CN1350038A - Energy-saving material with far infrared reflecting property and its prepn - Google Patents
Energy-saving material with far infrared reflecting property and its prepn Download PDFInfo
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- CN1350038A CN1350038A CN01134789A CN01134789A CN1350038A CN 1350038 A CN1350038 A CN 1350038A CN 01134789 A CN01134789 A CN 01134789A CN 01134789 A CN01134789 A CN 01134789A CN 1350038 A CN1350038 A CN 1350038A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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Abstract
The present invention relates to a kind of energy-saving material with far-infrared reflection property and its preparation method. It includes conductive polymer A whose conductivity is greater than or equal to 10 to the minus second power S/cm; self-supporting film make of the conductive polymer A; coated energy-saving material formed by filming the conductive polymer A on the organi cmaterial, inorganic material or metal matrix; section material B formed by using the conductive polymer A and organic base material and additive through the processes of mixing, extruding and forming; section material C made up by means of copolymerization of conjugated polymer monomer or its derivative monomer and organic monomer and energy-saving paint or energy-saving coating made up by adding conductive polymer A into paint or coating. Its reflectivity is greater than or equal to 50% in far infrared area.
Description
Technical field:
The present invention relates to a kind of energy-saving material and preparation method thereof with high far infrared reflectivity.
Background technology:
For a long time, people are seeking a kind of energy-saving material always, to reach attractive in appearance, energy-conservation, practical, economic effect again, as low emissivity glass (low-E Glass), ITO conductive glass etc., United States Patent (USP) 6,030,671 disclose a kind of low radiation fenestrated membrane, it consists of: (1) reflective metal film layer, can form by silver, gold, copper or aluminium or its alloy or its composition; (2) cover protecting materials thin film layer on the metal level, can also comprise vibrin, poly-para xylylene, silane in the protecting materials by titanium, nickel, chromium, niobium, gold, platinum or its alloy or stainless steel; (3) performance that has at least on one side at reflective metal layer increases thin film layer; (4) cover damage resistant and abrasive hard dope layer on the protecting materials.The core substance of this fenestrated membrane is an inorganic metal, needs a large amount of precious metals or its alloy, and is with high costs, and need plate four tunics at least, complex process, and final finished costs an arm and a leg.
Summary of the invention
It is that the far infrared zone reflectivity of 2500-25000nm is not less than energy-saving material of 50% and preparation method thereof at wavelength that the object of the invention provides several.
A kind of energy-saving material with far infrared reflecting property, it is electric conductivity 〉=10
-2The conductive polymers A of S/cm; The self-supported membrane that conductive polymers A makes; The plated film energy-saving material that conductive polymers A film forming on organic materials, inorganic materials or metal matrix forms; The section bar B that conductive polymers A and organic substrate and additive blend extruding form; The section bar C that the monomer of conjugated polymers or derivatives thereof and organic monomer copolymerization form, conductive polymers A join energy saving paint or the energy-saving coatings that forms in paint or the coating or join and make the energy-saving glass gloss varnish in the glass gloss varnish.
In the multipolymer of the conjugated polymers that described conductive polymers A is the conjugated polymers, the derivative that mixes the conjugated polymers of doping agent that mix doping agent, mix doping agent one or both and two or more mixtures; Or in the multipolymer of the derivative of conjugated polymers, conjugated polymers, conjugated polymers two kinds and two or more mixtures make after mixing doping agent; The derivative of conjugated polymers, conjugated polymers, the multipolymer of conjugated polymers or its two kinds and two or more mixture and doping agent are respectively by structure monomer mole ratio 4: 1-1: 1 mixes.Described doping agent can be that formula is that protonic acid, the formula of HxAy is
A kind of or its two kinds and two or more mixtures in the phenol compound;
In HxAy: x, y are the integer of 1-8, and H is H
+, A is a negatively charged ion, can be acid ion, also can be x-R, wherein x-is negatively charged ion SO
3 -, Cl
-, Br
-, RSO
3 -, R is CCl
3, CF
3, halogen Cl or F or be the alkyl or aryl of 1-30 carbon;
At general formula
In R can be hydrogen, methyl, ethyl, F, Cl ,-NO
2, a 1-20 carbon alkyl, but monosubstitution, but also double-basis replaces.
Described x-is preferably negatively charged ion RSO
3 -, SO
3 -
Described acid ion is preferably Cl
-, Br
-, I
-, SO
4 2-, PO
4 3-, ClO
4 -, CH
3SO
3 -
Described doping agent can also be M for general formula
aX
bHalogenide, and halogen X
2In one or both and two or more mixtures, at M
aX
bMiddle a, b are respectively the integer of 1-6, and M is a transition metal, and X is halogen F, Cl, Br, I, at X
2In X be a kind of among halogen F, Cl, Br, the I.
