can be 1:1~10:1, preferably 1:1~5:1, more preferably 1:1~2:1.Particle size is at least one
In a dimension be not more than 1um, preferably at least one dimension be not more than 100nm, more preferably in three dimensions no more than
100nm, such as 20~80nm.The graininess can be subsphaeroidal, oval, snowflake shape, cube, piece shape etc..
In addition, vanadium dioxide nano particle can also have external coating.The external coating is preferably transparent, Ke Yi
The whole visible light permeability of vanadium dioxide particle is not influenced while improving the stability of vanadium dioxide particle again.As outsourcing
One or more of the material of coating, including but not limited to carbon, silica, magnesia and aluminium oxide.The thickness model of external coating
Enclosing can be 2~20nm.
Vanadium dioxide can carry out compound in any proportion as needed with dentate conversion body in principle, but many experiments table
It is bright, the molar ratio preferred 9:1~1:9, more preferable 2:1~1:6, most preferably 1:1 of metal ion in vanadium dioxide and LETC material
~1:4.
The present invention is by combining vanadium dioxide material and LETC material to constitute a kind of completely new composite material, to make green wood
The thermo-chromic effects of material cover the insolation full band range including visible light and infrared band, in regulating power and comfortable journey
There is the progress of leap on degree.
It is clear that by the adjustment effect to the visible light wave range for accounting for insolation gross energy 50%, with traditional vanadium dioxide
Material is compared, and global solar radiation regulation rate has obtained conclusive promotion.
Simultaneously as enough visible changes that the apparent mediating effect+6 of visible light wave range generates, facilitate to customer
Strong effect demonstration is carried out, decisive impetus is played to the publicity popularization of product.It overcomes vanadium dioxide and adjusts model
It encloses and is mainly limited to infrared band, the problem of visible light wave range is almost without visual obvious mediating effect+6.
Meanwhile the absorption of LETC material visible-light specific wavelength, beneficial reconciliation is played to the intrinsic color development of vanadium dioxide
Effect.
Meanwhile vanadium dioxide has very strong barriering effect to insolation ultraviolet wavelength, can be used as nature in the composite
Ultraviolet absorber, substantially increase the uvioresistant ability of LETC material.
The thermochromism range of composite material of the invention covers 300~2500nm insolation all band, and has obvious view
Feel effect.The thermochromism reversible progress between 10 DEG C to 100 DEG C.
Composite material of the invention can exist in a variety of forms, including but not limited to slurry, coating, film etc..Wherein,
Between inorganic system's thermochromic material (vanadium dioxide) and organic system thermochromic material (dentate conversion body) there are relationships
Can also there are many, as long as the two exists simultaneously.In one example, the two can be present in admixture slurry,
In coating, film.In another example, inorganic system's thermochromic material and organic system thermochromic material are with immiscible conjunction state
In the presence of.This immiscible conjunction state include respectively be stratiform but interlayer contact, or respectively for stratiform and interlayer does not contact.For example, this hair
Bright composite material can be a kind of laminated film as made of vanadium dioxide film and dentate conversion body pellicular cascade.Multiple
It closes in film, both films can be respectively provided with one or more layers.Both films can be adjacent to stacking, can also be two
Separated between person with other nonwoven fabric from filaments.Layered object may be, for example, PET flexible (polyethylene terephthalate) film,
The glass etc. of rigidity.
In addition, can also contain polymeric substrate in composite material of the invention.The polymeric substrate is on the one hand as coordination
The bridge of body conversion, on the other hand can play dispersion, supporting role in composite materials, such as in the film as film forming
Agent.In one example, vanadium dioxide (the preferably hypovanadic oxide powder of nano-scale) is with LETC material appropriate suitably to compare
Example is compound, and is dispersed among polymeric substrate, forms the thermochromic thin film with height temperature control optical adjustment properties
Material.In addition, the polymeric substrate be preferably in composite material vanadium dioxide and dentate conversion body have intersolubility, from
And slurry is kept not generate precipitating, and keep the transparency of film.As an example, the polymeric substrate is chosen as polyacrylamide
Amine, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate,
Polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose,
In polyurethane, poly- 2- ethyl -2- oxazoline, polyvinylpyrrolidone and copolymer containing above-mentioned polymers functionality extremely
Few one kind.
