CN105713597B - A kind of composite type heat mutagens mill base material and preparation method thereof - Google Patents
A kind of composite type heat mutagens mill base material and preparation method thereof Download PDFInfo
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- CN105713597B CN105713597B CN201610111203.7A CN201610111203A CN105713597B CN 105713597 B CN105713597 B CN 105713597B CN 201610111203 A CN201610111203 A CN 201610111203A CN 105713597 B CN105713597 B CN 105713597B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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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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- 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
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Abstract
The present invention relates to a kind of composite type heat mutagens mill base material and preparation method thereof, the composite type heat mutagens mill base material includes：Vanadium dioxide nano powder as inorganic system's thermochromic material, dentate conversion body, polymeric substrate and the decentralized medium 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 with it is described change metal ion formed high absorbance complex high absorbance ligand.The composite type heat mutagens mill base material of the present 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, more particularly to thermochromic material and its section
It can environmental protection application.
Background technology
Global energy shortage problem getting worse, excessive carbon emission cause 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
Energy-saving and emission-reduction, one of 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 as building with extraneous
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 for being referred to as " Intelligent energy-saving window " just comes into being.
Intelligent energy-saving window uses the cause off-color material that optical property can be changed, the transflection generated to various physical stimulations using it
The variations such as performance are 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 simple in structure, material utilization amount is few, completely dispenses with switch or artificial energy source and controls energy
Temperature change of according with one's environment and realize the remarkable advantages such as automatic photo-thermal regulation and control, 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 as the main inventive person of above-mentioned technology, at the same notice above-mentioned vanadium dioxide temperature control Intelligent energy-saving window according to
So there is following several deficiencies：
(1) there is the higher amplitude of accommodation, but the visible light wave range to accounting for insolation gross energy 50% to insolation infrared band
Hardly there is adjustment effect, result to reduce global solar radiation regulation rate；
(2) due to not having apparent adjustment effect in visible light wave range, this adjust can not be utilized to generate enough regard
Feel variation, to be helpless to carry out strong regulating effect demonstration to customer, to product conduct promotion to cause it is decisive
Harmful 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.
Invention content
The thermochromism of dentate conversion body (Ligand Exchange Thermochromic abbreviation LETC) material passes through not
The synthermal lower metal ion that can change is combined from different dentates, the complex with different absorption coefficients is formed, to produce
Raw thermo-chromic effects, in general, at low temperature, metal ion is combined to form low absorption coefficient with low absorption coefficient dentate
Complex has higher transmitance；At high temperature, metal ion transfers to be combined to form high-selenium corn 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 Thermochromics
Wavelength band causes regulating power less than normal.It cannot more be adjusted due to being the mid and far infrared wave band most sensitive to human body warm sensation
Section can not carry out the adjusting for ensureing human body comfort.
In addition, LETC materials are 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, by testing repeatedly, finds to pass through knot for the first time
It closes vanadium dioxide material and constitutes a kind of completely new composite material with LETC materials, 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 composite type heat mutagens mill base material, including：Titanium dioxide as inorganic system's thermochromic material
Vanadium nano-powder, dentate conversion body, polymeric substrate and decentralized medium as organic system thermochromic material, the coordination
Base conversion body include can change metal ion, can with it is described change metal ion formed low absorbance complex low absorbance
Ligand and can with it is described change metal ion formed high absorbance complex high absorbance ligand.
The composite type heat mutagens mill base material of the present invention, its main feature is that thermochromism wavelength band covers including visible light
Entire insolation spectrum, thus compared with traditional vanadium dioxide thermochromic material have high global solar radiation regulation rate.Meanwhile
In the larger mediating effect+6 of visible light wave range, it is changed into visual significant change, the effect of product is shown and publicity is promoted
With decisive significance.In addition, due to increasing absorption of the visible light compared with long-wave band so that the intrinsic yellow color development of vanadium dioxide
Larger inhibition is obtained.