Described transition metal is preferably Fe, Mo, W, Sn, Rn, Ta, Sn.
Described doping agent also can be selected from Li, Na, K, Cs, NH
3, tetraethyl ammonium (TEA+), one or both in the TBuA (TbuA+) and two or more mixtures.
Described conjugated polymers is a kind of of polyaniline, polyacetylene, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, poly(p-phenylene).
A is dissolved in organic solvent with conductive polymers, makes conductive polymer solution after centrifugation; With conductive polymer solution with spray, divide, a kind of making it in the impregnating method covering on smooth inorganic matrix, 50 ℃-80 ℃ down insulation 2-10 hour and the energy-saving material self-supported membrane.
A is dissolved in organic solvent with conductive polymers, makes conductive polymer solution after centrifugation; Conductive polymer solution with wherein a kind of mode of spin coating, spraying, impregnating film forming on inorganic matrix, organic substrate, metal, under 50 ℃-80 ℃, is placed and made it solvent evaporates in 2-10 hour and form the plated film energy-saving material.
Organic solvent is selected from one or both and the two or more mixtures in N-Methyl pyrrolidone, chloroform, acetate, trifluoroacetic acid, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), phenol compound and the derivative.
Described temperature is preferably 40 ℃-100 ℃.
The described time is for being preferably 4-8 hour.
Described inorganic matrix is quartz, glass, pottery, grouan, cement.
Described metal is gold and silver, copper, iron, aluminium, tin, zinc, alloy, stainless steel.
With conductive polymers A and organic substrate by 1: 40-1: 10 weight ratio is mixed, and adds the turps of the 0.1%-5% of mixture weight again, and at 120-260 ℃, pressure is to be squeezed into section bar B under the 60-180Mpa.
The weight ratio of conductive polymers A and organic substrate is 1: 25-1: 15 is better.
Described organic substrate is that polyolefine, polyvinyl chloride, phenylethylene resin series, polyacrylic ester, polymeric amide, polycarbonate, polyoxymethylene improve polyphenylene oxide, thermoplastic polyester, polysulfones, polyphenylene sulfide, polyarylester, Resins, epoxy, insatiable hunger and close vibrin.
The monomer of conjugated polymers or derivatives thereof and organic monomer, additive form section bar C at-20 ℃-100 ℃ by monomer polymerization, wherein the monomer of conjugated polymers or derivatives thereof and organic monomer weight ratio are 1: 40-1: 5, and additive is the 0.1%-3% of gross weight.
With adulterated conductive polymers A is 1 by weight: 40-1: 10 join in the coating, make energy-conservation coating.
Is 1 with adulterated conductive polymers A by adding weight ratio: 40-1: 10 in paint, makes energy saving paint.
Described weight ratio is preferably 1: 25-1: 15.
Material of the present invention is that the far infrared zone reflectivity of 2500-25000nm is not less than 50% at wavelength; Owing to described material is to adopt the lower conjugated polymers of manufacturing cost and derivative thereof, multipolymer to mix and make, need not noble metal, so cost is low; Because one-pass film-forming or moulding can be processed and be obtained, so technology is simple, final product price is low again.
Embodiment:
Because conjugated polymers, the derivative of conjugated polymers, the multipolymer of conjugated polymers have strong chain interphase interaction, the indissoluble infusibility, its moldability is poor, usually doping agent is doped into doping agent with suitable concentration, adulterating method in the multipolymer of derivative, conjugated polymers of conjugated polymers, conjugated polymers and realizes its electroconductibility.Because conjugated polymers, the derivative of conjugated polymers, the multipolymer of conjugated polymers have particular structure feature and mechanism of doping effect, excellent physical chemistry and tempting technology application prospect, at present mainly studied its application in technical fields such as the energy such as secondary cell, solar cell and opto-electronic device, electromagnetic shielding, stealthy technique, transmitter, anti-corrosion of metal, molecular device and life sciences, the direction of some forward practicability develops.But test discovery repeatedly through us, at room temperature, a kind of or its two kinds and two or more mixtures in the multipolymer of the derivative of adulterated conjugated polymers, conjugated polymers, conjugated polymers, its electric conductivity 〉=10
-2Be that 2500-25000nm far infrared zone has higher reflectivity at wavelength during S/cm, its reflectivity is not less than 50%, and this known field before being is never mentioned, and can utilize its this performance to make various energy-saving materials, and this material has antistatic performance.With it is that raw material is made energy-saving material or class coating material, itself and paint, coating mixing manufacture energy saving paint, coating is replaced existing with alloy, inorganic substance such as precious metal are the energy-saving material of main constituent, as make energy-conservation self-supported membrane material, perhaps with it with spin coating, spraying, flood any mode and be coated onto that other is organic, inorganic sheet, film forming on the wire rod, or itself and organic substrate, additive blend extrusion molding or blend, can also be its monomer polymerization mould molding, or with paint, coating, the mixing of glass gloss varnish obtains energy-conservation paint, coating, the glass gloss varnish.
