CN106147719B - A kind of preparation method of the hot phase-change material of high transparency - Google Patents
A kind of preparation method of the hot phase-change material of high transparency Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the hot phase-change material of high transparency, vanadium-containing compound, Tungstenic compound, alcohol water mixed solvent, dispersing agent and reducing agent are put into the hydrothermal reaction kettle containing mill ball, the stirring rotator of high speed rotation hydrothermal reaction kettle, rotor speed is 1000-8000 revs/min, temperature in hydrothermal reaction kettle is 160-300 DEG C, pressure is 1-20kg, reacting jitter time is 16-100 hours, and the VO that primary particle size is not more than 10nm is obtained after grinding, reaction and dispersion2Precursor solution；Aforementioned VO2Precursor solution pours into crucible after freezing and drying, under the atmosphere of inert gas shielding, calcines 3-48 hours at 460-680 DEG C, after cooling, obtains the VO that primary particle size is not more than 20nm2Nano-powder, the as hot phase-change material of high transparency, it can be widely used for various transparent heat insulating coat fields and be added in the transparent substrates such as PET, PC, PE, PVB, EVA, TPU, more trap heats when its heat, more heats are penetrated when it is cool, play intelligent thermal control energy-saving effect cool in summer and warm in winter.
Description
Technical field
The present invention relates to a kind of production method of the hot phase-change material of high transparency, the prepared powder and nano pulp come out
Has the function of high transparency insulation thermal phase transformation.
Background technique
There are the patent and report of many associated hot phase-change materials both at home and abroad at present, the present inventor devotes a tremendous amount of time and essence
Power has consulted the related paper at home and abroad of a large amount of associated hot phase transformation heat-barrier material, patent and report, in these reports and patent
Appearance is all to limit in the micron-scale, the VO of submicron order2Relevant content, be all be confined to through traditional hydro-thermal reaction mode or
The mode of mixing prepares the VO in 100nm-200nm particle size range2Based on phase-change material, these materials are because of primary grain
Diameter is larger, the function of realizing more high transparency of having no idea, if it is desired to being applied to automobile front windshield or other high transparency are answered
It is promoted with field etc. again without method, does not reach requirement, still there is significant limitation for application field.
Such as: Chinese patent CN102066261A disclose a kind of thermochromic particulate and its dispersion liquid and manufacturing method with
And light modulation property coating, light modulation property film, light modulation property ink, the patent contain VO2The particle and TiO of (R phase)2Particle elaborates emphatically
The hot phase transition function light modulation of average grain diameter 200nm hot Phase-change particles below acts on, without illustrating high transparency heat-insulating and energy-saving
Function and effect.
For another example, carbon coating vanadium dioxide nano particle and preparation method thereof disclosed in Chinese patent CN103554997A
In, the nanoparticle being related to is that the three-dimensional dimension of the kernel core material of the vanadium dioxide used is also 100nm particle below
Pattern, and using carbon coating technology in situ in traditional hydro-thermal reaction, nanometer VO is prepared in production2WO is added in powder process3
And polysaccharide material, obtaining under pyroreaction can reduce phase transition temperature, the carbon coating with certain heat absorption, heat insulating function
VO2The vanadium oxide primary particle size of the related content of nano-powder, this method preparation is larger, and prepares VO2The technique mistake of powder
Cheng Huanjie is too many, and industrialization production product control is relatively difficult.
For another example, Chinese patent CN103073942In a kind of Vanadium dioxide composite powder disclosed in B and preparation method thereof,
Elaborate that vanadium dioxide primary particle size in 200nm state below, is only mentioned to using traditional mixing emphatically
Mode adulterates the various metallic elements of addition, and realizing has the preparation method of the composite granule of certain hot phase transition function, without relating to
And it is small to primary particle size, the preparation method of the hot phase-change material of high transparency, the major defect of these technical products is VO2Nanoparticle
The primary particle size of son is excessive, and dispersion performance is very limited, moreover, preparation process is excessively cumbersome and complicated, using these material institutes
The spectrophotometric data of the coating material prepared substantially all in visible light transmittance 40% hereinafter, IR rejection rate 40% with
Under.Therefore, maximum defect is that translucency is bad in use, and dispersibility is poor, and heat-insulating and energy-saving effect is very limited, city
Promote relatively difficult in field.
