CN103951850B - Photothermal response system, resin material and photothermal response intelligent glass - Google Patents
Photothermal response system, resin material and photothermal response intelligent glass Download PDFInfo
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- CN103951850B CN103951850B CN201410187436.6A CN201410187436A CN103951850B CN 103951850 B CN103951850 B CN 103951850B CN 201410187436 A CN201410187436 A CN 201410187436A CN 103951850 B CN103951850 B CN 103951850B
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- NTKVWOTYTNWGRK-UHFFFAOYSA-N P.Br.Br.Br Chemical compound P.Br.Br.Br NTKVWOTYTNWGRK-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 description 1
- NOFYXNPOENFGLQ-UHFFFAOYSA-M [P].[Br-].C(CCC)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Br-].C(CCC)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 NOFYXNPOENFGLQ-UHFFFAOYSA-M 0.000 description 1
- SHMJMQCAYFBDJE-UHFFFAOYSA-N [P].[I-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[I-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1 SHMJMQCAYFBDJE-UHFFFAOYSA-N 0.000 description 1
- IWSFTSIYMJBHGY-UHFFFAOYSA-M [P].[I-].C[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[I-].C[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 IWSFTSIYMJBHGY-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VXIXUWQIVKSKSA-UHFFFAOYSA-N benzotetronic acid Natural products C1=CC=CC2=C1OC(=O)C=C2O VXIXUWQIVKSKSA-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- PBLQDVYGPUHNBA-UHFFFAOYSA-N bromo-(2-methylpropyl)-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Br)(C=1C=CC=CC=1)(CC(C)C)C1=CC=CC=C1 PBLQDVYGPUHNBA-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- RISLXYINQFKFRL-UHFFFAOYSA-N dibutyl nonanedioate Chemical compound CCCCOC(=O)CCCCCCCC(=O)OCCCC RISLXYINQFKFRL-UHFFFAOYSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- GELSOTNVVKOYAW-UHFFFAOYSA-N ethyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 GELSOTNVVKOYAW-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 125000002577 pseudohalo group Chemical group 0.000 description 1
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- 239000012429 reaction media Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Joining Of Glass To Other Materials (AREA)
Abstract
The invention discloses a photothermal response system, a photothermal response resin material prepared by using the photothermal response system as a polymer processing aid, and photothermal response intelligent glass. The system is obtained by mixing transition metal ions, a polyol ligand compound, a photosensitive halide and an organic nitrogen compound and/or a phosphorus compound and then performing conformational transition of an organic transition metal complex. The invention can respond to light and heat, and can automatically change the color depth and the light transmittance according to the change of the environment temperature and the light intensity. The photothermal response resin material has wide application prospect in the fields of glass curtain walls, building door and window glass, automobile glass, agricultural greenhouse films and the like. The photo-thermal response intelligent glass has higher shading coefficient in seasons with lower temperature, can automatically reduce the shading coefficient in summer with intense hot high-temperature sunlight, and has the advantages of complete ultraviolet shielding, low heat conduction efficiency and automatic change of the sunlight shading coefficient.
Description
Technical field
The invention belongs to SMART OPTICS field, relate to a kind of photothermal response system of organotransition metal complex conformation transition, using the resin material that this photothermal response system is prepared as processing aid, and the photothermal response type intelligent power saving glass prepared by this resin material.
Background technology
Intelligent material refers to imitation Living system, energy perception environmental change, and can adjust in time according to the environmental parameter of institute's perception or change the performance perameter of material self, make desired and can with change after the matrix material of change that adapts to of environmental facies or the compound of material.Imitative vital sensibilities and self-control are the key characters of intelligent material.
Along with the development in epoch, material of construction intelligent construction is further deep, and the content of intelligent building and connotation constantly extend along with the development of science and technology, its function also in continuous expansion, to meet the growing various needs of people.Phone predicts shows, in the middle of this century, construction industry will step into high-tech building materials periods, and the building material being representative with intelligent building material will become main flow.
In numerous material of construction, glass plays an increasingly important role.Glass has irreplaceability as architectural lighting material, glass and finely processed product thereof expand year by year as the application of decorating and renovating material, and the multifunctional material of the optical characteristics manufacture utilizing glass material unique will be played an important role in Energy Conservation Green Construction.Except traditional energy-saving glass manufacture craft, beyond double glazing, antisolar glass and heat-reflecting glass, a lot of new technologies, product innovation are there is in recent years, as photochromic glass, thermo-color glass, liquid-crystalline glasses, electrochomeric glass and electrophoresis glass etc.
At traditional intelligent material mainly light activated photochromic material and thermochromic material.Typical photochromic material is silver halide compound, is also the material that tradition prepares photochromic glass.Under certain light wave radiation parameter, silver halide particle can absorb energy and decompose, production silver particles and elemental halogen.Nano silver particles and halogen can shut out the light and pass through, from but glass is dimmed.When removing radiation, elemental silver and the colourless silver halide compound of halogen laminating production, such glass can become more transparent.
Expensive with intelligent glass prepared by traditional silver halide, quality weight, strength of glass is poor.During in particular as building glass, in the winter of cold low temperature, people need high sunlight transmitance to reduce energy consumption to meet heating of house, and silver halide intelligent glass can not meet the demand of people as intelligent sunshade glass thus.