Conductive polymers A is mixed and get by one or both or two or more mixtures in the multipolymer of the derivative of conjugated polymers, conjugated polymers, conjugated polymers among the present invention, or one or both or two or more dopings mixing afterwards in the multipolymer of the derivative of conjugated polymers, conjugated polymers, conjugated polymers and get; Doping is by electrochemical process, chemical method its electric charge to be shifted under certain condition doping agent and conjugated polymers, the derivative of conjugated polymers, the multipolymer of conjugated polymers, after being the multipolymer of derivative, conjugated polymers of doping agent doping conjugated polymers, conjugated polymers, form various current carriers such as orphan, CHARGED SOLITON, polaron and bipolaron in the multipolymer of the derivative of conjugated polymers, conjugated polymers, conjugated polymers, doping agent itself has formed positively charged or negative electricity ion is attached on the conductive polymer subchain simultaneously.
Conjugated polymers is polyaniline, polyacetylene, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, poly(p-phenylene) among the present invention.
The preparation of polyaniline, its derivative and multipolymer thereof and adulterating method reference: ConductingPolymers, P105 ￣ 120, 1987by D.Reldel Publishing Company and United States Patent (USP) 5,254,670; 5,574,131; 5,403,913 and Chinese patent application publication number CN1158349A; The DimensionalSyntheticMetals according to Physics and Chemistry of Low, AbanoTerme (Italy) (1984), MolCrystLiqCryst117,1-486 (1985) are mixed in polyacetylene, its derivative and copolymer thereof and doping; With Conducting Polymers, 65-75,77-87, 1987 by DReidelPublishing Company, Handbook of Conducting Polymers, 45-79,1986.Polythiophene, its derivative and copolymer thereof and mix with reference to McCullough RD Lowe R D, JayaramanM, Anderson D LJOrgChem, 1993,58:904-912; McCullough R D, Nagle ST, Williams S P, Lowe R D, Jayaraman MJAmChemSoc, 1993,115:4910-4913.Polypyrrole, its derivative and copolymer thereof and doping are with reference to ToShima N, IhataOSynthMet, 1996,79:165-172; Machida S, Miyata, S, TechagumpuchASynthMet, 1989,31:311-318, the preparation of poly(p-phenylene), its derivative and multipolymer thereof and mix with reference to Gin DL Conticello VP, Trends in PolymSci, 1996,4:217-222; QianX, Pena M, Macromolecules, 1995,28:4415-4420; Polyphenylene sulfide, its derivative and copolymer thereof and mix with reference to Chance R R Schacklette L w, Miller G G, Lvory D M, Sowa JM, Elsenbaumer R L, Baughman R HJ chem soc, chem comm, 1980,34.Synthetic the reaching of polyphenylacetylene, its derivative and multipolymer thereof mixed with reference to AJHeeger WO92/16023; People's such as FWudt United States Patent (USP) 5,189,136.
Doping agent can be that formula is that protonic acid, the formula of HxAy is
In the phenol compound one or both and two or more mixtures.At general formula HxAy, x, y all can be integer 1,2,3,4,5,6,7,8, and x, the y value can be identical, also can be inequality, and H is H
+, A is a negatively charged ion, can be acid ion, is preferably Cl in the acid ion
-, Br
-, I
-, PO
3 -, SO
4 2-, PO
4 3-, ClO
4 -, CH
3SO
3 -, A also can be X-R, and wherein x is SO
3 -, Cl
-, Br
-, RSO
3 -In a kind of, SO
3 -, RSO
3 -Better, R is CCL
3, CF
3, halogen Cl or F, or be the alkyl or aryl of 1-30 carbon; Phenol compound
Among the R, R can be the alkyl of hydrogen, methyl, ethyl, fluorine, chlorine, nitro, a 1-20 carbon, but monosubstitution, but also double-basis replaces.
Doping agent also can be halogenide M
aX
bOr X
2, a wherein, b is respectively integer 1,2,3,4,5,6, a, the b value can be identical, also can be inequality, M is a transition metal, is preferably Fe, Mo, W, Sn, Rn, Ta; X is a halogens, is preferably F, Cl, Br, I.