Based on many defects existing for these product technologies, research and probe to solve nanometer VO2Powder and nano pulp
The problem of big problem of primary particle size, the not high problem of translucency, bad dispersibility, the limited problem of heat-proof quality have very
The urgent market demand.To greatly improve a nanometer VO2The practical performance and cost performance of powder and slurry, greatly improve
VO2The application and popularizations efficiency of nano-powder.With important economic value, use value.
Vanadium dioxide VO2There are several isomerisms to crystallize, this is not defined as A, B, C, D, M, R phase, wherein near room temperature
Most stable of crystal phase is R phase, has same crystalline texture with rutile, so also known as Rutile Type.R phase hypovanadic oxide VO2Tool
There is hot phase-change characteristic.
Hot phase-change characteristic refers to that the optical property of material such as penetrates, reflects or absorb the temperature change generation with material
The performance of reversible change.Such as infrared ray wave band, that is, it is greater than the variation of the wave band transmitance of 780nm, although naked eyes eyeball is invisible
It is to be changed with the change transmitance of material temperature, so that environment temperature also changes correspondingly, is defined as hot phase transformation.
Pure rutile phase hypovanadic oxide is monoclinic crystal (M phase) when being lower than 68 degree, is in characteristic of semiconductor, i.e., to infrared
Line has higher transmitance；When being higher than 68 degree, become regular crystal (R phase), is in metallic character, high reflection is become to infrared ray.
Vanadium dioxide VO2Phase transition temperature can by mix wolfram element amount or change structure regulating.Also there is patent report
It mixes other elements or compound and thinks temperature to change.So the VO in the present invention2(phase) nano-powder and slurry include tungsten
The rutile phase hypovanadic oxide VO of element mixed2。
Summary of the invention
For the above-mentioned deficiency of the prior art, according to an embodiment of the invention, being desirable to provide a kind of hot phase transformation of high transparency
The preparation method of material, it is intended to hot phase transformation main material nanometer VO2(R phase) powder and slurry are during preparing nanoparticle
Effectively control primary particle size size, gives VO2(R phase) powder and slurry assign reliably, more preferably, high transparency, easily disperse, heat
Under the premise of phase transition function, solves VO2The primary particle size of powder and slurry is big, translucency is not high, bad dispersibility, prepares powder
The excessively cumbersome and complicated problem of technique, the key for effectively controlling primary particle size is vanadium compounds in hydrothermal reaction process
In, especially V5+ is formed during V4+ and with tungsten compound cohesive process, is dispersed under high temperature and high pressure environment by ball milling
Mode, regular influence forms the effect of internal stress and external carbuncle during nanoparticle, to realize effectively
Control VO2The primary particle size method of forming process.
According to embodiment, a kind of preparation method of the hot phase-change material of high transparency provided by the invention, by following weight hundred
Vanadium-containing compound, Tungstenic compound, alcohol water mixed solvent, dispersing agent and the reducing agent of point content are put into the hydro-thermal containing mill ball
In reaction kettle, the stirring rotator of high speed rotation hydrothermal reaction kettle, rotor speed is 1000-8000 revs/min, in hydrothermal reaction kettle
Temperature be 160-300 DEG C, pressure 1-20kg, reaction jitter time be 16-100 hour, by grinding, reaction and disperse
The VO that primary particle size is not more than 10nm is obtained afterwards2Precursor solution；
1. vanadium-containing compound: 5%-20%；
2. Tungstenic compound: 0.1%-1%；
3. dispersing agent: 0.1-1%；
4. alcohol water mixed solvent: 80%-94.7%；
5. reducing agent: 0.1%-1%；
Aforementioned VO2Precursor solution pours into crucible after freezing and drying, under the atmosphere of inert gas shielding, in
It is calcined 3-48 hours at 460-680 DEG C, after cooling, obtains the VO that primary particle size is not more than 20nm2Nano-powder, abbreviation V powder, i.e.,
For the hot phase-change material of high transparency.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, by following weight hundred
The VO for dividing the primary particle size of content to be not more than 20nm2Nano-powder, organic solvent or deionized water, phosphoric acid and diameter 0.1mm
Zirconia ball is respectively charged into the dispersion tank in planet high speed rotation dispersion machine, and revolving speed is 12000 revs/min, is dispersed 3 hours
Afterwards, the VO that there is the primary particle size of hot phase transition function to be not more than 20 nanometers is obtained2Waterborne nano slurry,
1. primary particle size is not more than the VO of 20nm2Nano-powder 9.5%-30%；
2. organic solvent or deionized water 69%-90%；
3. phosphoric acid 0.5%-1%；
The dosage for the zirconia ball that diameter is 0.1mm is the VO that primary particle size is not more than 20nm2The 4-8 of nano-powder dosage
Times.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, mill ball is diameter
For one of the glass marble of 0.05mm-3mm, metal ball, zirconia ball, cerium oxide, alumina balls or a variety of；Mill ball and anti-
The volume ratio for answering object is (1-3): (1-30).
