CN1624029A - Vanadium dioxide sun heat reflection intelligent temp controll high polymer film - Google Patents

Vanadium dioxide sun heat reflection intelligent temp controll high polymer film Download PDF

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Publication number
CN1624029A
CN1624029A CN 200410051966 CN200410051966A CN1624029A CN 1624029 A CN1624029 A CN 1624029A CN 200410051966 CN200410051966 CN 200410051966 CN 200410051966 A CN200410051966 A CN 200410051966A CN 1624029 A CN1624029 A CN 1624029A
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Prior art keywords
powder
polymer film
vanadium dioxide
solar heat
temperature control
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Application number
CN 200410051966
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Chinese (zh)
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CN1273521C (en
Inventor
郑臣谋
雷德铭
储向峰
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Sun Yat Sen University
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Sun Yat Sen University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00Integration of renewable energy sources in buildings
    • Y02B10/20Solar thermal
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/40Solar thermal energy, e.g. solar towers

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  • Compositions Of Macromolecular Compounds (AREA)
  • Greenhouses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

A high polymer film with intelligent temp control function by reflecting solar heat or not is prepared from the phase-change material (VO2 and its doped powder), high polymer, antioxidizing agent or thermal O2 stabilizer, composite pigment, anti-UV stabilizer, plasticizer and nucleator. It features that full-band infrared light can be reflected when the temp is higher than its phase-change temp or not when the temp is lower than its phase-change temp. It can be used for building, green house, car, ship, etc.