Doping agent also can be selected from Li, Na, K, CS, NH
3, tetraethyl ammonium (TEA+), one or both in the TBuA (TbuA+) etc. and two or more mixtures.
Conjugated polymers, the derivative of conjugated polymers, in the multipolymer of conjugated polymers one or both and two or more mixture and doping agent are respectively by structure monomer mole ratio 4: 1-1: 1 makes conductive polymers A after mixing, also desirable two kinds and two or more adulterated conjugated polymers, the derivative of conjugated polymers, the multipolymer of conjugated polymers is mixed and made into conductive polymers A, i.e. polyacetylene, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, in the poly(p-phenylene) one or both and two or more mixtures mix, also polyacetylene, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, in the derivative of poly(p-phenylene) one or both and two or more mixtures mix, polyacetylene also, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, in the multipolymer of poly(p-phenylene) one or both and two or more mixtures mix and make conductive polymers A, polyacetylene also, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, a kind of and polyacetylene in the poly(p-phenylene), polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, mix in the derivative of poly(p-phenylene) or one or both and two or more mixing in multipolymer back, or will above-mentioned two kinds of making and two or more conductive polymers A is mixed must.
Conductive polymers A is dissolved in organic solvent, make conductive polymer solution after centrifugation, organic solvent is selected from one or both and the two or more mixtures in N-Methyl pyrrolidone, chloroform, acetate, trifluoroacetic acid, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), phenol compound and the derivative.
Above-mentioned conductive polymer solution can spraying, spin coating, divide, the impregnating method makes it covering on clean, smooth inorganic sheet materials such as exsiccant is quartzy, glass, grouan, pottery, under 50 ℃-80 ℃ best 40 ℃-100 ℃ temperature, be incubated 2-10 hour and be preferably 4-8 hour and the energy-saving material self-supported membrane.
Also can be with conductive polymer solution with spin coating, spraying, the any mode of impregnating is inorganic, organic substrate, film forming on the metal, at 50 ℃-80 ℃ best 40-100 ℃, be preferably 4-8 hour in 2-10 hour and make it solvent evaporates and form the plated film energy-saving material, inorganic matrix is a glass, quartzy, grouan, pottery, organic substrate is selected from polyolefine, polyvinyl chloride, phenylethylene resin series, polyacrylic ester, polymeric amide, polycarbonate, polyoxymethylene improves polyphenylene oxide, thermoplastic polyester, polysulfones, polyphenylene sulfide, polyarylester, Resins, epoxy, sheet materials such as vibrin are closed in insatiable hunger, a kind of in the wire rod, metal is a gold, silver, copper, iron, aluminium, tin, zinc, alloy, stainless steel.
Also can be with conductive polymers and organic substrate by 1: 40-1: 10 weight ratios be preferably 1: 25-1: 15 mixed, the turps that adds the 0.1%-5% of mixture weight again, in temperature is 120 ℃-260 ℃, and pressure is to be squeezed into section bar B under the 60Mpa-180Mpa.
The monomer and the organic monomer additive that can also be the derivative of the monomer of conjugated polymers or conjugated polymers form section bar C at-20 ℃-100 ℃ by monomer polymerization.
With conductive polymers by weight 1: 40-1: 10, be preferably 1: 25-1: 15 ratio joins in the various paint, becomes the energy-conservation coating of infrared external reflection; With conductive polymers by weight 1: 40-1: 10, be preferably 1; 25-1: 15 ratio joins in the various coating, becomes the energy-conservation coating of infrared external reflection.
Can be made into transparent or opaque goods according to different needs with material of the present invention, these goods comprise infrared external reflection energy-conserving plate material for building, the vehicles and furniture infrared external reflection energy-conserving plate material, infrared external reflection paint, coating, clothes heat-preservation clothing material.
Following examples are in order to explanation the present invention but do not limit the present invention.