Preferably, the vanadium dioxide nano powder is doped or non-doped rutile phase hypovanadic oxide.
Preferably, the grain size of the vanadium dioxide nano powder is 20~80nm.
Preferably, the metal ion that changes is at least one of Fe (II), Co (II), Ni (II), Cu (II), institute
It is dihydric alcohol, trihydroxylic alcohol, at least one of polyalcohol, preferably neopentyl glycol to state low absorbance ligand, trimethylolpropane,
Ethylene glycol, glycerine, 2- methyl-1s, at least one of 3-propanediol；The high absorbance ligand include can with can turn
Become the coordinating group that metal ion forms high absorbance complex, preferably tetrabutylammonium bromide, tetrabutylammonium chloride, four fourths
Base ammonium iodide, choline chloride, triphenylphosphine, at least one of tetrathiacyclotetradecane.
Preferably, vanadium dioxide is 9 with the molar ratio for changing metal ion in dentate conversion body:1~1:9, it is excellent
Select 2:1~1:6, more preferable 1:1~1:4.
Preferably, the polymeric substrate is polyacrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, gathers
Vinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, polyethylene
Yl pyridines, polyglycerolmethacrylate, hydroxyethyl cellulose, polyurethane, poly- 2- ethyl-2-oxazolines, polyvinylpyrrolidine
Ketone and at least one of copolymer containing above-mentioned polymers functionality.
Preferably, the decentralized medium is deionized water, ethyl alcohol, propyl alcohol, isopropanol, ethyl acetate, toluene, acetone, fourth
At least one of ketone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate.
Preferably, in the composite type heat mutagens mill base material, a concentration of 0.1~2mol/ of vanadium dioxide nano powder
L；The concentration ratio of vanadium dioxide nano powder and polymeric substrate is 1:9~9:1, preferably 1:9~5:1, more preferable 1:5~1:1；
A concentration of 0.5~5mol/L of metal ion can be changed.
On the other hand, the present invention also provides the preparation methods that any one of the above composite type heat mutagens mill base material applies, including
Following steps：
A. prepare vanadium dioxide nano powder and be scattered in decentralized medium, obtain dispersion liquid A；
B. soluble polymer is added in dispersion liquid A, stirring is completely dissolved to polymer, obtains dispersion liquid B；
C. dentate conversion body is added in dispersion liquid B, stirs to being completely dissolved, obtains dispersion liquid C；
D. it is persistently dispersed with stirring liquid C and heats, the extra decentralized medium of evaporation section obtains the composite type heat mutagens mill base
Material.
Preferably, a concentration of 0.01~1mol/L of vanadium dioxide, preferably 0.05~0.5mol/L in dispersion liquid A, more preferably
0.1~0.2mol/L；The concentration ratio of vanadium dioxide and polymer is 1 in dispersion liquid B:9~9:1, preferably 1:9~5:1, more preferably
1:5~1:1；A concentration of 0.01~the 5mol/L, 0.1~2mol/ for changing metal ion of dentate conversion body in dispersion liquid C
L, more preferable 0.5~1mol/L.
In another aspect, the present invention also provides a kind of compound thermochromic coatings, by any one of the above composite type heat
Mutagens mill base material is made.
Another aspect, the present invention also provides a kind of compound thermochromic thin films, by any one of the above composite type heat
Mutagens mill base material is made coated on matrix.
Description of the drawings
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 implementation mode
It is further illustrated the present invention 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 simultaneously containing 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
The synthermal lower metal ion that can change is combined from different dentates, the complex with different absorption coefficients is formed, to produce
Raw thermo-chromic effects, at low temperature, metal ion is combined to form low absorption coefficient complex with low absorbance ligand, is had
Higher transmitance；At high temperature, metal ion transfers to be combined to form high absorption coefficient complex 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 to be combined from 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 refer to 400~
1400nm wave-length coverage internal absorbances are less than 0.2, and the high absorbance refers to being in 400~1400nm wave-length coverage internal absorbances
0.8 or more.