In an implementation form, composite material of the invention is a kind of composite type heat mutagens mill base material, wherein comprising making
Vanadium dioxide nano powder for inorganic system's thermochromic material, the dentate conversion body as organic system thermochromic material,
Polymeric substrate and decentralized medium.
The decentralized medium include but is not limited to be deionized water, ethyl alcohol, propyl alcohol, isopropanol, ethyl acetate, toluene, third
One or more of ketone, butanone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate, preferred alcohol, isopropanol, acetone,
One or more of gamma-butyrolacton.
In the slurry, the concentration of vanadium dioxide nano powder can be 0.1~2mol/L, preferably 0.1~0.5mol/
L.The concentration of vanadium dioxide nano powder and polymeric substrate ratio can be 9:1~1:9, preferably 1:9~5:1, more preferable 1:5~1:
1.The concentration that metal ion can be changed can be 0.5~5mol/L, preferably 0.5~2mol/L.Vanadium dioxide and dentate are converted
The molar ratio for changing metal ion in body can be 9:1~1:9, preferably 2:1~1:6, more preferable 1:1~1:4 as described above.
The slurry can also include dispersing aid, the dispersing aid can be selected from polyethylene glycol, oleic acid, triethyl group oneself
Base phosphoric acid, silane coupling agent, lauryl sodium sulfate, methyl anyl alcohol, fatty acid polyethylene glycol ester, polyacrylate, polypropylene
Amide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, modified polyurethane and modified propylene acid dispersant
One or more of.
Also, one or more of UV absorbent, light stabilizer, thermal stabilizer and plasticizer can also be added.
Hereinafter, as an example, illustrating the preparation method of above-mentioned slurry.
Prepare vanadium dioxide nano powder and be scattered in decentralized medium, obtains dispersion liquid A.The vanadium dioxide nano powder
It can be and be made by hydro-thermal method.It can be rutile phase hypovanadic oxide.In dispersion liquid A vanadium dioxide concentration can for 0.01~
1mol/L, preferably 0.05~0.5mol/L, more preferable 0.1~0.2mol/L.It is helped in addition, dispersion can also be added in dispersion liquid A
Agent is 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,
Ball-milling Time can be 1~3 hour.
Soluble polymer is added 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 ratio is 1:9~9:1, preferably 1:9~5:1, more preferable 1:5~1:1.Soluble polymer can
For polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, poly- methyl-prop
E pioic acid methyl ester, polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, Kynoar, polyvinylpyridine, polymethylacrylic acid
Glyceride, hydroxyethyl cellulose, polyurethane, poly- 2- ethyl -2- oxazoline, polyvinylpyrrolidone and contain above-mentioned polymer
At least one of copolymer of functional group.According to selected decentralized medium, selection is dissolvable in water the phase emergencing copolymer of decentralized medium,
The bridge converted as film forming agent and ligand.
Dentate conversion body is added in dispersion liquid B, stirs to being completely dissolved, obtains dispersion liquid C, obtain the slurry.It should
Dentate conversion body can be the mixed of convertible metal ion source, above-mentioned low absorbance ligand and above-mentioned high absorbance ligand
Close object.This three can add simultaneously, can also be added separately.It can be corresponding metal salt as convertible metal ion source,
Such as metal halide, metal nitrate, metal tetrafluoroborate, metal acetate salt, metal carbonate, metal perchlorate
Deng.Dentate, which converts bulk concentration, in dispersion liquid C to be 0.01~5mol/L, preferably 0.1~2mol/L, more preferable 0.5~1mol/
L。
According to the requirement to slurry concentration, it can also persistently be dispersed with stirring liquid C again and heat, the extra dispersion of evaporation section is situated between
Matter.
Composite type heat mutagens mill base material of the invention can be prepared into thermochromic coatings and various pad pastings as needed
Or the thermochromic thin films such as intermediate coat.As the preparation method of thermochromic thin film, it can be and the slurry is coated on substrate
And it is formed.Coating method can choose the modes such as spraying, blade coating, brushing, showering or roller coating.Substrate include but is not limited to glass,
Or polypropylene (PP), polyethylene (PE), polyamide (PA), polyvinyl chloride (PVC), polyethylene terephthalate (PET) and
The plastic film of the materials such as polymethyl methacrylate (PMMA).