Embodiment 1
The aniline 20ml that newly heavily steamed is dissolved in the 1N hydrochloric acid soln of the new preparation of 300ml, be chilled to 0 ℃, in 2 minutes to wherein adding the 200ml1N hydrochloric acid solution be dissolved with 11.5 gram ammonium persulphates while stirring, and the maintenance temperature is 0 ℃, mixture was converted into deep green after about 5 minutes, keep 0 ℃ of temperature, continue to stir after 90 minutes mixture is carried out suction filtration, it is colourless until filtrate to leach solid with 1N salt acid elution, continue suction filtration to filter cake and obvious crackle occurs, the 0.1N NH of gained solid dispersed in the new preparation of 500ml
4Among the OH, magnetic agitation 24 hours, suction filtration is used 500ml 1N NH again
4After the OH washing, treat that obvious crackle appears in filter cake, collect, put into vacuum drying oven under-0.1Mpa pressure, under the room temperature dry 48 hours, collect products obtained therefrom, stand-by.It is the polyaniline of emeraldine base form, and its structural formula is as follows:
To restrain camphorsulfonic acid with polyaniline 0.579 gram and 0.742 of the emeraldine base form of method for preparing mixes, grind and add 20ml chloroform stirring 10 minutes under the room temperature of back, adding the 30ml meta-cresol again stirred 8 hours, separated 20 minutes the polyaniline solutions of the attitude that obtains mixing with separating centrifuge 3000rPm.
Embodiment 2:
Getting a clean length and width height is 40 * 40 * 2mm sheet glass, drip the polyaniline solutions of the doping attitude that 3ml embodiment 1 makes in the above, shakeout, after keeping 8 hours under 60 ℃ the temperature, treat its naturally cooling, take out, the film of tearing, and obtain having the self-supported membrane of far infrared reflecting property, its reflectivity is 55% in the far infrared zone, and its electric conductivity is 120S/cm.
Embodiment 3:
The polyaniline 0.375 that embodiment 1 is made restrains, be dissolved in the 40mlN-methyl-2-pyrrolidone, stir centrifugation in 10 hours after, add 0.188 gram methanesulfonic, stirred 10 minutes, film on the slide glass of 20mm * 20mm with spin-coating method, when rotating speed is that 500rpm drips above-mentioned solution 1ml, rotating speed is raised to 2000rPm after 10 seconds, kept 150 seconds, obtain conductive polymer membrane, its electric conductivity is 15S/cm, its reflectivity 51% in the far-infrared reflection district.
Embodiment 4:
O-ethoxyl amine 28.7ml is dissolved in the 1N hydrochloric acid soln of the new preparation of 300ml, be chilled to 0 ℃, in 2 minutes to wherein adding the 200ml 1N hydrochloric acid solution be dissolved with 11.5 gram ammonium persulphates while stirring and keeping 0 ℃ of temperature, mixture was converted into brown at about 20 minutes, keep 0 ℃ of temperature, continue to stir after 90 minutes mixture is carried out suction filtration.Colourless until filtrate with the solid that washing with acetone leaches, air drying 5 minutes is scattered in the gained pressed powder among the 0.1N NH4OH of the new preparation of 500ml, magnetic agitation 24 hours, suction filtration was used the 500ml washing with acetone again, air drying 10 minutes, collect, put into vacuum drying oven, under-0.1Mpa pressure, drying at room temperature 24 hours, collect products obtained therefrom, stand-by.
Embodiment 5:
Product 1.647 grams with embodiment 4 makes mix with 1.143 gram tosic acid, after grinding with pestle, mix after adding 5ml turps with 100 gram acetic acid-ethene-acetic acid, are squeezed into flat board at 140 ℃ of 130Mpa, and this product specific conductivity is 0.5S/cm; Reflectivity in the far infrared zone is 50%.
Embodiment 6
10ml aniline and 12.4ml ORTHO ANISIDINE are dissolved in the 1N hydrochloric acid soln of the new preparation of 300ml, be chilled to 0 ℃, in 2 minutes while stirring when wherein adding the 200ml1N hydrochloric acid solution be dissolved with 11.5 gram ammonium persulphates and keep 0 ℃ of temperature, it is pale purple that mixture gradually becomes, keep 0 ℃ of temperature, continue to stir after 90 minutes mixture is carried out suction filtration, it is colourless to be washed till filtrate with 1NHCL, continue suction filtration to filter cake and obvious crackle occurs, the 0.1N NH of gained solid dispersed in the new preparation of 500ml
4Among the OH, stirred 24 hours, suction filtration is used 500ml1NNH again
4After the OH washing, treat that obvious crackle appears in filter cake, collect that put into vacuum drying oven under-0.1Mpa pressure, drying at room temperature 48 hours is collected products obtained therefrom, and is stand-by.
0.108 gram and 5.4 gram H with above-mentioned products obtained therefrom
2SO
4After the mixing, add the 50ml alkydpaints and mix, obtain the infrared external reflection energy-saving coatings.Its reflectivity in the far infrared zone is that 51% its electric conductivity is 0.5S/cm.