Low absorbance ligand includes but not limited at least one of dihydric alcohol, trihydroxylic alcohol, polyalcohol, and preferably new penta 2
Alcohol, trimethylolpropane, ethylene glycol, glycerine, 2- methyl-1s, at least one of 3-propanediol.High absorbance ligand packet
Containing the coordinating group of high absorbance complex can be formed with metal ion can be changed, such as N, P can be contained, in S atom
At least one, and/or selected from chloride, bromide, iodide, at least one of 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 and 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
Include not necessarily polymer in dentate conversion body, has and do not need polymer in the presence of solvent, solvent and polymer can be mutual
Mutually substitution converts bridge as ligand.The polymer include but 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- ethyls -2- oxazoles
Quinoline, polyvinylpyrrolidone and at least one of the copolymer containing above-mentioned polymers functionality.
Vanadium dioxide in the present invention can be undoped vanadium dioxide, can also be 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 arbitrary 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 be controlled
Very little and pattern, or can also regulate and control the phase transition temperature of vanadium dioxide simultaneously.
In the present invention, vanadium dioxide can be powder, preferably graininess, i.e., 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 1 μm, 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
It can be 2~20nm to enclose.
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 preferably 9 of vanadium dioxide and metal ion in LETC materials:1~1:9, more preferable 2:1~1:6, most preferably 1:1
~1:4.
The present invention is by combining vanadium dioxide material and LETC materials 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 of the visible light wave range to 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, contribute 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 apparent mediating effect+6.
Meanwhile the absorption of LETC material visible-light specific wavelengths, 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 materials.
The thermochromism range of the composite material of the present invention covers 300~2500nm insolation all bands, and has and obviously regard
Feel effect.The thermochromism reversible progress between 10 DEG C to 100 DEG C.
The composite material of the present 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 be respectively stratiform but interlayer contact, or be respectively that stratiform and interlayer do not contact.For example, this hair
Bright composite material can be a kind of laminated film 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 with other nonwoven fabric from filaments between person.Layered object may be, for example, PET flexible (polyethylene terephthalate) film,
The glass etc. of rigidity.
In addition, can also contain polymeric substrate in the composite material of the present invention.The polymeric substrate is on the one hand as coordination
On the other hand the bridge of body conversion 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) with LETC materials appropriate suitably to compare
Example is compound, and is dispersed among polymeric substrate, and it is compound to form the thermochromism with height temperature control optical adjustment properties
Thin-film material.In addition, the polymeric substrate be preferably in composite material vanadium dioxide and dentate conversion body have dissolve each other
Property, to keep slurry not generate precipitation, and keep the transparency of film.As an example, the polymeric substrate is chosen as gathering
Acrylamide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethylacrylic acid
Methyl esters, polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, polyvinylpyridine, polyglycerolmethacrylate, ethoxy are fine
Tie up element, polyurethane, poly- 2- ethyl-2-oxazolines, polyvinylpyrrolidone and the copolymer containing above-mentioned polymers functionality
At least one of.
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 includes but not limited to for 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 ratio of vanadium dioxide nano powder and polymeric substrate can be 1:9~9:1, 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 is converted with dentate
The molar ratio for changing metal ion in body can be 9 as described above:1~1:9, preferably 2:1~1:6, more preferable 1:1~1:4.
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, can also add one or more of UV absorbents, light stabilizer, thermal stabilizer and plasticizer.
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
Can be made by hydro-thermal method.It can be rutile phase hypovanadic oxide.In dispersion liquid A vanadium dioxide concentration can be 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 ratio of vanadium dioxide and polymer 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-oxazolines, 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.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.
The composite type heat mutagens mill base material of the present invention can be prepared as needed as thermochromic coatings and various pad pastings
Or the thermochromic thin films such as intermediate coat.Can be that the slurry is coated on base material as the preparation method of thermochromic thin film
And it is formed.Coating method can select the modes such as spraying, blade coating, brushing, showering or roller coating.Base material include but 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 base, you can prepare building and vehicle
With thermochromism Energy Saving Windows.