By above-mentioned slurry, coating and film are applied to different types of transparent substrate, can prepare building and vehicle
With thermochromism Energy Saving Windows.
Such as building or automobile energy-saving demand, by the doping to vanadium dioxide or different LETC materials can be selected
Material cooperation, makes the reversible progress between 10 DEG C to 100 DEG C of huge optical effect caused by thermochromism laminated film.
The hypovanadic oxide-based thermochromic composite of high-performance of the invention, its main feature is that thermochromism wavelength band covers
Entire insolation spectrum.Compared with traditional vanadium dioxide thermochromic material, there is the present invention higher insolation to adjust efficiency.Together
When, since there is biggish mediating effect+6 in visible light wave range, thus apparent visible change is produced, the effect exhibition to product
Show and publicize popularization that there is decisive significance.The present invention is low in cost, is suitble to high-volume industrial production, can be widely used for intelligent section
The energy conservation and environmental protections such as energy window.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention, some non-intrinsically safes that those skilled in the art's above content according to the present invention is made
Modifications and adaptations all belong to the scope of protection of the present invention.Following specific technological parameters of example etc. are also only in OK range
One example, i.e. those skilled in the art can be done in suitable range by the explanation of this paper and be selected, and not really want to be defined in
Hereafter exemplary specific value.
Embodiment 1
The vanadic anhydride solution 100ml containing 0.01mol/L is prepared first, and 0.01g oxalic acid is added and is stirred into uniform
Solution.Above-mentioned solution is added in reaction kettle and is sealed, for 24 hours in 240 DEG C of reactions.It is taken out after cooling, is centrifuged, washs, is dried to obtain
Hypovanadic oxide powder.
Take vanadium dioxide nano powder made from the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone that 100g ethyl alcohol is added
Dispersion liquid simultaneously after ultrasonic disperse 30min, is transferred to ball grinder, ball milling 1h obtains vanadium dioxide under the conditions of 900r/min by middle stirring
Alcohol dispersion liquid；Above-mentioned dispersion liquid, stirring to dissolution is added in 10g polyvinyl butyral；Continuously add 6.5g nickelous perchlorate,
6g neopentyl glycol and 24g tetrabutylammonium bromide, stirring is to being completely dissolved and be uniformly mixed；Above-mentioned dispersion liquid is persistently stirred at 90 DEG C
30min is to get to vanadium dioxide and dentate conversion body composite type heat mutagens mill base material.Above-mentioned slurry is coated uniformly on commercially available
Surface of ordinary glass obtains hypovanadic oxide-based thermochromism glass.
With the spectrophotometer (Hitachi U-3010) with heating attachment under low temperature (20 DEG C) and high temperature (80 DEG C) state
The visual light transmission rate of glass has been calculated further according to formula for the spectrophotometric transmittance spectrum for determining the thermochromism glass
(TLum:380-780nm) and different-waveband under solar energy transmitance (Tsol, 260-380nm, 380-780nm, 780-
2600nm), calculation formula is as follows:
Wherein, T (λ) indicates the transmitance of af at wavelength lambda, φlum(λ) is the relative spectral luminous efficiency of human eye, φsol(λ)
For the solar radiation curve of spectrum.
Test and calculated result as shown in Table 1.As it can be seen that with common vanadium dioxide thermochromism glass phase ratio, the present invention
Glass have high visible light transmittance；Even if also, under the premise of up to 68.32% visible light transmittance, by
The sunlight regulation rate that temperature change generates is more than 18%.At the same time, from the superficial to the deep, color is also by yellowish-brown discoloration for plexiglass tint
For blackish green (Fig. 1, the text in figure is the background being arranged to show the transparency of film).That is, dimming process is adjoint
Visible change is apparent.Fig. 2 shows absorption curve of the composite type heat mutagens mill base material institute's made membrane at 20 DEG C and 80 DEG C, can
It is remarkably reinforced with finding out that film absorbs at high temperature, and characteristic absorption peak occurs near 750nm and 1300nm wavelength, point
It Dui Yingyu not LETC and VO2。
Table 1
Embodiment 2
The oxygen vanadium sulphate solution 100ml containing 0.01mol/L is prepared first, and the water that 5g mass fraction is 10% is added and joins
Then ammonia is 7 formation suspensions using sodium hydroxide titration to pH, disperses precipitating filtration washing in 100mL water again and stir
Mix uniform solution.Above-mentioned solution is added in reaction kettle and is sealed, for 24 hours in 260 DEG C of reactions.It is taken out after cooling, in reaction kettle
Middle addition 0.1g glucose, capping kettle then at 180 DEG C of reaction 8h and are cooled to room temperature, are centrifuged, wash, are dried to obtain carbon
The hypovanadic oxide powder of cladding.