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, vanadium-containing compound is
Vanadium pentoxide V2O5, sodium metavanadate NaVO3, vanadic sulfate VOSO4·nH2O, vanadyl oxalate VOC2O4·nH2O or vanadium oxytrichloride
VOCl3。
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, Tungstenic compound is
Phosphotungstic acid, sodium phosphotungstate and WO3At least one of.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, reducing agent is second two
At least one of amine, triethanolamine and N.N- dimethylethanolamine.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the present invention, dispersing agent be phosphoric acid,
At least one of nitric acid, hydrochloric acid and oxalic acid.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, alcohol water mixed solvent
For the mixed liquor of methanol and deionized water volume ratio 1:1.
According to one embodiment, in the preparation method of the aforementioned hot phase-change material of high transparency of the invention, calcining crucible is oxygen
Change aluminium crucible.
According to embodiment, the hot phase transformation of high transparency of the preparation method acquisition of the aforementioned hot phase-change material of high transparency of the present invention
Material is added in PVB, EVA, PET, PC, PP, PE, PMMA or TPO, and stirring squeezes out acquisition with the hot phase transformation function of high transparency
The functional plastic master batch and plate or coiled material product of energy.
Subsequent embodiment will demonstrate that, using the coating light come out prepared by the aforementioned hot phase-change material of high transparency of the present invention
85%, IR rejection rate can be greater than greater than 60% by learning index light transmittance.The aforementioned hot phase-change material of high transparency of the present invention has very
The transparency well, dispersibility, hot phase transformation critical-temperature are lower than 68 degree.
After the hot phase-change material of high transparency of the present invention mixes reconstruction function master batch with common PET slice, then with common PET
Be sliced the thermal insulation film for the 23um thickness that 1:1 mixing is drawn, optical wavelength the near infrared range of 950nm point can be with to IR rejection rate
Reach 60% or more, it is seen that light transmission rate is greater than 85%.
By the hot phase-change material of high transparency of the present invention be added in the polyvinyl butyral powder in PVB raw materials for production according to
Certain ratio adds, stirring, squeezes out the PVB adiabatic gum for obtaining the intelligent various thickness with the hot phase transition function of high transparency
Film.
In the polyester slice or polyester powder material that the hot phase-change material of high transparency of the present invention is added in PET raw materials for production
It adds, stir according to a certain percentage, extrusion acquisition has the intelligent PET heatpiston of the hot phase transition function of light high transparency female
Grain and various functional PET films and sheet metal coil.
The hot phase-change material of high transparency of the present invention is added to the slice of the polyethylene in PE raw materials for production or polyethylene powder
It adds, stir according to a certain percentage in material, squeezing out the intelligent PE heatpiston for obtaining and there is the hot phase transition function of high transparency
Master batch and sheet metal coil.
In the polyester slice or polyester powder material that the hot phase-change material of high transparency of the present invention is added in PC raw materials for production
It adds according to a certain percentage, stir, squeeze out the intelligent PC heatpiston master batch for obtaining and there is the hot phase transition function of high transparency
And sheet metal coil.
By the hot phase-change material of high transparency of the present invention be added to the PMMA in PMMA raw materials for production slice or powder material in by
According to certain ratio addition, stirring, squeeze out the heat-insulated master batch of intelligent PMMA and plate for obtaining and there is the hot phase transition function of high transparency
Material.
By the hot phase-change material of high transparency of the present invention be added in the EVA particle or EVA powder material in EVA raw materials for production by
The EVA for obtaining the intelligent various thickness with the hot phase transition function of high transparency according to certain ratio addition, stirring, extrusion is heat-insulated
Glue film.