Such as building or automobile energy-saving demand, the different LETC materials of doping to vanadium dioxide or selection can be passed through
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 present 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 larger 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 of low cost, is suitble to high-volume industrial production, can be widely used for intelligent section
The energy saving field of environment protection 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 the above 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 concrete numerical 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, centrifuges, washs, is dried to obtain
Hypovanadic oxide powder.
Take vanadium dioxide nano powder made from the above-mentioned hydro-thermals of 0.5g and 0.25g polyvinylpyrrolidones 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 dissolving is added in 10g polyvinyl butyrals；Continuously add 6.5g nickelous perchlorates,
6g neopentyl glycols 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 result of calculation as shown in Table 1.As it can be seen that compared with common vanadium dioxide thermochromism glass, 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 word 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 fractions are 10% is added and joins
Then ammonia uses sodium hydroxide titration to form suspensions to pH for 7, precipitation filtration washing is scattered in again in 100mL water and is stirred
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, centrifuge, 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-thermals of 1g and 0.5g polyvinylpyrrolidones that 100g is added
It is stirred in acetone and after ultrasonic disperse 30min, 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 dissolving is added in 10g polymethyl methacrylates；Continuously add 15g high chlorine
Sour nickel, 12g trimethylolpropanes 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 the present 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 acids 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, in 260 DEG C of reactions
24h.It is taken out after cooling, centrifuges, washs, is dried to obtain hypovanadic oxide powder.
Take vanadium dioxide nano powder made from the above-mentioned hydro-thermals of 0.5g and 0.25g polyvinylpyrrolidones 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 dissolving is added in 10g polymethyl methacrylates；Continuously add 4g cobaltous bromides, 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 is compared, and glass of the invention has high visible light transmittance；Even if also, up to
Under the premise of 66.12% visible light transmittance, the sunlight regulation rate generated by temperature change is more than 18%.At the same time,
From the superficial to the deep, color also becomes bottle green from yellowish-brown, and (Fig. 3, the word 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 fractions are 10% is added and joins
Then ammonia uses sodium hydroxide titration to form suspensions to pH for 7, precipitation filtration washing is scattered in again in 100mL water and is stirred
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 absolute ethyl alcohols, adds 10mL deionized waters, 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.
Silica cladding vanadium dioxide nano powder and 0.5g polyvinylpyrrolidones made from the above-mentioned hydro-thermals of 1g is taken to be added
It is stirred in 100g ethyl alcohol and after ultrasonic disperse 30min, 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 dissolving is added in 10g polyvinyl butyrals；Continuously add 9g bromines
Change cobalt, 14g neopentyl glycols 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 the present 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-thermals of 0.5g and 0.25g polyvinylpyrrolidones 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 dissolving is added in 9g polyvinyl butyrals；Above-mentioned point is persistently stirred at 90 DEG C
Dispersion liquid 30min is to get to 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 using only
Under the premise of vanadium dioxide is as thermochromic material, to obtain 1 comparable visible light transmittance of embodiment, 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 acids 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, in 260 DEG C of reactions
24h.It takes out, centrifuges after cooling, washing is dried to obtain hypovanadic oxide powder.Take vanadium dioxide nano made from the above-mentioned hydro-thermals of 1g
Powder and 0.5g polyvinylpyrrolidones, which are added in 100g ethyl alcohol, to be stirred and after ultrasonic disperse 30min, 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 butyrals are added above-mentioned
Dispersion liquid, stirring to dissolving；Above-mentioned dispersion liquid 30min is persistently stirred at 90 DEG C to get to vanadium dioxide thermochromism slurry.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 using 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 methacrylates and is stirred to dissolving, 15g perchloric acid is then added sequentially
Nickel, 14g neopentyl glycols and 52g tetrabutylammonium bromide, stirring to dissolving 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 materials, though there is coated glass higher visible light transmittance and apparent temperature control vision to 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 materials 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
The progress for having leap on degree, can be widely used for the energy saving field of environment protection such as Intelligent energy-saving window.
