CN1554713A - Collagen base nano infrared low emissivity colouring pigment and preparing method - Google Patents
Collagen base nano infrared low emissivity colouring pigment and preparing method Download PDFInfo
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- CN1554713A CN1554713A CNA2003101127340A CN200310112734A CN1554713A CN 1554713 A CN1554713 A CN 1554713A CN A2003101127340 A CNA2003101127340 A CN A2003101127340A CN 200310112734 A CN200310112734 A CN 200310112734A CN 1554713 A CN1554713 A CN 1554713A
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Abstract
The collagen base nano coloring pigment with low infrared emissitivity is in core-shell structure with inner core of nano metal oxide coloring pigment and outer collagen grafting copolymer. Collagen molecule is first adsorbed onto the surface of nano pigment particle to modify and stabilize the nano particle, lipophilic grafting branch chain is then introduced to the collagen molecule via solution grafting copolymerization under the action of initiator and the collagen grafting copolymer coats the coloring pigment. The collagen base nano coloring pigment has relatively low infrared emissivity and good dispersivity in organic solvent or water, and it has pigment particle size smaller than 100 nm and outer shell thickness less than 20 nm. It is used in preparing stealth coating and stealth costume and can realize visible light stealth and infrared stealth without damaging radar stealth.
Description
Technical field
The present invention relates to prepare infrared stealth coating, infrared stealth clothes etc. used have the tinting pigment of infrared low-emissivity at 8～14 mu m wavebands, be meant that especially the characteristic of utilizing collagenic material prepares all finely disseminated nanometer infrared low-emissivity tinting pigment in organic solvent or water.
Background technology
Along with the development of various Detection Techniques, more and more higher to the requirement of infrared stealth coating or clothes, general camouflage coating all will be taken into account the requirement of visible light and radar wave camouflage.Stealthy for visible light, all add tinting pigment in the camouflage coating usually, at present used tinting pigment is organic and inorganic two kinds.Wherein organic coloring pigment has high infrared emittance mostly, thereby less use.Use the more metal oxide that is in the inorganic coloring pigment, metal hydroxides, sulfide etc., its emittance is also higher, add that simultaneously mineral dye is when mixing with organic adhesion agent, easily dispersion is inhomogeneous, and infrared emittance generally all raises, so the screening of tinting pigment is the difficult point of preparation infrared stealth coating or clothes, stealthy net etc. always.The method of current use is to add the infrared emittance that metallic pigment reduce coating again after adding tinting pigment.But the adding of metallic pigment has certain limit and is unfavorable for the stealthy of radar wave.In order to realize the compatible stealthy of infrared and radar wave, now to study more tinting pigment is through mixing or the compound nano-inorganic substance, as complex metal oxides, and blended metal oxide.Because the small-size effect of nano particle, these inorganic complex great majority still have higher powder infrared emittance, and in use owing to disperse the inhomogeneous infrared emittance that also can further increase coating.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of Collagon base nanometer infrared low-emissivity tinting pigment and preparation method.To overcome existing nano-metal-oxide tinting pigment infrared emittance height, mix uneven deficiency with tackiness agent.
Technical scheme: the technical solution adopted for the present invention to solve the technical problems is: this granules of pigments has nucleocapsid structure, and promptly kernel is nano-metal-oxide or nano composite metal oxide tinting pigment, and outer field shell is the collagen graft copolymer.