The hot phase-change material of high transparency of the present invention is added in the resin slurry in oil paint raw materials for production according to one
Fixed ratio adds, stirring, disperses to obtain the intelligent oiliness insulating moulding coating with the hot phase transition function of high transparency.
By the hot phase-change material of high transparency of the present invention be added in the water-base resin slurry in water paint raw materials for production by
The intelligent Water-based thermal insulation coating with the hot phase transition function of high transparency is obtained according to certain ratio addition, stirring, dispersion.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture (TEM) of precursor solution according to an embodiment of the present invention.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is further explained.These embodiments are interpreted as being only used for
It is bright the present invention rather than limit the scope of the invention.After having read the content of the invention recorded, art technology
Personnel can make various changes or modifications the present invention, these equivalence changes and modification equally fall into the claims in the present invention and limited
Fixed range.
Embodiment 1
First taking diameter is the zirconia ball 400g of 0.1mm, is packed into ready 1L high-temperature high-pressure reaction kettle, then take respectively
①V2O5Powder: 20g；2. tungsten oxide WO3Powder: 0.4g；3. the mixed solvent 378.8g of methanol and deionized water 1:1；4. dispersing
Agent: phosphoric acid 0.4g；5. reducing agent: mono- dimethylethanolamine of N, N: 0.4g.
1. 2. 3. 4. 5. pouring into high-temperature high-pressure reaction kettle, lid, electrified regulation pressurization, high speed rotation reaction kettle are covered
Stirring rotator, temperature are set as 260 degree, and pressure is set as 15kg, and revolving speed is set as 6000 revs/min, and reaction jitter time is set
It is set to 24 hours.The VO that primary particle size is not more than 10nm is obtained after reaction in 24 hours, grinding, dispersion2(B phase) precursor is molten
Liquid, as shown in Figure 1.
Again the VO of above-mentioned acquisition2(B phase) precursor solution obtains VO by freeze-drying2(B phase) nano-powder.
Again the VO obtained in above-mentioned steps2(B phase) nano-powder pours into aluminium crucible, refills the atmosphere protected into argon gas
In furnace, furnace temperature is set as 580 degree, and calcination time is set as 12 hours, and fire door is opened after furnace temperature Temperature fall to room temperature and takes out powder
Body obtains the VO that primary particle size is not more than 20nm2(R phase) nano-powder.Referred to as: V1 powder.
Again the VO obtained by above-mentioned steps2(R phase) nano-powder takes 10g, deionized water 89.9g, phosphoric acid 0.1g, directly
Diameter is the zirconia ball 300g of 0.1mm, is sequentially loaded into the dispersion tank in planet high speed rotation dispersion machine, and lid starting electricity is covered tightly
Source, revolving speed are set as 12000 revs/min, and jitter time is set as 3 hours.It is taken out after shutdown, obtains primary particle size and be not more than 20
The VO of nanometer2Waterborne nano slurry.
After the V1 powder that embodiment 1 obtains takes 2% to be sliced with 98% common PET and mix reconstruction function master batch, then with commonly
PET is sliced after 1:1 mixing and draws film sample, the thermal insulation film of 23um thickness, in wavelength in the close red of 950nm point with small-scale test machine
Outside line region can achieve 60% or more to IR rejection rate, it is seen that light transmission rate is greater than 85%, 44 degree of hot phase transition temperature.
V1 powder is added in the polyvinyl butyral powder in PVB raw materials for production according to the ratio of mass ratio 2/10000ths,
Squeezing out to obtain with small-scale test machine after being sufficiently mixed uniformly with high speed powder stirring machine with a thickness of 0.38mm there is heat to want to become function
The heat-insulated glue film of energy measures visible light transmittance VLT with the optical testing instrument that wavelength is 950nm and obstructs lv greater than 86%, IR
Greater than 68%, phase transition temperature is 44 degree.
Embodiment 2
First taking diameter is the zirconia ball 500g of 0.1mm, is packed into ready 1L high-temperature high-pressure reaction kettle, then take respectively
1. Pian vanadic acid amine (NH4VO3) powder: 40g；2. phosphotungstic acid powder: 1.2g；3. the mixed solvent of methanol and deionized water 1:1
356.4g；4. dispersing agent: phosphatase 11 .2g；5. reducing agent: mono- dimethylethanolamine 1.2g of N, N.