Embodiment 7
With 1.0 grams 2, two (chloromethyl)-1-methoxyl group-4-(2-ethyl hexyl oxy) benzene of 5-are dissolved in the 20ml anhydrous tetrahydro furan, following above-mentioned drips of solution of room temperature added in the 80ml anhydrous tetrahydro furan that is dissolved with 2.12 grams, 95% potassium tert.-butoxide of stirring, reaction solution continues to stir after 24 hours under the room temperature, reaction solution is poured in the 500ml methyl alcohol of stirring, the gained red precipitate with deionized water wash after, with tetrahydrofuran (THF)/methyl alcohol recrystallize, drying obtains poly-(the 1-methoxyl group-4 (2-ethyl hexyl oxy-2,5-phenylacetylene) of product under vacuum condition at last.
Above-mentioned products obtained therefrom 0.4 gram is dissolved in the 15ml tetrahydrofuran (THF), and clean sheet glass immerses in the tetrahydrofuran solution, at the uniform velocity takes out, and allows after the solvent evaporates, and the sheet glass that is coated with the phenylacetylene film is put into I
2In the steam 24 hours, obtain adulterated polyphenylacetylene derivant material, its specific conductivity 6 is 80S/cm, region of ultra-red (2500-25000nm) reflectivity 50%.
Embodiment 8
Polyaniline 0.112 gram of the made emeraldine base form of embodiment 1 method is mixed with embodiment 4 made poly-(O-ethoxyl amine) 0.137 gram, be dissolved in the 20ml dimethyl formamide, stir after 10 hours, adding 1ml 1-propane sulfonic acid stirred 30 minutes, film on polystyrene plates with embodiment 3 described spin-coating methods, make the electric conductivity 0.8s/cm of product, its far infrared reflectivity is 53%.
Embodiment 9
Polyaniline 1.043 gram of the made emeraldine base form of embodiment 1 method and embodiment 6 made aniline are restrained with the multipolymer 0.302 of ORTHO ANISIDINE mix, adding tosic acid 0.133 gram grinds, join in the 15ml methyl-sulphoxide, film on polycarbonate plate with embodiment 3 described spin-coating methods, make the electric conductivity 1.1s/cm of product, its far infrared reflectivity 53%.
Embodiment 10
Embodiment 4 made poly-(O-ethoxyl amine) 0.0685 gram and embodiment 6 made aniline are restrained with the multipolymer 0.108 of ORTHO ANISIDINE mix, be scattered in the 100ml 1N HCL solution and stirred 24 hours, suction filtration, newly prepare the HCL filter wash with 200ml 1N again and go out thing, collection leached the thing vacuum drying oven dry 48 hours, collected product, and this product is dissolved in the 50ml alkydpaints, make energy-saving coatings, its far infrared region reflectivity 55%.
Embodiment 11
(O-ethoxyl amine) 0.014 restrains polyaniline 0.091 gram of the emeraldine base form that embodiment 1 method is made and 0.124 gram camphorsulfonic acid mixes with made the gathering of embodiment 4 methods, after the aniline that will make with embodiment 6 methods and multipolymer 0.011 gram and 0.54 of ORTHO ANISIDINE restrain methanesulfonic and mix again, all join in the 20mlN-methyl-2-pyrrolidone solution, stirred 8 hours, and made conductive polymer solution.Above-mentioned solution is sprayed onto on the polyvinyl-chloride plate material by spraying method, under 60 ℃ of temperature, kept 4 hours, make energy-conservation polyvinyl-chloride plate material, its electric electric conductivity 1s/cm; The reflectivity 54% in far infrared zone.
Embodiment 12
On sheet glass, make the polyacetylene film with Bai Chuanying tree method, polyaniline 0.091 gram of again that embodiment 1 method is made emeraldine base form is dissolved in the 10ml tetrahydrofuran (THF), stirred 4 hours, with embodiment 3 described spin-coating methods after filming on the polyacetylene film, this sheet glass of filming is put into the space that is full of iodine vapor to be kept 24 hours, make energy-saving film, its conductance is 120s/cm, the reflectivity 56% in far infrared zone.
Embodiment 13
Use Toshima N, Ihata 0SynthMet, 1996, the polypyrrole 0.33 that the 79:165-172 method makes restrains, and is scattered in the HCLO of 100ml 1.3M
4Stirred 24 hours in the liquid, filter, collect and leached thing vacuum-drying 24 hours, it is stand-by to collect product.
With made O-ethoxyl amine polymer 0.14 gram of embodiment 4 methods, be scattered in the H of 100ml 1.5M
2SO
4In the liquid, stirred 24 hours, filter, collect and leach thing, vacuum-drying 36 hours, it is stand-by to collect product.