At first in water, tropocollagen molecule is adsorbed on metal oxide tinting pigment nano grain surface, promptly utilize the interface interaction between tropocollagen molecule and metal oxide nanoparticles surface, as hydrogen bond, charge neutrality effect, surface adsorption one deck wetting ability collagen at metal oxide nanoparticles, the emulsion graft copolymerization that causes by initiator reacts on 50～60 ℃ in ethanol or methanol aqueous solution, grafting oleophylic side chain on the tropocollagen molecule on metal oxide nanoparticles surface then.Here used tinting pigment is metal oxide or complex metal oxides, and as ferric oxide, aluminum oxide, Indium sesquioxide, chromic oxide, zinc oxide, tin-doped indium oxide etc., its grain diameter should be generally below the 50nm less than 100nm.The infrared emittance of these nano-metal-oxides is all more than 0.80.Collagen is a kind of natural organic macromolecule, constitute by three peptide chain spirals, storing the electric dipole and the molecule bound charge of higher density, present tangible electret state, has polarization, performances such as static, and be rich in the molecule metal oxide, metal ion has the O of affinity, elements such as N, and the atom number on metal oxide nanoparticles surface is many, the atom of these atoms and granule interior is different, lack adjacent atom on every side many dangling bondss are arranged, play pendulum, it mainly is non-electric neutrality, three kinds of situations of non-stoichiometric and coordination less than, thereby the strong trend of these atoms and the oriented stable state transformation of chemical bond, have higher activity, so collagen can be modified and the stable metal oxide nano-particles.We utilize collagen macromole and metal oxide nanoparticles table and between reaction, in the aqueous solution, make the collagen macromole be adsorbed on the metal oxide nanoparticles surface.Contained active group such as C=O group in the collagen macromole, carboxylic group on the side chain etc., reaction such as hydrogen bond, charge neutrality, coordination takes place with the lip-deep unsatuated metal ligand ion of metal oxide nanoparticles or non-electric neutrality point isoreactivity point and be adsorbed on particle surface, thereby the metal oxide particle surface is modified, and the collagen macromole has been eliminated the active site of nano grain surface thereby has also been stablized metal oxide nanoparticles in the absorption of particle surface.Be adsorbed on the active group that the lip-deep tropocollagen molecule of metal oxide nanoparticles still has a part, can continue to carry out graft copolymerization with some vinyl monomers.We utilize free radical to cause the emulsion graft copolymerization method, in temperature of reaction is 50～60 ℃, in ethanol or the methanol in water and ceric ammonium nitrate, Diisopropyl azodicarboxylate, persulphates etc. can provide the initiator of free radical to cause down, on the collagen macromole on metal oxide nanoparticles surface, introduced the lipophilicity side chain, grafted oleophylic side chain is the methyl methacrylate side chain on the tropocollagen molecule on metal oxide nanoparticles surface, butyl methacrylate, the N-vinyl pyrrolidone, Jia Jibingxisuanyizhi, methyl acrylate, ethyl propenoate, butyl acrylate, N, the N-DMAA makes all had good dispersiveness by the metal oxide tinting pigment nano particle behind the collagen graft copolymer parcel in organic solvent and water.The prepared general particle diameter of metal oxide tinting pigment nano particle through collagen graft copolymer parcel is no more than 100nm, outer field collagen graft copolymer shell thickness generally is no more than 20nm, collagen content in its aqueous solution is 0.5～1%, pH value of aqueous solution is controlled at 3.5～7, the tropocollagen molecule adsorption time is 24～48h, to reach adsorption equilibrium.The aqueous solution is methanol aqueous solution or aqueous ethanolic solution, wherein methyl alcohol or ethanol: water=1: 1～3.
Because the reaction on tropocollagen molecule and metal oxide nanoparticles surface has changed the molecule on collagen and the metal oxide particle contact interface, the mode of motion of atom, be equivalent to form an interfacial layer all different with the body of tropocollagen molecule layer and metal oxide particle at the biphase contact interface, thereby make the tinting pigment behind the absorption tropocollagen molecule receive particle to have lower infrared emittance, simultaneously because the active site of nanoparticle surface has been eliminated in the absorption of tropocollagen molecule, thereby also stablized nanoparticle.
Beneficial effect: the invention has the beneficial effects as follows, can be simultaneously at the natural colored that keeps virgin metal oxide coloring pigment, effectively reduce the infrared emittance of virgin metal oxide coloring pigment, and in organic solvent and water, all can be uniformly dispersed, also can uniform distribution in coating.Simultaneously can be according to selected adhesive type, select different grafted monomer for use, as select for use polyurethane tackifier can select acrylamide monomers for use, because this class polymer of monomers and polyurethane tackifier have good intermiscibility, if select for use resol class tackiness agent then can select acrylic ester monomer for use.This invention making method is simple, can show the color of kernel metal oxide.Owing to the coating of outer collagen graft copolymer, stable metal oxide coloring pigment nano particle makes nano particle be difficult for reuniting, and is uniformly dispersed, can uniform distribution in camouflage coating simultaneously.In addition, have interfacial interaction between the collagen layer of absorption and the metal oxide nanoparticles, the tinting pigment particle after make coating has lower infrared emittance, minimumly reaches 0.45.