Description

Specification sheets vanadium dioxide solar heat intelligent temperature control polymer film
Technical field
The present invention relates to a kind of solar heat reflection and transmission intelligent temperature control polymer film automatically, particularly relate to a kind of VO 2And mix the powder-modified solar heat of Mo or W hotchpotch reflection and transmission intelligent temperature control polymer film automatically.It belongs to the polymer modification technical field.
Background technology
The wave band of sunlight is divided into UV-light (0.2-0.4 μ m), visible light (0.4-0.8 μ m) and near infrared light (0.8-2.6 μ m), and its energy distribution is approximately UV-light 5%, visible light 45% and near infrared light 50%.Solar light irradiation is when body surface, and object mainly absorbs the energy of near infrared light and its surface temperature is raise.In summer, solar radiation is when metal sheet or building surface, and surface temperature can reach 70-80 ℃, needs this moment reflects infrared light that the body surface temperature is reduced; And in the winter time,, need to see through the infrared light insulation because temperature is low.Existing solar heat reflecting and heat insulating polymer film only has the effect of reflects infrared light, sees through the function of infrared light, therefore attemperation automatically.The present invention invented a kind of price quite, high temperature can reflects infrared light, low temperature sees through the infrared light and the film of visible light transmissive simultaneously, can realize intelligent temperature control.This film is more far better than the film performance of existing reflection solar heat, can accomplish that the cool summer in winter is warm, plays using no or little air-conditioning, the effect of save energy and protection environment.
VO 2Be converted to high temperature four directions metallographic phase mutually by low temperature monocline semi-conductor in the time of about 68 ℃, its transformation temperature Tc can regulate by mixing, and as whenever mixing 1% Mo or W atom, Tc reduces 11 or 26 ℃ respectively, makes that this material is suitable for using under the room temperature.VO 2Be accompanied by the sudden change of infrared light (λ=0.7-20 μ m) transmissivity and reflectivity during the series phase transformation.All wave band reflects infrared light when temperature is higher than Tc, all wave band sees through infrared light when temperature is lower than Tc, and this variation is reversible, thereby realizes intelligent temperature control.The present invention proposes for the first time with VO 2Series powder and superpolymer are compound, give good solar insulation of superpolymer and intelligent temperature control usefulness.If at construction industry (roof, door and window); transport trade (car, ship door and window); this film of one deck is sticked on the surface of Industrial Metal container, makes insulation film at agricultural greenhouse, will effectively reduce surface and the internal temperature that is exposed to the equipment under the sun heat radiation in summer; improve its surface and internal temperature in the winter time; play cool in summer and warm in winterly, the effect of sun-shielding antifreeze can be saved and even do not used air-conditioning; not only save energy but also protect environment improved production security simultaneously.
The patent No. is that the patent of invention of ZL00117321.9 has been invented a kind of VO 2The preparation method of nano-powder and hotchpotch nano-powder thereof.This method is with V 2O 5, hydrochloric acid, oxalic acid and NH 4HCO 3Be starting raw material, synthetic presoma vanadyl (IV) basic carbonate ammonium and Mo or W doping presoma, this chemical doping method makes Mo or W ion evenly enter the precursor lattice, then precursor thermolysis in containing the oxygen inert atmosphere is got (V 1-xM x) O 2Powder.The Mo of this powder and W ion evenly enter VO 2Lattice demonstrates (V 1-xM x) O 2Intrinsic crystal property and with the performance of infrared light effect.Particularly importantly, this chemical doping method greatly reduces existing VO 2Powder, mix the VO of Mo or W 2Powder is by the preparation cost of the traditional method of solid-solid reaction preparation; Simultaneously, the granularity of powder can be controlled from the nano level to the micron order by the pyrolytic process of precursor.This has guaranteed VO 2And hotchpotch powder price is lower, and material infrared light excellent performance is for realizing that the present invention prepares solar heat intelligent temperature control polymer film and provides material base.
Summary of the invention
The object of the present invention is to provide a kind of vanadium dioxide intelligent temperature control film, this film is solar heat reflection rate height when high temperature, and when low temperature the transmissive solar heat, simultaneously can see through visible light.
Thin film composition of the present invention comprises superpolymer, oxidation inhibitor or thermal oxidation stabilizer, uvioresistant stablizer, softening agent and nucleator, and the shared parts by weight of each component are as follows:
Superpolymer 10-35;
Oxidation inhibitor or thermal oxidation stabilizer 0.05-0.2;
Composite pigment 3-12;
Uvioresistant stablizer 0.01-0.03;
Nucleator 0.01-0.05;
Wherein superpolymer is polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene dichloride, terylene or dacron terylene etc.; Oxidation inhibitor is 1010, and thermal oxidation stabilizer is organotin or 2,6,4; Composite pigment is by (V 1-xM x) O 2Powder or (V 1-xM x) O 2One or more compositions in powder and Rutile type Titanium Dioxide or the zinc oxide, wherein M=Mo, W, 0≤x<0.045; The uvioresistant stablizer is UV-531; Nucleator is DBS.In addition, this film composition also comprises phthalic ester plasticizer.