Responsive to temperature type intelligent glass can present by transparent to opaque phase co-conversion with envrionment temperature.When temperature is lower than the temperature set, responsive to temperature type intelligent glass has good light permeable rate, and when temperature is higher than the temperature set, this material will decline to a great extent to visible ray or sightless transmitance, and intelligent glass will become opaque.Responsive to temperature type intelligent glass can be used as Intelligent temp controlled energy-saving material and is widely used in intelligent building.In the season that temperature is low, responsive to temperature type intelligent glass can allow sunlight enter interior of building through intelligent glass to greatest extent.When the temperature that room temp feels comfortably cool higher than people, during as 24-25 DEG C, intelligent glass changes the vitreous state by high permeability into low transmission or opaque, and at this moment sunlight will farthest be reflected.So just can realize the intelligent control to interior of building temperature, reduce the use of air-conditioning.Artificially to intelligent glass heating, intelligent glass can also be facilitated by transparent to opaque transformation, thus interior of building light regulated.
Typical Reversible Thermochromic Materials has at present, the inorganic reversible color material of crystal formation conversion, organic lcd reversible color material.The compound that the iodide of typical silver, copper, mercury and cobalt salt, nickel salt and hexamethylenetetramine are formed.As, when red mercury iodide temperature is lower than 137 degree, be redness, when temperature becomes blueness higher than when 137 degree.This kind of thermochromic material aberration is large, and fatigue resistance is good, and variable color is sensitiveer.But this kind of material discoloring temperature is high, particularly has color before and after variable color.The intelligent glass of this and energy saving temperature controlling requires water white transparency under cryogenic, and high temperature colour developing low light is larger through gap.The typical organic reversible color material of another kind of photochromic material.Typical Reversible Thermochromic Materials comprises chromogenic reagent, developer and solvent and forms.Chromogenic reagent is with fluorane, schiff bases for typical thing, and developer is with dihydroxyphenyl propane, and 4 hydroxy coumarin etc. provide Louis protonic acid, solvent with alcohols such as n-dodecanols for representative.This kind of thermochromic material discoloring temperature is low, and the life-span is long and highly sensitive.But it is coloured to the colourless transformation of high temperature that the variable color of this kind of material can only appear at low temperature, or by a certain color of low temperature to another kind of color transition.Particularly, under cryogenic, be difficult to the existence of water white transparency state, therefore this kind of material is difficult to apply in intelligent sunshade glass.
A metal-organic complex particularly Organotransitionmetal complex can manifest shades of colour.Some a metal-organic complex has characteristic [H.A.Good.Coord, Chem.Rev.1976,18,293 of the spin crossover of thermal response, M.A.Halcrow, Chem.Soc.Rev.2011, 40, 4119], simultaneously with the change [O.Kahn occurring magnetic moment and color, C.J.Martinez, Science1998, 279, 44], this reversible organo-metallic spin crossover presents reversible equilibrium state under condition of different temperatures, therefore a kind of organometallic complex presents the transparency states of colourless height at ambient temperature, the heterogeneous states of spin crossover is produced at higher state of temperature, present coloured stronger photoabsorption simultaneously, for the heat sensitive intelligent color-changing glass of preparation, there is important using value.
Have the characteristic of the spin crossover of metal complexes thermal initiation, molecular structure is said be exactly the plane configuration of four-coordination, the octoploids structure changing hexa-coordinate into changes.As shown in Figure 1:
Above-mentioned Me representation metal ion, L
aand L
brepresent the organic ligand of metallic compound.Some polyvalent alcohols can as La part, and halogen atom can as typical L
bpart.Thermochromic systems has been reported at MarkovaT.S.andYanushO.V.PhysichemicalstdudiesandProcesse s (2008,18 (5) 744-750).The research of current majority is all also under solution condition.Prepare solid-state thermochromism resin, for expansion thermochromic material in intelligent glass field, particularly the use of intelligent sun shading and energy-saving glass is significant.
Responsive to temperature type intelligent glass has boundless market outlook, except as intelligent building material, as in construction industry for outside the window of mansion, senior house, airport and harbour etc. and glass curtain wall, the little sun glasses worn to people, the large porthole to vehicles such as automobile, train, steamer and aircrafts and protective film, be all widely used field.At present, the conceptual product of existing intelligent glass occurs both at home and abroad.Representational is abroad the Pro-display company of Britain, and the product of the said firm is called can change intelligent glass (switchableintelligentglass), and in USA New York, new World Trade Organization mansion is applied.The representative firm of China's intelligent glass is Nanjing Zhixian Science and Technology Co., Ltd. and Beijing Wei Hao intelligent glass company limited in Nanjing.At present, the said products is all prepared by sensitive material technically with liquid crystal.As everyone knows, liquid crystal is the material preparing flat panel Liquid Crystal TV.And existing intelligent glass is owing to have employed the technology preparing flat panel Liquid Crystal TV display material, therefore price is very expensive.It is reported, external product price be roughly equal to 15000 Renminbi/square metre, the price of home products is minimum at 4000 yuan-6000 yuan/square metres.
Chinese patent 201110311787.X, 201110397060.8 and 201310007523.4 provides a kind of intelligent glass of the temperature control prepared based on nanophase isolation technique.This glass can have comparatively significant condition ability at 300-2000 nano waveband.Sheltering coefficient reaches 0.8 at ambient temperature, temperature higher than design temperature as 30 degree time, sheltering coefficient is reduced to 0.3.The maximum shortcoming of this glass is that perviousness is poor, affects sight line when the phase transformation of temperature height.
Summary of the invention
Technical problem: the photothermal response system that the invention provides a kind of organotransition metal complex conformation transition, using the resin material that this photothermal response system is prepared as processing aid, and the photothermal response type intelligent power saving glass prepared by this resin material.