Said two products is joined in the 10 gram paint, stir, mix and obtain energy saving paint, its electric conductivity is 0.5s/cm, far infrared zone internal reflection rate 51%.
Embodiment 14
With made O-ethoxyl amine polymer 0.137 gram of embodiment 4 methods, poly-(1-methoxyl group-4 (the 2-ethyl hexyl oxy-2 that embodiment 7 methods are made, the 5-phenylacetylene)) 0.265 gram, be dissolved in the 20ml tetrahydrofuran (THF), stirred 4 hours, and after filming on the slide glass of 20mm * 20mm, this slide glass was presented in the vessel that are full of iodine vapor and placed 24 hours with the described spin-coating method of embodiment 3 methods, obtain the electric conductivity 13S/cm of sample, the reflectivity in the far infrared zone is 53%.
Claims (23)
1. energy-saving material with far infrared reflecting property is characterized in that: it is electric conductivity 〉=10
-2The conductive polymers A of S/cm; The self-supported membrane that conductive polymers A makes; The plated film energy-saving material that conductive polymers A film forming on organic materials, inorganic materials or metal matrix forms; The section bar B that conductive polymers A and organic substrate and additive blend extruding form; The section bar C that the monomer of conjugated polymers or derivatives thereof and organic monomer copolymerization form, conductive polymers A join energy saving paint or the energy-saving coatings that forms in paint or the coating or join and make the energy-saving glass gloss varnish in the glass gloss varnish.
2. the energy-saving material with far infrared reflecting property as claimed in claim 1 is characterized in that: one or both in the multipolymer of the conjugated polymers that conductive polymers A is the conjugated polymers, the derivative that mixes the conjugated polymers of doping agent that mix doping agent, mix doping agent and two or more mixtures; Or in the multipolymer of the derivative of conjugated polymers, conjugated polymers, conjugated polymers two kinds and two or more mixtures make after mixing doping agent; The derivative of conjugated polymers, conjugated polymers, the multipolymer of conjugated polymers or its two kinds and two or more mixture and doping agent are respectively by structure monomer mole ratio 4: 1-1: 1 mixes.
3. the energy-saving material with far infrared reflecting property as claimed in claim 2 is characterized in that: described doping agent can be that formula is that protonic acid, the formula of HxAy is
A kind of or its two kinds and two or more mixtures in the phenol compound;
In HxAy: x, y are the integer of 1-8, and H is H
+, A is a negatively charged ion, can be acid ion, also can be x-R, wherein x-is negatively charged ion SO
3 -, Cl
-, Br
-, RSO
3 -, R is CCl
3, CF
3, halogen Cl or F or be the alkyl or aryl of 1-30 carbon;
At general formula
In R can be hydrogen, methyl, ethyl, F, Cl ,-NO
2, a 1-20 carbon alkyl, but monosubstitution, but also double-basis replaces.
4. the energy-saving material with far infrared reflecting property as claimed in claim 3 is characterized in that: x-is negatively charged ion RSO
3 -, SO
3 -
5. the energy-saving material with far infrared reflecting property as claimed in claim 3 is characterized in that: described acid ion is Cl
-, Br
-, I
-, SO
4 2-, PO
4 3-, ClO
4 -, CH
3SO
3 -
6. the energy-saving material with far infrared reflecting property as claimed in claim 2 is characterized in that: described doping agent can be M for general formula
aX
bHalogenide, and halogen X
2In one or both and two or more mixtures, at M
aX
bMiddle a, b are respectively the integer of 1-6, and M is a transition metal, and X is halogen F, Cl, Br, I, at X
2In X be a kind of among halogen F, Cl, Br, the I.
7, the energy-saving material with far infrared reflecting property as claimed in claim 6 is characterized in that: described transition metal is Fe, Mo, W, Sn, Rn, Ta, Sn.
8. as having the energy-saving material of far infrared reflecting property as described in the claim 2, it is characterized in that: described doping agent also can be selected from Li, Na, K, Cs, NH
3, tetraethyl ammonium (TEA+), one or both in the TBuA (TbuA+) and two or more mixtures.
9. have the energy-saving material of far infrared reflecting property as claimed in claim 1 or 2, it is characterized in that: described conjugated polymers is a kind of of polyaniline, polyacetylene, polypyrrole, Polythiophene, polyphenylene sulfide, polyphenylacetylene, poly(p-phenylene).
10. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, it is characterized in that: A is dissolved in organic solvent with conductive polymers, makes conductive polymer solution after centrifugation; With conductive polymer solution with spray, divide, a kind of making it in the impregnating method covering on smooth inorganic matrix, 50 ℃-80 ℃ down insulation 2-10 hour and the energy-saving material self-supported membrane.
11. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, it is characterized in that: A is dissolved in organic solvent with conductive polymers, makes conductive polymer solution after centrifugation; Conductive polymer solution with wherein a kind of mode of spin coating, spraying, impregnating film forming on inorganic matrix, organic substrate, metal, under 50 ℃-80 ℃, is placed and made it solvent evaporates in 2-10 hour and form the plated film energy-saving material.
12. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 10,11, it is characterized in that: organic solvent is selected from one or both and the two or more mixtures in N-Methyl pyrrolidone, chloroform, acetate, trifluoroacetic acid, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), phenol compound and the derivative.
13. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 10,11, it is characterized in that: described temperature is 40 ℃-100 ℃.
14. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 10,11, it is characterized in that: the described time is 4-8 hour.
15. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 10,11, it is characterized in that: described inorganic matrix is quartz, glass, pottery, grouan, cement.
16. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 11, it is characterized in that: described metal is gold and silver, copper, iron, aluminium, tin, zinc, alloy, stainless steel.
17. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, with conductive polymers A and organic substrate by 1: 40-1: 10 weight ratio is mixed, the turps that adds the 0.1%-5% of mixture weight again, at 120-260 ℃, pressure is to be squeezed into section bar B under the 60-180Mpa.
18. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 17, the weight ratio of conductive polymers A and organic substrate is 1: 25-1: 15.
19. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 11,17, described organic substrate is that polyolefine, polyvinyl chloride, phenylethylene resin series, polyacrylic ester, polymeric amide, polycarbonate, polyoxymethylene improve polyphenylene oxide, thermoplastic polyester, polysulfones, polyphenylene sulfide, polyarylester, Resins, epoxy, insatiable hunger and close vibrin.
20. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, the monomer of conjugated polymers or derivatives thereof and organic monomer, additive form section bar C at-20 ℃-100 ℃ by monomer polymerization, wherein the monomer of conjugated polymers or derivatives thereof and organic monomer weight ratio are 1: 40-1: 5, and additive is the 0.1%-3% of gross weight.
21. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, be 1 by weight with adulterated conductive polymers A: 40-1: 10 join in the coating, make energy-conservation coating.
22. have the preparation method of the energy-saving material of far infrared reflecting property according to claim 1, be 1 with adulterated conductive polymers A by adding weight ratio: 40-1: 10 in paint, makes energy saving paint.
23. as having the preparation method of the energy-saving material of far infrared reflecting property as described in the claim 21,22, described weight ratio is 1: 25-1: 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01134789A CN1350038A (en) | 2001-11-13 | 2001-11-13 | Energy-saving material with far infrared reflecting property and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01134789A CN1350038A (en) | 2001-11-13 | 2001-11-13 | Energy-saving material with far infrared reflecting property and its prepn |
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| CN1350038A true CN1350038A (en) | 2002-05-22 |
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ID=4672748
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245241B (en) * | 2007-02-14 | 2010-12-29 | 厦门市华星化工实业有限公司 | Far infrared light wave energy-saving material and product |
| CN102627828A (en) * | 2012-03-19 | 2012-08-08 | 上海锦湖日丽塑料有限公司 | Resin composition capable of reducing surface temperature of automotive interior product having deep color and preparation method thereof |
| CN103328591A (en) * | 2011-02-03 | 2013-09-25 | 长濑化成株式会社 | Infrared-reflecting substrate |
| CN110983267A (en) * | 2019-10-23 | 2020-04-10 | 武汉大学 | Preparation method of cement hydration product self-supporting nano film |
-
2001
- 2001-11-13 CN CN01134789A patent/CN1350038A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245241B (en) * | 2007-02-14 | 2010-12-29 | 厦门市华星化工实业有限公司 | Far infrared light wave energy-saving material and product |
| CN103328591A (en) * | 2011-02-03 | 2013-09-25 | 长濑化成株式会社 | Infrared-reflecting substrate |
| EP2671929A1 (en) * | 2011-02-03 | 2013-12-11 | Nagase ChemteX Corporation | Infrared-reflecting substrate |
| EP2671929A4 (en) * | 2011-02-03 | 2014-06-18 | Nagase Chemtex Corp | Infrared-reflecting substrate |
| CN102627828A (en) * | 2012-03-19 | 2012-08-08 | 上海锦湖日丽塑料有限公司 | Resin composition capable of reducing surface temperature of automotive interior product having deep color and preparation method thereof |
| CN110983267A (en) * | 2019-10-23 | 2020-04-10 | 武汉大学 | Preparation method of cement hydration product self-supporting nano film |
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