The present invention relates to VO 2And the hotchpotch nano level, submicron order and micron-sized powder and preparation thereof, its preparation method is similar to Chinese patent ZL 00117321.9.With V 2O 5, oxalic acid and hydrochloric acid are raw material, preparation VOCl 2Solution is then with VOCl 2Solution and NH 4HCO 3Reaction obtains vanadyl (IV) basic carbonate ammonium presoma; If at VOCl 2Add MoCl in the solution 2Or the reduzate of ammonium molybdate or WOCl 2, again with NH 4HCO 3Reaction can be mixed molybdenum, be mixed vanadyl (IV) the basic carbonate ammonium presoma of tungsten; With VOCl 2Solution and ammonium tungstate and NH 4HCO 3Mixture reaction also can obtain to mix tungsten vanadyl (IV) basic carbonate ammonium presoma.Presoma is broken or not broken, containing under the oxygen protection of inert gas, can obtain (the V of different-grain diameter then 500 ℃ of-900 ℃ of thermolysiss 1-xM x) O 2Powder.Wherein powder granularity can be by the degree of crushing of presoma, thermolysis heat-up rate and temperature of reaction control.
Polymer film preparation technology of the present invention is as follows: with the even back hot melt granulation of each mixing of materials, make film, the about 10-50 μ of film thickness m with blown film method or casting method or membrane method by prescription then.The mensuration of the infrared reflectivity of gained film, the detection method of defined in the employing MIL STD.
The vanadium dioxide polymer film that adopts technique scheme to make has following advantage:
1, in superpolymer, introduces (V with phase transition function 1-xM x) O 2Powder, can be when temperature be higher than Tc all wave band (O.7-20 μ m) reflects infrared light, infrared light reflection efficient height, good cooling effect; All wave band sees through infrared light when temperature is lower than Tc, and infrared light sees through the efficient height, high insulating effect, thus realize intelligent temperature control.Simultaneously can see through visible light, indoor have brightness preferably.
2, control temperature is by (V 1-xM x) O 2Transformation temperature Tc decision, can adjust as required.
3, every mechanical property of vanadium dioxide solar heat intelligent temperature control polymer film can keep the index of original macromolecular material, and the intensity that has is also strengthened to some extent.Especially use (V 1-xM x) O 2Nano-powder can improve the packing ratio of stopping composition, improves the rheological of material in the course of processing, improves material shielding effect to corrosive medium in application process.
The present invention has a extensive future, and at the door and window of buildings, train and boats and ships, the facilities such as metallic surface of agricultural film and industrial plants are used, and both save energy was protected environment, improved production security again.
Embodiment
Embodiment 1-8
Vanadium dioxide intelligent temperature control film is made up of superpolymer, oxidation inhibitor or thermal oxidation stabilizer, composite pigment, uvioresistant stablizer, softening agent and nucleator, and the shared weight of each component is as shown in table 1.
(V 1-xM x) O 2The synthetic method of powder:
Use V 2O 5, oxalic acid and hydrochloric acid reaction prepare VOCl 2Solution, this solution and bicarbonate of ammonia or volatile salt are at CO then 2Stirring reaction under the air-flow protection, synthetic vanadyl (IV) basic carbonate ammonium presoma.If the molybdenum presoma is mixed in preparation, can be at VOCl 2Add MoCl in the solution 2Or the ammonium molybdate reduzate, the same building-up reactions of carrying out.If the tungsten presoma is mixed in preparation, can be at VOCl 2Add WOCl in the solution 2, the same reaction; Or in bicarbonate of ammonia or volatile salt, add ammonium tungstate solution, the same reaction.Mo/V or W/V ratio in doping vanadyl (IV) the basic carbonate ammonium are determined by Mo/V in the reaction system or W/V ratio.Presoma is crushed to different grain size, then at oxygen containing N 2Or the pyrolysis that in Reaktionsofen, heats up under the Ar gas shiled, controlling different heat-up rates and different pyrolysis temperatures, insulation 0.5h promptly gets (V 1-xM x) O 2Powder, it the results are shown in table 2.
The preparation method of vanadium dioxide solar heat intelligent temperature control polymer film:
By prescription with each mixing of materials evenly after, hot melt granulation is made polymer film with blown film method or casting method or membrane method then.Measure its infrared reflectivity, it the results are shown in table 1.
Table 1:VO 2Solar heat intelligent temperature control polymer film composition weight
Raw material (gram) Embodiment
??1 ??2 ??3 ??4 ??5 ??6 ?7 ?8
Polymkeric substance (consumption) Polyethylene 35 Polyethylene 35 Polypropylene 10 Polyvinyl chloride 16 Polyvinylidene dichloride 25 Polystyrene 28 Terylene 20 Dacron terylene 30
Oxidation inhibitor or thermal oxidation stabilizer (consumption) ??1010 ??0.2 ??1010 ??0.2 ??1010 ??0.05 Organotin 0.1 Organotin 0.13 ??2,6,4 ??0.15
??(V 1-xM x)O 2Pigment (consumption) Nanometer VO 2??11 Nanometer VO 2??11 Submicron V 0.983W 0.017O 2??3 Nanometer V 0.983W 0.014O 2????7 Submicron V 0.986W 0.014O 2??12 Micron V 0.983W 0.017O 2????7 Nanometer V 0.970Mo 0.030O 2?6 Nanometer V 0.981Mo 0.019O 2?10
Other pigment (consumption) Titanium dioxide 0.5 Titanium dioxide 0.2 Zinc oxide 0.5
Ultraviolet light stablizer (consumption) ??UV-531 ??0.03 ??UV-531 ??0.03 ??UV-531 ??0.01 ??UV-531 ??0.02 ??UV-531 ??0.03 ??UV-531 ??0.03
Softening agent (consumption) Phthalic ester Phthalic ester 12 Phthalic ester 5
Nucleator (consumption) ??DBS ??0.05 ??DBS ??0.05 ??DBS ??0.01
??Tc(℃) ??~68 ??~68 ??~33 ??~37 ??~37 ??~33 ?~39 ?~51
The solar heat reflection rate, % ??90 ??90 ??83 ??85 ??81 ??55 ?75 ?80
The table 2: (V under the different thermolysis conditions 1-xM x) O 2Powder
Precursor particle size (μ m) Heat-up rate Thermostat temperature (℃) Powder granularity Granular
????≤2 Fast ????550 ??<30nm Spherical
????≤2 Fast ????700 ??<100nm Spherical
????≤10 Middling speed ????800 ??<500nm Torispherical
About 20 At a slow speed ????900 ??>1μm Torispherical