1. 2. 3. 4. 5. pouring into high-temperature high-pressure reaction kettle, lid, electrified regulation pressurization, high speed rotation reaction kettle are covered
Stirring rotator, temperature are set as 260 degree, and pressure is set as 15kg, and revolving speed is set as 6000 revs/min, and reaction jitter time is set
It is set to 24 hours.The VO that primary particle size is not more than 10nm is obtained after reaction in 24 hours, grinding, dispersion2(B phase) precursor is molten
Liquid.
Again the VO of above-mentioned acquisition2(B phase) solution obtains VO by freeze-drying2(B phase) nano-powder.
Again the VO obtained in above-mentioned steps2(B phase) nano-powder pours into aluminium crucible, refills the atmosphere protected into argon gas
In furnace, furnace temperature is set as 580 degree, and calcination time is set as 12 hours, and fire door is opened after furnace temperature Temperature fall to room temperature and is taken out
Powder obtains the VO that primary particle size is not more than 20nm2(R phase) nano-powder.Referred to as: V2 powder.
Again the VO obtained by above-mentioned steps2(R phase) nano-powder takes 10g, toluene 89.9g, nitric acid 0.1g, and diameter is
The zirconia ball 300g of 0.1mm is sequentially loaded into the dispersion tank in planet high speed rotation dispersion machine, covers tightly lid startup power supply,
Revolving speed is set as 12000 revs/min, and jitter time is set as 3 hours.It is taken out after shutdown, obtains primary particle size and received no more than 20
The VO of rice2Oiliness nano pulp.
It is obtained in example 2] V2 powder take 4/10000ths be added to common PC powder mixing after extruding machine prepare
The transparent heat-insulated plate of the hot phase transformation of PC of 1mm thickness can achieve IR rejection rate in the near infrared range of 950nm point in optical wavelength
51% or more, it is seen that light transmission rate is greater than 84%, 38 degree of hot phase transition temperature.
V2 powder is added in the EVA powder in EVA raw materials for production according to 2/10000ths ratio, is stirred with high speed powder
The EVA adiabatic gum with hot phase transition function that machine is obtained after being sufficiently mixed uniformly with small-scale test machine extrusion with a thickness of 0.38mm
Film measures visible light transmittance VLT with the optical testing instrument that wavelength is 950nm and is greater than 50% greater than 85%, IR rejection rate, phase
Temperature is 38 degree.
Embodiment 3
First taking diameter is the zirconia ball 350g of 0.1mm, is packed into ready 1L high-temperature high-pressure reaction kettle, then take respectively
1. vanadic sulfate (VOSO4·nH2O:60g；2. sodium phosphotungstate powder: 2g；3. the mixed solvent of methanol and deionized water 1:1
334g；4. dispersing agent: phosphoric acid 2g；5. reducing agent: mono- dimethylethanolamine 2g of N, N.
1. 2. 3. 4. 5. pouring into high-temperature high-pressure reaction kettle, lid, electrified regulation pressurization, high speed rotation reaction kettle are covered
Stirring rotator, temperature are set as 260 degree, and pressure is set as 15kg, and revolving speed is set as 6000 revs/min, and reaction jitter time is set
It is set to 24 hours.The VO that primary particle size is not more than 10nm is obtained after reaction in 24 hours, grinding, dispersion2(B phase) precursor is molten
Liquid.
Again the VO of above-mentioned acquisition2(B phase) solution obtains VO by freeze-drying2(B phase) nano-powder.
Again the VO obtained in above-mentioned steps2(B phase) nano-powder pours into aluminium crucible, refills the atmosphere protected into argon gas
In furnace, furnace temperature is set as 580 degree, and calcination time is set as 12 hours, and fire door is opened after furnace temperature Temperature fall to room temperature and is taken out
Powder obtains the VO that primary particle size is not more than 20nm2(R phase) nano-powder.Referred to as: V3 powder.
It is obtained in embodiment 3] after V3 powder takes 2% to mix reconstruction function master batch with 98% common PE slice, then
With small-scale test machine membrane sample, the thermal insulation film of 23um thickness, in optical wavelength in 950nm point after being mixed with common PE slice 1:1
Near infrared range 54% or more can achieve to IR rejection rate, it is seen that light transmission rate be greater than 83%, 40 degree of hot phase transition temperature.