Claims (21)
1. a kind of composite type heat mutagens mill base material, which is characterized in that including：Vanadium dioxide as inorganic system's thermochromic material
Nano-powder, dentate conversion body, polymeric substrate and decentralized medium as organic system thermochromic material, the dentate
Conversion body includes that can change metal ion, can be formed in 400~1400nm wave-length coverage interior suctions with the metal ion that changes
Luminosity is less than the low absorbance ligand of 0.2 complex and can be formed in 400~1400nm with the metal ion that changes
The high absorbance ligand for the complex that wave-length coverage internal absorbance is 0.8 or more, the metal ion that changes are selected from Fe
(II), at least one of Co (II), Ni (II), Cu (II),
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 composite type heat mutagens mill base material is prepared via a method which：
A. preparing vanadium dioxide nano powder and be scattered in decentralized medium, ball milling, rotational speed of ball-mill is 500~1000r/min,
Obtain dispersion liquid A；
B. soluble polymer is added in dispersion liquid A, stirring is completely dissolved to polymer, obtains dispersion liquid B；
C. dentate conversion body is added in dispersion liquid B, stirs to being completely dissolved, obtains dispersion liquid C；
D. it is persistently dispersed with stirring liquid C and heats, the extra decentralized medium of evaporation section obtains the composite type heat mutagens mill base material；
Wherein, in step a,
Vanadium dioxide nano powder is the vanadium dioxide nano particle with external coating, and the thickness range of the external coating is
The material of 2~20nm, the external coating are at least one of carbon, silica, magnesia and aluminium oxide；And/or
Vanadium dioxide nano powder and dispersing aid are scattered in decentralized medium, the dispersing aid is selected from polyethylene glycol, oil
Acid, triethyl group hexyl phosphoric acid, silane coupling agent, lauryl sodium sulfate, methyl anyl alcohol, fatty acid polyethylene glycol ester, polypropylene
Hydrochlorate, polyacrylamide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, modified polyurethane and modification
One or more of acrylic acid dispersant.
2. composite type heat mutagens mill base material according to claim 1, which is characterized in that the vanadium dioxide nano powder is
Doped or non-doped rutile phase hypovanadic oxide.
3. composite type heat mutagens mill base material according to claim 1, which is characterized in that the low absorbance ligand is more
At least one of first alcohol；The high absorbance ligand includes that can form high absorbance coordinationization with that can change metal ion
Close object coordinating group, the high absorbance ligand be selected from tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide,
At least one of choline chloride, triphenylphosphine, tetrathiacyclotetradecane.
4. composite type heat mutagens mill base material according to claim 3, which is characterized in that the low absorbance ligand is two
At least one of first alcohol, trihydroxylic alcohol.
5. composite type heat mutagens mill base material according to claim 4, which is characterized in that the low absorbance ligand is new
At least one of pentanediol, trimethylolpropane, ethylene glycol, glycerine, 2- methyl-1,3-propanediols.
6. composite type heat mutagens mill base material according to claim 1, which is characterized in that vanadium dioxide and dentate conversion body
In the molar ratio for changing metal ion be 9:1~1:9.
7. composite type heat mutagens mill base material according to claim 6, which is characterized in that vanadium dioxide and dentate conversion body
In the molar ratio for changing metal ion be 2:1~1:6.
8. composite type heat mutagens mill base material according to claim 7, which is characterized in that vanadium dioxide and dentate conversion body
In the molar ratio for changing metal ion be 1:1~1:4.
9. composite type heat mutagens mill base material according to claim 1, which is characterized in that the polymeric substrate is polypropylene
Amide, poly hydroxy ethyl acrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, poly-methyl methacrylate
Ester, polyvinylmethyl ethers, poly-hydroxyethyl methyl acrylate, polyvinylpyridine, polyglycerolmethacrylate, hydroxy ethyl fiber
In element, polyurethane, poly- 2- ethyl-2-oxazolines, polyvinylpyrrolidone and copolymer containing above-mentioned polymers functionality
At least one.