Take carbon coating vanadium dioxide nano powder made from the above-mentioned hydro-thermal of 1g and 0.5g polyvinylpyrrolidone that 100g is added
After stirring simultaneously ultrasonic disperse 30min in acetone, dispersion liquid is transferred to ball grinder, ball milling 1h obtains dioxy under the conditions of 900r/min
Change vanadium acetone dispersion liquor；Above-mentioned dispersion liquid, stirring to dissolution is added in 10g polymethyl methacrylate；Continuously add 15g high chlorine
Sour nickel, 12g trimethylolpropane and 52g tetrabutylammonium bromide, stirring is to being completely dissolved and be uniformly mixed；It is persistently stirred at 90 DEG C
Above-mentioned dispersion liquid 30min is to get to vanadium dioxide and dentate conversion body composite type heat mutagens mill base material.Above-mentioned slurry is uniform
Coated in commercially available surface of ordinary glass, hypovanadic oxide-based thermochromism glass is obtained.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 2.As it can be seen that of the invention
For glass under the premise of visible light transmittance is more than 50%, sunlight regulation rate reaches 24.59%.Since regulation rate improves,
Color change becomes apparent.
Table 2
Embodiment 3
The vanadic anhydride solution 100ml containing 0.01mol/L is prepared first, and 0.005g tungstic acid and 0.5g mass is added
The water hydrazine that score is 10%, stirs into uniform solution.Above-mentioned solution is added in reaction kettle and is sealed, is reacted in 260 DEG C
24h.It is taken out after cooling, is centrifuged, washs, is dried to obtain hypovanadic oxide powder.
Take vanadium dioxide nano powder made from the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone that 100g acetone is added
Dispersion liquid simultaneously after ultrasonic disperse 30min, is transferred to ball grinder, ball milling 1h obtains vanadium dioxide under the conditions of 900r/min by middle stirring
Acetone dispersion liquor；Above-mentioned dispersion liquid, stirring to dissolution is added in 10g polymethyl methacrylate；Continuously add 4g cobaltous bromide, 5g
Trimethylolpropane and 24g tetrabutylammonium bromide, stirring is to being completely dissolved and be uniformly mixed；Above-mentioned dispersion is persistently stirred at 90 DEG C
Liquid 30min is to get to vanadium dioxide and dentate conversion body composite type heat mutagens mill base material.Above-mentioned slurry is coated uniformly on city
Surface of ordinary glass is sold, hypovanadic oxide-based thermochromism glass is obtained.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 3.As it can be seen that with common
Vanadium dioxide thermochromism glass phase ratio, glass of the invention have high visible light transmittance；Even if also, up to
It is more than 18% by the sunlight regulation rate that temperature change generates under the premise of 66.12% visible light transmittance.At the same time,
From the superficial to the deep, color also becomes bottle green from yellowish-brown, and (Fig. 3, the text in figure is to show the transparent of film to plexiglass tint
Property and the background being arranged).That is, dimming process it is adjoint visible change it is apparent.
Table 3
Embodiment 4
The oxygen vanadium sulphate solution 100ml containing 0.01mol/L is prepared first, and the water that 5g mass fraction is 10% is added and joins
Then ammonia is 7 formation suspensions using sodium hydroxide titration to pH, disperses precipitating filtration washing in 100mL water again and stir
Mix uniform solution.Above-mentioned solution is added in reaction kettle and is sealed, for 24 hours in 260 DEG C of reactions.It is taken out after cooling, by reaction solution
It is added in 100mL dehydrated alcohol, adds 10mL deionized water, 5mL ammonium hydroxide stirs evenly, 2.5mL is then being added dropwise just
Silester stirs 5h at room temperature, filters, and washs, dry, and annealing obtains the hypovanadic oxide powder of silica cladding.