V3 powder is added in fiber glass resin according to 2/10000ths ratio, it is thick that rear mold molding 1mm is mixed evenly
The heat-insulated glory watt with hot phase transition function, it is big to measure visible light transmittance VLT with the optical testing instrument that wavelength is 950nm
It is greater than 51% in 70%, IR barrier lv, phase transition temperature is 40 degree.
Embodiment 4
First taking diameter is the zirconia ball 380g of 0.1mm, is packed into ready 1L high-temperature high-pressure reaction kettle, then take respectively
1. sodium metavanadate (NaVO3): 42g；2. wolframic acid H2WO4Powder: 1.2g；3. the mixed solvent 160g of methanol and deionized water 1:1；
4. dispersing agent: phosphatase 11 .3g；5. reducing agent: mono- dimethylethanolamine 1.3g of N, N.
1. 2. 3. 4. 5. pouring into high-temperature high-pressure reaction kettle, lid, electrified regulation pressurization, high speed rotation reaction kettle are covered
Stirring rotator, temperature are set as 260 degree, and pressure is set as 15kg, and revolving speed is set as 6000 revs/min, and reaction jitter time is set
It is set to 24 hours.The VO that primary particle size is not more than 10nm is obtained after reaction in 24 hours, grinding, dispersion2(B phase) precursor is molten
Liquid.
Again the VO of above-mentioned acquisition2(B phase) solution obtains VO by freeze-drying2(B phase) nano-powder.
Again the VO obtained in above-mentioned steps2(B phase) nano-powder pours into aluminium crucible, refills the atmosphere protected into argon gas
In furnace, furnace temperature is set as 580 degree, and calcination time is set as 12 hours, and fire door is opened after furnace temperature Temperature fall to room temperature and is taken out
Powder obtains the VO that primary particle size is not more than 20nm2(R phase) nano-powder.Referred to as: V4 powder.
It is obtained in example 4] V4 powder takes 1% weight percent to mix reconstruction with common PP polypropylene powder
Small-scale test machine membrane sample, the phase-change thin film of 36um thickness, in light are used after functional agglomerate, then after mixing with common PP slice 1:1
Wavelength can achieve 52% or more to IR rejection rate in the near infrared range of 950nm point, it is seen that light transmission rate is greater than 83%, heat
52 degree of phase transition temperature.
Claims (8)
1. a kind of preparation method of the hot phase-change material of high transparency, which is characterized in that following weight percent is contained vanadium
It closes object, Tungstenic compound, alcohol water mixed solvent, dispersing agent and reducing agent to be put into the hydrothermal reaction kettle containing mill ball, high speed
The stirring rotator of hydrothermal reaction kettle is rotated, rotor speed is 1000-8000 revs/min, and the temperature in hydrothermal reaction kettle is 160-
300 DEG C, pressure 1-20kg, reaction jitter time is 16-100 hours, obtains primary grain after grinding, reaction and dispersion
Diameter is not more than the VO of 10nm2Precursor solution；
1. vanadium-containing compound: 5%-20%；
2. Tungstenic compound: 0.1%-1%；
3. dispersing agent: 0.1-1%；
4. alcohol water mixed solvent: 80%-94.7%；
5. reducing agent: 0.1%-1%；
Vanadium-containing compound is vanadium pentoxide V2O5, sodium metavanadate NaVO3, vanadic sulfate VOSO4·nH2O, vanadyl oxalate VOC2O4·
nH2O or vanadium oxytrichloride VOCl3；The Tungstenic compound is phosphotungstic acid, sodium phosphotungstate and WO3At least one of；
Aforementioned VO2Precursor solution pours into crucible after freezing and drying, under the atmosphere of inert gas shielding, in 460-
It is calcined 3-48 hours at 680 DEG C, after cooling, obtains the VO that primary particle size is not more than 20nm2Nano-powder, as high transparency heat
Phase-change material.
2. the preparation method of the hot phase-change material of high transparency according to claim 1, which is characterized in that by following weight hundred
The VO for dividing the primary particle size of content to be not more than 20nm2Nano-powder, organic solvent or deionized water, phosphoric acid and diameter 0.1mm
Zirconia ball is respectively charged into the dispersion tank in planet high speed rotation dispersion machine, and revolving speed is 12000 revs/min, is dispersed 3 hours
Afterwards, the VO that there is the primary particle size of hot phase transition function to be not more than 20 nanometers is obtained2Waterborne nano slurry,
1. primary particle size is not more than the VO of 20nm2Nano-powder 9.5%-30%；
2. organic solvent or deionized water 69%-90%；
3. phosphoric acid 0.5%-1%；
The dosage for the zirconia ball that diameter is 0.1mm is the VO that primary particle size is not more than 20nm24-8 times of nano-powder dosage.