10. composite type heat mutagens mill base material according to claim 1, which is characterized in that the decentralized medium is deionization
In water, ethyl alcohol, propyl alcohol, isopropanol, ethyl acetate, toluene, acetone, butanone, gamma-butyrolacton, chloroform, propylene glycol methyl ether acetate
At least one.
11. composite type heat mutagens mill base material according to any one of claim 1 to 10, which is characterized in that described multiple
In mould assembly thermochromism slurry, a concentration of 0.1~2mol/L of vanadium dioxide nano powder；Vanadium dioxide nano powder with polymerize
The concentration ratio of object base material is 1:9~9:1；A concentration of 0.5~5mol/L of metal ion can be changed.
12. composite type heat mutagens mill base material according to claim 11, which is characterized in that vanadium dioxide nano powder with it is poly-
The concentration ratio for closing object base material is 1:9~5:1.
13. composite type heat mutagens mill base material according to claim 12, which is characterized in that vanadium dioxide nano powder with it is poly-
The concentration ratio for closing object base material is 1:5~1:1.
14. composite type heat mutagens mill base material according to claim 1, which is characterized in that vanadium dioxide concentration in dispersion liquid A
For 0.01~1 mol/L；The concentration ratio of vanadium dioxide and polymer is 1 in dispersion liquid B:9~9:1；Dentate turns in dispersion liquid C
Change a concentration of 0.01~5 mol/L for changing metal ion of body.
15. composite type heat mutagens mill base material according to claim 14, which is characterized in that vanadium dioxide is dense in dispersion liquid A
Degree is 0.05~0.5 mol/L.
16. composite type heat mutagens mill base material according to claim 15, which is characterized in that vanadium dioxide is dense in dispersion liquid A
Degree is 0.1~0.2 mol/L.
17. composite type heat mutagens mill base material according to claim 14, which is characterized in that in dispersion liquid B vanadium dioxide with
The concentration ratio of polymer is 1:9~5:1.
18. composite type heat mutagens mill base material according to claim 17, which is characterized in that in dispersion liquid B vanadium dioxide with
The concentration ratio of polymer is 1:5~1:1.
19. composite type heat mutagens mill base material according to claim 14, which is characterized in that dentate is converted in dispersion liquid C
A concentration of 0.1~2 mol/L for changing metal ion of body.
20. composite type heat mutagens mill base material according to claim 19, which is characterized in that dentate is converted in dispersion liquid C
A concentration of 0.5~1 mol/L for changing metal ion of body.
21. a kind of compound thermochromic thin film, which is characterized in that by compound described in any one of claim 1 to 20
Thermochromism slurry is made coated on matrix.
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| CN106634533B (en) * | 2016-12-26 | 2019-04-16 | 北京东方雨虹防水技术股份有限公司 | A kind of thermochromism polyurethane water-proof paint |
| CN109913071B (en) * | 2017-12-12 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Temperature control composite energy-saving material |
| CN107868588A (en) * | 2017-12-12 | 2018-04-03 | 广东韩亚薄膜科技有限公司 | Reversible thermochromic coating and preparation method and application |
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| CN110691818A (en) | 2018-03-02 | 2020-01-14 | 上海创始实业（集团）有限公司 | Polymer, thermochromic and/or hydrogel compositions and devices, including products embodying same, and methods and processes for making same |
| CN108410242A (en) * | 2018-04-04 | 2018-08-17 | 江苏新亿源环保科技有限公司 | A kind of preparation method of thermochromic coatings |
| CN109575797B (en) * | 2018-11-12 | 2021-02-12 | 中国科学院上海硅酸盐研究所 | Color development adjustable vanadium dioxide-based thermochromic composite material and application thereof |
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