Technical scheme: photothermal response system of the present invention, by transition metal ion, polyalcohols ligand compound, photosensitivity halogenide, and organic nitrogen compound and/or phosphorus compound mixing after, obtained by organotransition metal complex conformation transition, wherein photosensitivity halogenide is one or more the mixing in silver chloride, Silver monobromide, Silver iodide, calcium iodide.
In a kind of preferred version of photothermal response system of the present invention, transition metal ion accounts for 0.1-2 mass parts, and polyalcohols ligand compound is 0.2-20 mass parts, and photosensitivity halogenide is 0.2-5 mass parts, and organic nitrogen compound and/or phosphorus compound are 0.4-20 part.
In a kind of preferred version of photothermal response system of the present invention, also comprise the solubilizing agent of 40-60 mass parts.
In a kind of preferred version of photothermal response system of the present invention, transition metal ion is one or more the mixing in Fe (II), Co (II), Cu (II), Ni (II), Mn (II), Cr (II).
In a kind of preferred version of photothermal response system of the present invention, organic nitrogen compound and/or phosphorus compound are N (R)
3, P (R)
3, N
+(R)
3r
ix
-, P
+(R)
3r
ix
-, one or more mixing in glyoxaline compound and benzimidazoles compound, wherein, R is aromatic group or alkyl, R
1for alkyl, X is halogen atom.
Photothermal response resin material of the present invention, by above-mentioned photothermal response system, melt extrudes after mixing with fluoropolymer resin and polymer processing aids, or lysigenous mixture after mixing.
In a kind of preferred version of photothermal response resin material of the present invention, the mass percentage content of fluoropolymer resin is 40-80%, and the mass percentage content of polymer processing aids is 1-30%.
Photothermal response intelligent glass of the present invention, obtains by adhering to above-mentioned photothermal response resin material on the glass substrate.
Photothermal response system of the present invention, by transition metal ion, polyalcohols ligand compound, photosensitivity halogenide, and organic nitrogen compound and/or phosphorus compound mixing after, obtained by organotransition metal complex conformation transition, wherein photosensitivity halogenide is one or more the mixing in silver chloride, Silver monobromide, Silver iodide, calcium iodide.Transition metal ion is one or more the mixing in Fe (II), Co (II), Cu (II), Ni (II), Mn (II), Cr (II), concrete employing Fe (II), Co (II), Cu (II), Ni (II), the form such as nitrate, vitriol, villaumite, bromine salt, perchlorate, acetate of Mn (II), Cr (II).Preferred Fe (II), Co (II), nitrate, the haloid of Ni (II) and Mn (II).
In photothermal response system of the present invention, the polyalcohols ligand compound adopted is Virahol, ethylene glycol, propylene glycol, 1, one or more mixtures such as 4 butyleneglycols, 1,3 butylene glycol, neopentyl glycol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, tetramethylolmethane, Xylitol, sorbyl alcohol, polyvinyl alcohol, polyvinyl alcohol contracting suceinic aldehyde ester.Transition metal ion and alcohols part form organometallic complex, and this title complex should have good solvability, have colourless or more shallow color simultaneously.Preferred propylene glycol, Isosorbide-5-Nitrae butyleneglycol, 1,3 butylene glycol, neopentyl glycol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, tetramethylolmethane, Xylitol, sorbyl alcohol, polyvinyl alcohol, polyvinyl alcohol contracting suceinic aldehyde ester.
In photothermal response system of the present invention, the organonitrogen of employing, phosphorus compound and halide salts thereof are triethylamine, tributylamine, three hexyl amines, three octyl amine, triphenylamine, trimethylammonium phosphorus, triethyl phosphine, tributyl phosphorus, triphenyl phosphorus, three adjacent phenmethyl phosphorus, three n-octyl phosphorus, thricyclohexyl phosphorus, three (diphenylphosphine ethyl) phosphorus, Tetrabutyl amonium bromide, tetrabutylammonium iodide, four hexyl brometo de amonios, 4-hexyl iodide, four heptyl brometo de amonios, four heptyl brometo de amonios, tetramethyl-bromo-phosphonium, tetramethyl-iodate phosphorus, tetraethyl-bromo-phosphonium, tetraethyl-iodate phosphorus, tetrabutyl phosphonium bromide phosphorus, tetrabutyl iodate phosphorus, Tetraphenylphosphonium Bromide, tetraphenylphosphoniiodide iodide phosphorus, methyltriphenylphospbromide bromide phosphorus, methyltriphenylphosphonium iodide phosphorus, Ethyltriphenylphosphonium brimide, ethyltriphenylphosphiodide iodide phosphorus, butyltriphenylphosphonium bromide phosphorus, butyl base triphenyl phosphonium iodide phosphorus, isobutyl-tri-phenyl-phosphorus bromide, isobutyl-triphenyl phosphonium iodide phosphorus, povidon iodine, glyoxal ethyline, 2-ethyl 4-methylimidazole, 1-acetyl imidazole, benzoglyoxaline, 4,5-diphenyl-imidazole, 2-sulfenyl benzoglyoxaline, TSIM, 2,5,6 trimethylammonium benzoglyoxalines, 2-methylol benzoglyoxaline, 2-tolimidazole, 2-ethyl benzo imidazole, 2-propylbenzimidazole, 2-isobutyl-benzoglyoxaline, 2-amyl group benzoglyoxaline, 2-heptyl benzoglyoxaline, 5-methoxybenzimidazol, 2-phenylimidazole, one or more mixing of 1,1-dithio carbonylic imidazole.Preferred tributylamine, triphenylamine, tributyl phosphorus, triphenyl phosphorus and haloalkyl salt thereof and 2-alkyl benzimidazole.