3. the preparation method of the hot phase-change material of high transparency according to claim 1 or 2, which is characterized in that mill ball is
Diameter is one of the glass marble of 0.05mm-3mm, metal ball, zirconia ball, cerium oxide ball, alumina balls or a variety of；Grinding
The volume ratio of ball and reactant is (1-3): (1-30).
4. the preparation method of the hot phase-change material of high transparency according to claim 1 or 2, which is characterized in that reducing agent is
Ethylenediamine, triethanolamine and N, at least one of N- dimethylethanolamine.
5. the preparation method of the hot phase-change material of high transparency according to claim 1 or 2, which is characterized in that dispersing agent is
At least one of phosphoric acid, nitric acid, hydrochloric acid and oxalic acid.
6. the preparation method of the hot phase-change material of high transparency according to claim 1 or 2, which is characterized in that the mixing of alcohol water
Solvent is the mixed liquor of methanol and deionized water volume ratio 1:1.
7. the preparation method of the hot phase-change material of high transparency according to claim 1 or 2, which is characterized in that calcining crucible
For alumina crucible.
8. any one of claim 1-7 preparation method obtain the hot phase-change material of high transparency be added to PVB, EVA, PET,
In PC, PP, PE, PMMA or TPO, stirring squeezes out the functional plastic master batch and plate for obtaining and having the hot phase transition function of high transparency
Material or coiled material product.
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| CN106957456B (en) * | 2017-04-11 | 2019-08-30 | 武汉纺织大学 | A kind of temperature sensing material and its synthetic method of the vanadium dioxide synthesis using witch culture |
| CN107746472B (en) * | 2017-10-27 | 2020-04-21 | 四川大学 | Film and preparation method thereof |
| CN107936617A (en) * | 2017-11-22 | 2018-04-20 | 上海沪正实业有限公司 | A kind of weather-proof low-transmittance inorganic thermal insulation pigment of superelevation and preparation method thereof |
| CN109836780B (en) * | 2017-11-28 | 2021-08-27 | 上海沪正实业有限公司 | Ultrahigh weather-proof low-light-transmittance high-heat-insulation inorganic functional master batch |
| CN108285174B (en) * | 2018-04-04 | 2020-04-03 | 东莞市石鼓污水处理有限公司 | WO (WO)3-ZrO2Preparation method of photocatalytic sewage treatment membrane |
| CN110921678A (en) * | 2019-11-29 | 2020-03-27 | 正大能源材料(大连)有限公司 | Synthesis method of SAPO-34 molecular sieve with controllable small particle size |
| CN112662140B (en) * | 2020-12-11 | 2022-05-24 | 浙江强盟实业股份有限公司 | Infrared barrier master batch, infrared barrier polyester film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481142A (en) * | 2009-02-18 | 2009-07-15 | 大连理工大学 | Method for preparing hypovanadic oxide doped powder material |
| CN101792182A (en) * | 2010-03-11 | 2010-08-04 | 西安理工大学 | Tungsten-doped vanadium dioxide powder material and preparation method thereof |
| CN102502824A (en) * | 2011-11-15 | 2012-06-20 | 武汉大学 | Preparation method for vanadium dioxide and doped powder thereof |
| CN103435100A (en) * | 2013-07-13 | 2013-12-11 | 宿州学院 | Method for reducing phase transition temperature of vanadium dioxide through W<6+> doping |
-
2015
- 2015-04-24 CN CN201510203516.0A patent/CN106147719B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481142A (en) * | 2009-02-18 | 2009-07-15 | 大连理工大学 | Method for preparing hypovanadic oxide doped powder material |
| CN101792182A (en) * | 2010-03-11 | 2010-08-04 | 西安理工大学 | Tungsten-doped vanadium dioxide powder material and preparation method thereof |
| CN102502824A (en) * | 2011-11-15 | 2012-06-20 | 武汉大学 | Preparation method for vanadium dioxide and doped powder thereof |
| CN103435100A (en) * | 2013-07-13 | 2013-12-11 | 宿州学院 | Method for reducing phase transition temperature of vanadium dioxide through W<6+> doping |
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