The cladding vanadium dioxide nano powder of silica made from the above-mentioned hydro-thermal of 1g and 0.5g polyvinylpyrrolidone is taken to be added
After stirring simultaneously ultrasonic disperse 30min in 100g ethyl alcohol, dispersion liquid is transferred to ball grinder, ball milling 1h is obtained under the conditions of 900r/min
Vanadium dioxide alcohol dispersion liquid；Above-mentioned dispersion liquid, stirring to dissolution is added in 10g polyvinyl butyral；Continuously add 9g bromine
Change cobalt, 14g neopentyl glycol and 52g tetrabutylammonium bromide, stirring is to being completely dissolved and be uniformly mixed；It is persistently stirred at 90 DEG C above-mentioned
Dispersion liquid 30min is to get to vanadium dioxide and dentate conversion body composite type heat mutagens mill base material.Above-mentioned slurry is uniformly coated
In commercially available surface of ordinary glass, hypovanadic oxide-based thermochromism glass is obtained.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 4.As it can be seen that of the invention
For glass under the premise of visible light transmittance is more than 50%, sunlight regulation rate reaches 21.91%.Since regulation rate improves,
Color change becomes apparent.
Table 4
Comparative example 1
The vanadic anhydride solution 100ml containing 0.01mol/L is prepared first, and 0.01g oxalic acid is added and is stirred into uniform
Solution.Above-mentioned solution is added in reaction kettle and is sealed, for 24 hours in 240 DEG C of reactions.It is taken out after cooling, centrifugal drying obtains titanium dioxide
Vanadium powder body.Take vanadium dioxide nano powder made from the above-mentioned hydro-thermal of 0.5g and 0.25g polyvinylpyrrolidone that 100g ethyl alcohol is added
Dispersion liquid simultaneously after ultrasonic disperse 30min, is transferred to ball grinder, ball milling 1h obtains vanadium dioxide under the conditions of 900r/min by middle stirring
Alcohol dispersion liquid；Above-mentioned dispersion liquid, stirring to dissolution is added in 9g polyvinyl butyral；Above-mentioned point is persistently stirred at 90 DEG C
Dispersion liquid 30min to get arrive vanadium dioxide thermochromism slurry.Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, is obtained
Obtain hypovanadic oxide-based thermochromism glass.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 5.As it can be seen that being used only
Under the premise of vanadium dioxide is as thermochromic material, to obtain the comparable visible light transmittance of embodiment 1, sunlight is adjusted
Rate only has before and after the half of embodiment 1.Meanwhile from fig. 4, it can be seen that glass does not generate visual tone variations when dimming.
Table 5
Comparative example 2
The vanadic anhydride solution 100ml containing 0.01mol/L is prepared first, and 0.005g tungstic acid and 0.5g mass is added
The water hydrazine that score is 10%, stirs into uniform solution.Above-mentioned solution is added in reaction kettle and is sealed, is reacted in 260 DEG C
24h.It takes out, is centrifuged after cooling, washing is dried to obtain hypovanadic oxide powder.Take vanadium dioxide nano made from the above-mentioned hydro-thermal of 1g
After stirring simultaneously ultrasonic disperse 30min in powder and 0.5g polyvinylpyrrolidone addition 100g ethyl alcohol, dispersion liquid is transferred to ball
Grinding jar, ball milling 1h obtains the alcohol dispersion liquid of vanadium dioxide under the conditions of 900r/min；9g polyvinyl butyral is added above-mentioned
Dispersion liquid, stirring to dissolution；Above-mentioned dispersion liquid 30min is stirred at 90 DEG C persistently to get vanadium dioxide thermochromism slurry is arrived.It will
Above-mentioned slurry is coated uniformly on commercially available surface of ordinary glass, obtains hypovanadic oxide-based thermochromism glass.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 6.As it can be seen that being used only
Under the premise of vanadium dioxide is as thermochromic material, such as increase vanadium dioxide solid content, sunlight regulation rate is also increased
Add and reach 12.23%, still, visible light transmittance quickly falls to only 40% or so.In addition, not observed when light modulation bright
Aobvious tone variations.
Table 6
Comparative example 3
100g acetone is added in 10g polymethyl methacrylate and is stirred to dissolving, 15g perchloric acid is then added sequentially
Nickel, 14g neopentyl glycol and 52g tetrabutylammonium bromide, stirring to dissolution obtain dispersion liquid.Using spin-coating method by dispersion in city
Surface of ordinary glass is sold, acquisition contains only polymer-based thermochromism glass.