Claims (4)

1, a kind of vanadium dioxide solar heat intelligent temperature control polymer film, it is characterized in that this thin film composition comprises that superpolymer, oxidation inhibitor or thermal oxidation stabilizer, composite pigment, uvioresistant stablizer, softening agent and nucleator form, the shared parts by weight of each composition are as follows:
Superpolymer 10~35;
Oxidation inhibitor or thermal oxidation stabilizer 0.05~0.2;
Composite pigment 3~12;
Uvioresistant stablizer 0.01~0.03;
Nucleator 0.01~0.05;
Wherein superpolymer is polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene dichloride, terylene or dacron terylene etc.; Oxidation inhibitor or thermal oxidation stabilizer are 1010, organotin or 2,6,4; Composite pigment is by (V 1-xM x) O 2Powder or (V 1-xM x) O 2One or more compositions in powder and Rutile type Titanium Dioxide or the zinc oxide, wherein M=Mo, W, 0≤x<0.045; The uvioresistant stablizer is UV-531; Nucleator is DBS.
2, vanadium dioxide solar heat intelligent temperature control polymer film as claimed in claim 1 is characterized in that this film composition also comprises phthalic ester plasticizer.
3, vanadium dioxide solar heat intelligent temperature control polymer film as claimed in claim 1 is characterized in that described (V 1-xM x) O 2Powder can be micron order, submicron order powder or nanometer grade powder.
4, vanadium dioxide solar heat intelligent temperature control polymer film as claimed in claim 1 or 2 is characterized in that described (V 1-xM x) O 2Powder by vanadyl (IV) basic carbonate ammonium and mix molybdenum or the tungsten presoma in oxygen containing inert atmosphere at the powder of 500 ℃~900 ℃ of thermolysis gained.
CN 200410051966 2004-10-28 2004-10-28 Vanadium dioxide sun heat reflection intelligent temp controll high polymer film Expired - Fee Related CN1273521C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100486421C (en) * 2005-07-04 2009-05-13 北京瑞雪环球科技有限公司 Removable protective membrane technique for green house
CN103709689A (en) * 2013-12-30 2014-04-09 上海紫东薄膜材料股份有限公司 Preparation method of PET (polyester) film with uniformly dispersed vanadium dioxide
CN103756271A (en) * 2013-12-30 2014-04-30 上海紫东薄膜材料股份有限公司 Preparation method of modified PET (polyether) film with uniformly dispersed vanadium dioxide
CN102333998B (en) * 2008-12-30 2015-08-05 3M创新有限公司 Broadband reflector, light collecting type solar power system and use their method
CN104895462A (en) * 2015-06-18 2015-09-09 南京二十六度建筑节能工程有限公司 Intelligent hollow vanadium dioxide sunshade glass
CN105254185A (en) * 2015-09-15 2016-01-20 中国建材国际工程集团有限公司 Method for preparing porous-structure VO2 film with polystyrene bead as soft template
CN111077603A (en) * 2019-12-30 2020-04-28 哈尔滨工业大学 Flexible film with adjustable infrared emissivity and preparation method thereof
CN111378189A (en) * 2020-01-19 2020-07-07 天津大学 Intelligent temperature adjusting material based on radiation cooling and preparation method thereof
CN111499957A (en) * 2020-06-12 2020-08-07 济南大学 Composite film with heat insulation effect and preparation method
CN111607151A (en) * 2020-06-12 2020-09-01 山东莘纳智能新材料有限公司 Heat-insulation light-conversion agricultural film and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100486421C (en) * 2005-07-04 2009-05-13 北京瑞雪环球科技有限公司 Removable protective membrane technique for green house
CN102333998B (en) * 2008-12-30 2015-08-05 3M创新有限公司 Broadband reflector, light collecting type solar power system and use their method
US9523516B2 (en) 2008-12-30 2016-12-20 3M Innovative Properties Company Broadband reflectors, concentrated solar power systems, and methods of using the same
CN103709689B (en) * 2013-12-30 2015-11-11 上海紫东薄膜材料股份有限公司 The preparation method of the homodisperse PET film of a kind of vanadium dioxide
CN103756271B (en) * 2013-12-30 2015-11-04 上海紫东薄膜材料股份有限公司 The preparation method of the homodisperse modified PET film of a kind of vanadium dioxide
CN103756271A (en) * 2013-12-30 2014-04-30 上海紫东薄膜材料股份有限公司 Preparation method of modified PET (polyether) film with uniformly dispersed vanadium dioxide
CN103709689A (en) * 2013-12-30 2014-04-09 上海紫东薄膜材料股份有限公司 Preparation method of PET (polyester) film with uniformly dispersed vanadium dioxide
CN104895462A (en) * 2015-06-18 2015-09-09 南京二十六度建筑节能工程有限公司 Intelligent hollow vanadium dioxide sunshade glass
CN105254185A (en) * 2015-09-15 2016-01-20 中国建材国际工程集团有限公司 Method for preparing porous-structure VO2 film with polystyrene bead as soft template
CN105254185B (en) * 2015-09-15 2020-04-28 中国建材国际工程集团有限公司 Preparation of porous structure VO by using polystyrene pellets as soft template2Method for making thin film
CN111077603A (en) * 2019-12-30 2020-04-28 哈尔滨工业大学 Flexible film with adjustable infrared emissivity and preparation method thereof
CN111378189A (en) * 2020-01-19 2020-07-07 天津大学 Intelligent temperature adjusting material based on radiation cooling and preparation method thereof
CN111499957A (en) * 2020-06-12 2020-08-07 济南大学 Composite film with heat insulation effect and preparation method
CN111607151A (en) * 2020-06-12 2020-09-01 山东莘纳智能新材料有限公司 Heat-insulation light-conversion agricultural film and preparation method thereof

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