In photothermal response system of the present invention, the photosensitivity halogenide of employing is one or more combination of calcium iodide, silver chloride, Silver monobromide, Silver iodide.Can there is redox reaction in photosensitivity halogenide, be decomposed into silver or the calcium of simple substance, produce iodine simultaneously under solar radiation condition.The elemental silver produced can develop the color when piling up cluster, and the elemental silver simultaneously produced has stronger infrared-reflecting power.The halogen of the simple substance produced by organic amine or phosphide compound, can become the part of transition metal complex, changes the balance of equation (1).The colour developing direction that the spin crossover of such organometallic complex balances to four-coordination tilts.Make system under sunlight intense conditions than light weaker condition under have stronger thermochromic temperature effect under the same condition of temperature.
In photothermal response system of the present invention, the solubilizing agent of employing is one or more the mixing of the compounds such as ethyl acetate, butyrolactone, methylbutyrolactone, caprolactone, tetrahydrofuran (THF), dioxane, dimethyl succinate, Methyl glutarate, dimethyl adipate, Polycizer W 260, diisobutyl adipate, dimethyl phthalate, triglycol two 2-ethylhexoate.In whole system, play the solvent action of the responsive system of photo-thermal, for photochromic reactions and thermochromism reaction provide reaction medium, whole variable color system is dissolved.Simultaneously as solubilizing agent, intelligent color-changing system is disperseed better at macromolecular material.Also play the part of plastification simultaneously, be beneficial to film forming processing.
The photothermal response system of transition organometallic complex conformation transition of the present invention is in mass fraction, and its composition comprises:
(a) transition metal ion 0.1-2 part
(b) polyvalent alcohol ligand compound; 0.2-20 part
(c) organonitrogen, phosphorus compound; 0.4-20 part
(d) photosensitivity halogenide; 0.2-5 part
(e) solubilizing agent 10-60 part
In the present invention, by (a) transition metal ion; (b) polyvalent alcohol ligand compound; (c) organonitrogen, phosphorus compound; (d) photosensitivity halogenide; E photo-thermal intelligent color-changing system that () solubilizing agent is formed, is mixed by singe screw or twin screw extruder granulation as processing aid and common macromolecule resin and common oxidation inhibitor, thermo-stabilizer, also can be mixed by dissolution with solvents.The mixture of preparation can by blown film, casting films, blowing, thickness that common complete processing the processes film at 2 μ-2mm such as to extrude.The selection of solubilizing agent is very important for the processing of resin film forming.Suitable solubilizing agent can make photo-thermal intelligent color-changing system have better photo-thermal color changeable effect, and the temperature sensitive photochromic polymeric film of light prepared can be made to have better transparency, lower mist degree, better processed-type.
Common Polymers resin comprises: polystyrene, polymethylmethacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl alcohol suceinic aldehyde ester, polyethylene, polypropylene, poly-polyethylene terephthalate ester, polyethylene vinyl acetate multipolymer.Above-mentioned polymer plays dispersion, supporting role for photo-thermal intelligent color-changing system.This require selected by resin and photo-thermal intelligent color-changing system there is good mutual solubility, can ensure that the photothermal response smart membrane of preparation there will not be in wide temperature range like this and be separated, whole mould material there will not be vaporific opaque state.
In order to better adaptation material prepares film forming by screw extrusion press curtain coating blowing mode, prevent material producing heat-dissipating from degrading and oxidative degradation, in composite resin material, oxidation inhibitor and thermo-stabilizer will be added.Oxidation inhibitor comprises: 2, 6-di-t-butyl Pyrogentisinic Acid, 2, 4, 6-tri-butyl-phenol, 2, 6-bis-(octadecyl)-4-methylphenol, 2, 6-di-t-butyl-a-dimethylamino-p-cresol, 2, 4-dimethyl-6-tert.-butyl phenol, 4, 4-two (2, 6-DI-tert-butylphenol compounds) 4, 4-thiobis (6-tert-butyl-m-cresol) hexylene glycol [B-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], triphenyl phosphite, phenylbenzene isocaprylic acid phosphorous acid ester, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, pentaerythritol bis-phosphite two (stearyl alcohol), Tyox B, thio-2 acid two (13) ester, thiodipropionate polyester, four (dodecyl thiohydracrylic acid) pentaerythritol ester.
Thermo-stabilizer wherein comprises: calcium stearate, stearic acid tin, dibutyitin maleate etc.
In the photothermal response system that organotransition metal complex structure item changes, the resin molding prepared as auxiliary agent is in mass fraction, and its composition comprises:
1. photothermal response system 5-30 part
2. fluoropolymer resin 60-90 part
3. thermo-stabilizer 1-10 part
4. oxidation inhibitor 1-10 part
Photoresponse system and other auxiliary agents and common resin are as polystyrene, polymethylmethacrylate, polyvinyl chloride (PVC), polyvinyl alcohol, polyvinyl alcohol suceinic aldehyde ester (PVB), polyethylene, polypropylene, poly-polyethylene terephthalate ester (PET), polyethylene vinyl acetate multipolymer etc. (EVA), first mixed by high mixer, and then by twin screw extruder extruding pelletization.By the pellet prepared again by the film being prepared into thickness 10 μm of-2mm by plastic working instruments such as curtain coating forcing machine or inflation film manufacturing machines.The film of preparation also can be the composite membrane of multilayer different photoresponse system mould material.PVC and EVA for the photo-thermal intelligent response of preparation can be used as agricultural plastic film; PET film for the photo-thermal intelligent response of preparation can be used as the adhering film to glass of automobile or building; For the film that the EVA of preparation, PVB and polymethylmethacrylate photothermal response intelligent color-changing film can be prepared as doubling glass.