The performance of glass is evaluated with 1 same method of embodiment, the results are shown in Table 7.As it can be seen that individually making
Under conditions of LETC thermochromic material, though coated glass visible light transmittance with higher and apparent temperature control vision become
Change, but it is only 2.75% that the temperature control amplitude of accommodation within the scope of insolation infrared band is very faint, does not have good infrared adjusting
Effect.Meanwhile the glass entirety infrared transmittivity is excessively high, does not have good infrared barrier effect in summer.
Table 7
The present invention is by combining vanadium dioxide material and LETC material to constitute a kind of completely new composite material, to make green wood
The thermo-chromic effects of material cover the insolation full band range including visible light and infrared band, in regulating power and comfortable journey
There is the progress of leap on degree, can be widely used for the energy conservation and environmental protections such as Intelligent energy-saving window.
Claims (13)
1. a kind of hypovanadic oxide-based thermochromic composite of high-performance characterized by comprising as inorganic system's thermochromism
The vanadium dioxide of material and dentate conversion body as organic system thermochromic material, the dentate conversion body include that can turn
Become metal ion, 400~1400nm wave-length coverage internal absorbance matching less than 0.2 can be formed in the metal ion that changes
It closes the low absorbance ligand of object and extinction in 400~1400nm wave-length coverage can be formed in the metal ion that changes
The high absorbance ligand for the complex that degree is 0.8 or more,
Inorganic system's thermochromic material exists with organic system thermochromic material with admixture,
The vanadium dioxide exists in the form of vanadium dioxide nano particle, and the particle size range of the vanadium dioxide nano particle is
20~80nm,
The vanadium dioxide nano particle has external coating, and the thickness range of the external coating is 2~20nm, the outsourcing
The material of coating is at least one of carbon, silica, magnesia and aluminium oxide,
It further include polymeric substrate in the composite material.
2. composite material according to claim 1, which is characterized in that the vanadium dioxide is doping and/or undoped gold
Red stone phase hypovanadic oxide.
3. composite material according to claim 1, which is characterized in that the metal ion that changes is Fe (II), Co
(II), at least one of Ni (II), Cu (II).
4. composite material according to claim 1, which is characterized in that the low absorbance ligand is dihydric alcohol, polynary
At least one of alcohol；The high absorbance ligand includes that can form high absorbance ligand compound with that can change metal ion
The coordinating group of object is selected from least one of chloride, bromide, iodide, Pseudohalides.
5. composite material according to claim 4, which is characterized in that the polyalcohol is trihydroxylic alcohol.
6. composite material according to claim 1, which is characterized in that the low absorbance ligand be neopentyl glycol, three
Hydroxymethyl-propane, ethylene glycol, glycerine, 2- methyl-1, at least one of 3-propanediol.
7. composite material according to claim 1, which is characterized in that the high absorbance ligand is selected from tetrabutyl phosphonium bromide
Ammonium, tetrabutylammonium chloride, tetrabutylammonium iodide, choline chloride, triphenylphosphine, at least one of tetrathiacyclotetradecane.
8. composite material according to claim 1, which is characterized in that vanadium dioxide and changing in dentate conversion body
The molar ratio of metal ion is 9:1~1:9.
9. composite material according to claim 8, which is characterized in that vanadium dioxide and changing in dentate conversion body
The molar ratio of metal ion is 2:1~1:6.
10. composite material according to claim 9, which is characterized in that vanadium dioxide turns with dentate conversion body
Become the molar ratio of metal ion as 1:1~1:4.
11. composite material according to claim 10, which is characterized in that the polymeric substrate is polyacrylamide, gathers
Hydroxyethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyethylene
Base methyl ether, poly-hydroxyethyl methyl acrylate, polyvinylpyridine, polyglycerolmethacrylate, hydroxyethyl cellulose, poly- ammonia
At least one in ester, poly- 2- ethyl -2- oxazoline, polyvinylpyrrolidone and copolymer containing above-mentioned polymers functionality
Kind.
12. composite material according to claim 1, which is characterized in that the thermochromism of the composite material is arrived at 10 DEG C
Reversible progress between 100 DEG C.
13. composite material according to any one of claim 1 to 12, which is characterized in that the composite material is with thermotropic
The form for slurry, thermochromic coatings or the thermochromic thin film of changing colour exists.
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