PVB and the EVA film of the intelligent doubling glass of the photothermal response for preparation are prepared into conventional 0.38mm by flow casting molding, the doubling glass film of 0.76mm and 1.35mm.Ripe dry lamination glass making processes is adopted to prepare doubling glass.Glass is common float glass, low-E glass, heat-reflecting glass etc.
Intelligent sunshade glass based on photothermal response of the present invention is that one with environmental change refined condition light penetration, when the permeability that maintenance glass is good, can have better thermal resistance coefficient, adjustable sheltering coefficient.When winter, glass remains high sunlight transmitance, summer particularly sunlight strong in, the reduction that the shading coefficient of glass is autonomous, plays the effect of external sunshade.Such intelligent glass material maximum sun when winter, reduces heating energy consumption, independently stops sunlight to enter indoor in summer, reduce the use of air-conditioning.The glassy product of this high intelligence can be building energy conservation, particularly plays important using value at the exterior-shading energy-saving of glass-wall building.
Beneficial effect: the present invention compared with prior art, has the following advantages:
Photochromic metal halide is a kind of typical photochromic material.Under the illumination condition of specific band, can there is light activated Reversible redox reaction in metal halide.Silver monobromide for common: as shown in Equation 2:
The silver element of simple substance piles up cluster, can reach the object of colour developing.Comprising of common photochromic metal halide: calcium iodide, silver chloride, Silver monobromide, Silver iodide etc.This photochromic glass is expensive, and the strength of glass of preparation is poor, and weight is high.This kind of glass has very large obstacle equally being applied to building energy saving field.This kind of photochromic glass will be dimmed under the condition of terrestrial solar radiation, and like this in time autumn and winter, people need also to shield Yanguan Pass during sunlight, so just prevent the utilization of sun power.
Chinese patent 201110311787.X, 201110397060.8 and 201310007523.4 provides a kind of intelligent glass of the temperature control prepared based on nanophase isolation technique.This glass can have comparatively significant condition ability at 300-2000 nano waveband.Sheltering coefficient reaches 0.8 at ambient temperature, temperature higher than design temperature as 30 degree time, sheltering coefficient is reduced to 0.3.The maximum shortcoming of this glass is that perviousness is poor, affects sight line when the phase transformation of temperature height.This glass of what is more important is that intelligent gel rubber material and traditional glass are formed with sandwich structure interlayer, and the tack of gel to glass is poor, can not use as shatter proof glass.
Prepared by the photothermal response system of the outer photaesthesia of collection of the present invention and the temperature sensitive organic transition metal mixture conformation transition basis based on the ingenious combination of the conformational isomerism of photochromic halogenide and organometallic complex.Photothermal response system comprises (a) transition metal ion; (b) polyvalent alcohol ligand compound; (c) organonitrogen, phosphorus compound; D the components such as () photosensitivity halogenide (e) solubilizing agent are formed.Be made up of reversible photoresponse system and reversible hot system in this individual system.This two individual system influences each other, and synergy constitutes the photothermal response system of multistage variable color.Photoresponse system is alternative under illumination condition, and whether photochromic control glass, and the degree of variable color, and chromic systems produces the part of the isomery of thermal response system simultaneously, produces hot tone-on-tone effect under making the easier condition raised in temperature of hot system.Such photo-thermal coordinative role effect can produce multistage color changeable effect, overcomes the problem of background color under cryogenic of simple thermal response system simultaneously, makes the photothermal response intelligent glass prepared have better energy-saving effect.
Photo-thermal variable color is based on such principle:
In above equation, X is halogen atom, itself is the isomery part (L of the transition metal complex of thermal control
b), its also can with N (R)
3, P (R)
3or 2-alkyl imidazole or 2-alkyl benzimidazole compound form the higher isomery part of efficiency.
As can be seen from above photochemical and thermal reaction mechanism, in the reversible balanced reaction of part isomery of the thermal initiation that equation (4) is formed, when temperature reduces, transition metal complex is with hexa-coordinate mode Me (L
a)
6exist, when the temperature increases, organometallic complex is with four-coordination mode Me (L
b)
4content increases, and colour developing appears in such transition organometallic complex.At certain L
aand L
bduring mol ratio, at ambient temperature without under direct sunlight condition time whole system present water white transparency, when the temperature increases, system changes to coloured direction.Reaction equation (3) constitutes light-initiated reversible balanced reaction.When non-illuminated conditions, system mainly exists with colourless MX.When illumination is strong, system produces reversible redox reaction, produces M and X.M itself can according to select the difference of metal species show or colourless.X can as L
bor with other material composition generations L
b, make the balance of reaction equation (1) be more conducive to right direction like this and transform.Like this under strong illumination condition, light activated halogen compounds meeting photolysis, produces halogen and the metal of simple substance.By using kind and the amount of different types of photosensitive halogen compounds, the degree whether whole photo-thermal system develops the color or develop the color can be controlled.Slight variable color is favourable for whole photothermal response system, particularly prepares photothermal response intelligent sunshade glass.Slightly develop the color under strong illumination condition, can effectively prevent dizzy, the better extinction of glass can be made to carry out photothermal conversion simultaneously.The preferred silver-colored Pseudohalides of photosensitivity halogenide, the elemental silver produced when silver halide photolysis has extraordinary heat reflection performance.The photothermal response intelligent sunshade glass prepared is made to have better heat-insulating property like this.Photosensitive halogenation object light decomposes the isomery part (L that the halogen atom produced itself is the transition metal complex of thermal control
b), its also can with N (R)
3, P (R)
3or 2-alkyl imidazole or 2-alkyl benzimidazole compound form the higher isomery part of efficiency.Therefore, when the temperature of system raises, transition metal complex just thinks that the colour developing heterogeneous states of four-coordination changes.Therefore, intensity of solar radiation is higher, and envrionment temperature is higher, and photothermal response intelligent sunshade glass colour developing degree is stronger, and its sunshade ability is higher.Otherwise under dark condition, photosensitive halogenation thing can not provide the part of isomery for the transition metal complex of thermochromism, even if the temperature of system raises, is also difficult to make system develop the color.
In a word, photothermal response system of the present invention, photothermal response resin, the photothermal response intelligent sunshade glass be particularly composited by the glass that photothermal response resin compounded is traditional, in the winter that temperature is lower, under terrestrial solar radiation intense conditions, more shallow or colorless state can be presented, higher light permeable rate (sheltering coefficient Se > 0.6) can be kept.Such people can utilize sun power preferably, reduce the consumption of the heating energy.In the summer of sweltering heat, when the higher and ambient light of envrionment temperature has deficiency, the intelligent sunshade glass of photothermal response remains water white transparency state, and glass itself has very low sheltering coefficient, allows outdoor light to enter indoor.And in the summer of sweltering heat, when envrionment temperature is high, when solar ray irradiation is strong, what glass was autonomous becomes dark, and the light permeable rate of glass declines, and sheltering coefficient reduces (sheltering coefficient Se > 0.6), such prevention sunlight enters indoor, reduces the use of cooling-down air conditioner.The present invention prepare based on photothermal response system, the photothermal response intelligent sunshade glass of preparation has high intelligent, while comfortable environment is provided for people, condition sheltering coefficient that can be independently clever, make people's better utilised and cover sun power, existing external sunshade equipment can be substituted, for building energy conservation makes significant contribution.
In a word, the intelligent glass of photothermal response of the present invention has the advantage of the following aspects:
Realization of the present invention is based upon on the photo-isomerisable basis of the transition organometallic complex of photothermal response.
Of the present inventionly realize photothermal response system, the reversible photolysis of metal halide is caused by illumination, cause preliminary colour developing, the halogen atom simultaneously decomposing generation changes transition metal complex and is changed to four-coordination direction by hexa-coordinate, Promotion system transforms to colour developing direction more, thus making system under the condition that the larger temperature of intensity of illumination is higher, color is darker, and light permeable rate is lower.
The doubling glass of photothermal response of the present invention for ambient temperature conditions change autonomous produce stress behavior, not needing people to give the object that signal (as energising) reaches response, is therefore a kind of intelligent power saving product truly.
The technology adopted environmental protection more.The macromolecular material that intelligent glass of the present invention adopts is a kind of nontoxic, stable, eco-friendly macromolecular material.If damaging or abandoning appears in intelligent glass, can not bring any environmental pollution, the production process of this macromolecular material also can not bring environmental pollution simultaneously.
Intelligent glass raw materials cost of the present invention is low, and preparation for processing is simple.
Intelligent glass product of the present invention has better environmental stability and work-ing life.This product can use within 20 ~ 50 years, undergo no deterioration continuously under-20 ~ 80 DEG C of outdoor homes, can meet the application under various environment.
Intelligent sunshade glass of the present invention, particularly covers based on PVB and EVA material, can have and use as splinter-proof glass, have extraordinary security, heat-proof quality and low heat conductivity.
Photothermal response type Intelligent Composite opticglass of the present invention can be widely used in glass curtain wall, the vehicles.
Accompanying drawing explanation
Fig. 1 is the conformation transition schematic diagram that transition metal complex temperature causes.
Embodiment
Below by embodiment, specific description is in detail done further to the present invention.
Embodiment 1:
By CoCL2 6H2O 1 part, propylene glycol 0.2 part, triphenyl phosphorus 10 parts, Tetrabutyl amonium bromide 10 parts, calcium iodide 1 part, is dissolved in 50 milliliters of anhydrous tetrahydrofuran solutions.Add the polystyrene of 60 parts in the solution, 40 parts of dioxane, 1.5 part of 2,6-di-t-butyl Pyrogentisinic Acid and 1 part of stearic acid tin.By polymers soln spin coating on a glass, the film of 0.2 mm thick is prepared.After dissolving volatilization completely, enclose another layer of glass at film surface, keep 20 minutes under 100 degree of 1 MPa, prepare the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.76, under 60 degree of conditions, Se=0.65 during unglazed photograph, becomes yellow-green colour, sheltering coefficient Se=0.3 under 60 degree of sunburst illuminate conditions.
Embodiment 2
By CoCL2 6H2O 0.1 part, 1,3 butylene glycol 10 parts, triphenyl phosphorus 0.4 part, Tetrabutyl amonium bromide 10 parts, 10 parts, tetrabutyl phosphonium bromide phosphorus, silver chloride 0.2 part, is dissolved in 50 milliliters of anhydrous butyrolactone solution.Add the polyvinyl alcohol of 90 parts in the solution, 50 parts of dioxane, 2, the 6-di-t-butyl-a-dimethylamino-p-cresol of 0.5 part and the stearic acid tin of 10 parts prepare the film of wide 20 cm thick 0.4 millimeter.Be placed in by the film of preparation between two sheet glass, under 120 degree of 2 MPa condition, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.72, under 60 degree of conditions, Se=0.67 during unglazed photograph, becomes deep green, sheltering coefficient Se=0.28 under 60 degree of sunburst illuminate conditions.
Embodiment 3
By CoCL2 6H2O 2 parts, polyvinyl alcohol 10 parts, triphenyl phosphorus 15 parts, 5 parts, ethyltriphenylphosphiodide iodide phosphorus, calcium iodide 5 parts, is dissolved in 50 milliliters of adipic acid dimethyl ester solution.Add the polystyrene of 61 parts in the solution, 60 parts of dioxane, 4,4-two (2,6 di t butyl phenols) of 1 part and the dibutyitin maleate of 5 parts, by polymers soln spin coating on a glass, prepare the film of 0.5 mm thick.Prepare the film of wide 20 cm thick 0.5 millimeter.Be placed in by the film of preparation between two sheet glass, under 120 degree of 2 MPa condition, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.74, under 60 degree of conditions, Se=0.68 during unglazed photograph, becomes light green, sheltering coefficient Se=0.26 under 60 degree of sunburst illuminate conditions.
Embodiment 4
By nickelous nitrate 0.1 part, glycerine 0.2 part, triethylamine 0.4 part, silver chloride 1 part, 60 parts of polyvinyl alcohol, 15 parts of adipic acid dibutylesters, 0.2 part 4,4-thiobis (6-tert-butyl-m-cresol) and the calcium stearate of 0.3 part are dissolved in the mixing solutions of (50:50) benzene and water, and the film of wide 10 cm thick 0.6 millimeter is prepared in spin coating.Be placed in by the film of preparation between two sheet glass, under 120 degree of 2 MPa condition, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.75, under 60 degree of conditions, Se=0.65 during unglazed photograph, becomes scarlet, sheltering coefficient Se=0.23 under 60 degree of sunburst illuminate conditions.
Embodiment 5
By cupric nitrate 2 parts, Xylitol 20 parts, three 6 parts, n-octyl phosphorus, Silver monobromide 0.2 part, 80 parts of poly-second chlorine alkene, 16 parts of ethyl acetate, 2,4, the 6-tri-tert Pyrogentisinic Acids of 10 parts and the calcium stearate of 1 part are dissolved in toluene solution.By polymers soln spin coating on a glass, the film of 0.7 mm thick is prepared.The film of preparation to be placed between sheet glass hot pressing under 120 degree of 2 MPa condition and to become the laminated glass of sandwich structure.Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.75, becomes deep green under 60 degree of sunburst illuminate conditions, sheltering coefficient Se=0.26.
Recipe ingredient is dissolved in dissolving by embodiment 6-50, prepares film by spin-coating method.After solvent evaporates complete drying, be placed in by the film of preparation between two sheet glass, under 120 degree of 2 MPa condition, hot pressing becomes the test structure of the laminated glass of sandwich structure.
Embodiment 51
By manganous nitrate 0.1 part, glycerine 0.2 part, tri hydroxy methyl butane 10 parts, four heptyl brometo de amonios 0.4 part, silver chloride 1 part, polyvinyl alcohol 60 parts, adipic acid dibutylester 15 parts, 2,6-di-t-butyl Pyrogentisinic Acid 0.2 part and calcium stearate 0.3 part are by twin screw extruder granulation.Screw extrusion press melt zone temperature 120 DEG C, die temperature 145 DEG C.The pellet of preparation, by curtain coating extrusion shaping machine, prepares the film of wide 10 cm thick 0.3 millimeter.Injection moulding machine die temperature 125 DEG C.Be placed in by the film of preparation at 120 DEG C between sheet glass, under 2MPa, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.75, under 60 degree of conditions, Se=0.63 during unglazed photograph, becomes scarlet, sheltering coefficient Se=0.23 under 60 degree of sunburst illuminate conditions
Embodiment 52
By Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 2 parts, Xylitol 20 parts, 6 parts, tetramethyl-iodate phosphorus, Silver monobromide 0.2 part, polyvinyl alcohol 80 parts, dibutyl azelate 16 parts, 2,4,6-tri-tert Pyrogentisinic Acid 10 parts and calcium stearate 1 part are by twin screw extruder granulation.Screw extrusion press melt zone temperature 120 DEG C, die temperature 145 DEG C.The pellet of preparation, by curtain coating extrusion shaping machine, prepares the film of wide 20 cm thick 0.4 millimeter.Casting machine die temperature 125 DEG C.Be placed in by the film of preparation at 120 DEG C between sheet glass, under 2MPa, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.76, under 60 degree of conditions, Se=0.66 during unglazed photograph, becomes deep green, sheltering coefficient Se=0.26 under 60 degree of sunburst illuminate conditions
Embodiment 53
By Manganese dibromide 0.5 part, neopentyl glycol 5 parts, three (diphenyl-ethyl phosphorus ethyl) 20 parts, phosphorus, silver chloride 5 parts, polyvinyl alcohol 90 parts, adipic acid dibutylester 15 parts, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester 0.2 part and calcium stearate 0.3 part are by the film of curtain coating extrusion mechanism for generous 0.5 millimeter.Casting machine die temperature 125 DEG C.Be placed in by the film of preparation between two sheet glass, at 120 DEG C, under 2MPa, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.77, under 60 degree of conditions, Se=0.67 during unglazed photograph, becomes yellow-green colour, sheltering coefficient Se=0.25 under 60 degree of sunburst illuminate conditions
Embodiment 54
By nickelous perchlorate 0.2 part, propylene glycol 20 parts, 10 parts, thricyclohexyl phosphorus, Tetrabutyl amonium bromide 10 parts, calcium iodide 3 parts, polystyrene 50 parts, dioxane 15 parts, 2,4-dimethyl-6-di-t-butyl Pyrogentisinic Acid 0.5 part and 0.2 part, stearic acid tin are by twin screw extruder granulation.Screw extrusion press melt zone temperature 120 DEG C, die temperature 145 DEG C.The pellet of preparation, by curtain coating extrusion shaping machine, prepares the film of wide 20 cm thick 0.6 millimeter.Casting machine die temperature 125 DEG C.Be placed in by the film of preparation between two sheet glass, at 120 DEG C, under 2MPa, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.72, under 60 degree of conditions, Se=0.65 during unglazed photograph, becomes blackish green, sheltering coefficient Se=0.28 under 60 degree of sunburst illuminate conditions
Embodiment 55
By chromium chloride hexahydrate 0.3 part, polyvinyl alcohol 4 parts, 4 parts, tripropyl phosphorus, 3 parts, Silver iodide, poly-polyethylene ethylene alcohol copolymer 65 parts, adipic acid dibutylester 15 parts, triphenyl phosphite 0.2 part and calcium stearate 0.3 part are by twin screw extruder granulation.Screw extrusion press melt zone temperature 120 DEG C, die temperature 145 DEG C.The pellet of preparation, by curtain coating extrusion shaping machine, prepares the film of wide 20 cm thick 0.7 millimeter.Casting machine die temperature 125 DEG C.Be placed in by the film of preparation between two sheet glass, at 120 DEG C, under 2MPa, hot pressing becomes the laminated glass of sandwich structure.
Glass is at 20 degree without water white transparency under sunlight condition, and sheltering coefficient Se=0.74, under 60 degree of conditions, Se=0.65 during unglazed photograph, becomes intense violet color, sheltering coefficient Se=0.28 under 60 degree of sunburst illuminate conditions
Following examples are standby by curtain coating extrusion mechanism.Thickness is 0.4 millimeter, the sandwich structure prepared by the white glass of two-layer 3 mm thick.
Above-described embodiment should be understood only for illustration of the embodiment of technical solution of the present invention, and be not used in and limit the scope of the invention.After having read the present invention, those skilled in the art are to the amendment of various equivalents of the present invention and replace the protection domain all falling within the application's claim and limit.
Claims (8)
1. a photothermal response system, it is characterized in that, this system is by transition metal ion, polyalcohols ligand compound, photosensitivity halogenide, and organic nitrogen compound and/or phosphorus compound mixing after, obtained by organotransition metal complex conformation transition, described photosensitivity halogenide is one or more the mixing in silver chloride, Silver monobromide, Silver iodide, calcium iodide.
2. photothermal response system according to claim 1, it is characterized in that, described transition metal ion accounts for 0.1-2 mass parts, and polyalcohols ligand compound is 0.2-20 mass parts, photosensitivity halogenide is 0.2-5 mass parts, and organic nitrogen compound and/or phosphorus compound are 0.4-20 part.
3. photothermal response system according to claim 2, is characterized in that, this system also comprises the solubilizing agent of 10-60 mass parts.
4. the photothermal response system according to claim 1,2 or 3, it is characterized in that, described transition metal ion is one or more the mixing in Fe (II), Co (II), Cu (II), Ni (II), Mn (II), Cr (II).
5. the photothermal response system according to claim 1,2 or 3, is characterized in that, described organic nitrogen compound and/or phosphorus compound are N (R)
3, P (R)
3, N
+(R)
3r
1x
-, P
+(R)
3r
1x
-, one or more mixing in glyoxaline compound and benzimidazoles compound, wherein, R is aromatic group or alkyl, R
1for alkyl, X is halogen atom.
6. a photothermal response resin material, is characterized in that, this material, by the photothermal response system described in claim 1,2,3,4 or 5, melt extrudes after mixing with fluoropolymer resin and polymer processing aids, or lysigenous mixture after mixing.
7. photothermal response resin material according to claim 6, is characterized in that, the mass percentage content of described fluoropolymer resin is 40-80%, and the mass percentage content of polymer processing aids is 1-30%.
8. a photothermal response intelligent glass, is characterized in that, this intelligent glass is obtained by the photothermal response resin material on the glass substrate described in attachment claim 6 or 7.
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| CN105713238A (en) * | 2016-02-02 | 2016-06-29 | 付国东 | Nano composite photo-thermal response system, resin material and intelligent glass |
| CN108454200A (en) * | 2017-12-08 | 2018-08-28 | 常州市交通设施有限公司 | A kind of intelligent power saving composite membrane |
| 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 |
| CN109679582B (en) * | 2018-12-17 | 2021-12-07 | 中国人民大学 | Liquid photo-thermal conversion material and preparation method and application thereof |
| CN113666633A (en) * | 2021-08-23 | 2021-11-19 | 中方县明兴玻璃有限公司 | Color-changing glass and preparation method thereof |
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| CN103085393A (en) * | 2013-01-09 | 2013-05-08 | 付国东 | Thermo-sensitive type intelligent composite optical glass based on renewable resources |
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| CN103085393A (en) * | 2013-01-09 | 2013-05-08 | 付国东 | Thermo-sensitive type intelligent composite optical glass based on renewable resources |
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