This tinting pigment grain diameter is not more than 100nm, has nucleocapsid structure.Shell is the collagen graft copolymer, and kernel is a metal oxide nanoparticles.This particle not only all disperses evenly in organic solvent and water but also has lower infrared emittance, can also keep the original color of its kernel metal oxide simultaneously, has infrared low-emissivity (0.45～0.65) at 8～14 mu m wavebands.
Embodiment
That make by sol-gel method or buy metal oxide nanoparticles, particle diameter is at 20～50nm.0.4～1g metal oxide nanoparticles places 0.5～1% the collagenic aqueous solution of 100～150ml, adsorption time be 24～48h to reach adsorption equilibrium, the pH value of solution is controlled at about 3.5～7.Adsorbed solution is through centrifugation, and 40 ℃～50 ℃ dry down.In reactor, add exsiccant collagen-oxide particle and quantitative methanol aqueous solution or aqueous ethanolic solution (methyl alcohol or ethanol: water=1: 1～3); behind ultrasonic concussion 5～15min; under nitrogen protection, be warming up to 50～60 ℃, add required monomer and initiator, reaction 14～24h.Reaction mixture separates through suction filtration, washes with water, and 40～50 ℃ dry down.Dried sample is looked added monomer and is adopted different solvent extractions, purifies to remove homopolymer.
Example 1, with the Indium sesquioxide nano particle that sol-gel method is made, particle diameter is about 30nm.0.8g the Indium sesquioxide nano particle, place 0.5% the collagenic aqueous solution of 100ml, pH is 5.3, absorption 24h. is centrifugal, 40 ℃ of dryings.In a four-necked bottle, add the 60ml methanol aqueous solution (methyl alcohol: water=1: 1) and 0.5g adsorb Indium sesquioxide particle behind the collagen, ultrasonic concussion 5 minutes.Under nitrogen protection, be warming up to 50 ℃, add the Diisopropyl azodicarboxylate initiator of the ceric ammonium nitrate of the methyl methacrylate monomer of 0.5mol/L and 0.01mol/L and 0.01mol/L or only add the ceric ammonium nitrate initiator of 0.01mol/L, reaction 16h.Reaction product is separated through suction filtration, drying.The Indium sesquioxide nanoparticle of dried collagen-methylmethacrylate copolymer parcel is removed homopolymer through acetone extract.Grain diameter is 45nm, and the powder infrared emittance is 0.58.
Example 2, the aluminium oxide nano particle that sol-gel method is made, particle diameter is about 40nm.0.6g the aluminium oxide nano particle, place 0.6% collagenic aqueous solution of 100ml, pH value of solution is 5.1, absorption 24h is centrifugal, 40 ℃ of dryings.In a four-necked bottle, add the 70ml aqueous ethanolic solution (ethanol: water=1.1) and 0.6g adsorb aluminium oxide particles behind the collagen, ultrasonic concussion 6 minutes.Under nitrogen protection, be warming up to 50 ℃, add the methyl methacrylate monomer of 0.45mol/L and the ceric ammonium nitrate initiator of 0.01mol/L, reaction 20h.Reaction product is separated through suction filtration, drying.Dried product is removed homopolymer through acetone extract.The alumina particle particle diameter of collagen-methylmethacrylate copolymer parcel is 60nm, and the powder infrared emittance is 0.52.
Claims (8)
1, a kind of Collagon base nanometer infrared low-emissivity tinting pigment is characterized in that this granules of pigments has nucleocapsid structure, and promptly kernel is nano-metal-oxide or nano composite metal oxide tinting pigment, and outer field shell is the collagen graft copolymer.
2, Collagon base nanometer infrared low-emissivity tinting pigment according to claim 1, it is characterized in that metal oxide or complex metal oxides are a kind of or its mixture in ferric oxide, aluminum oxide, Indium sesquioxide, chromic oxide, the tin-doped indium oxide, this kind tinting pigment grain diameter is less than 100nm.
3, Collagon base nanometer infrared low-emissivity tinting pigment according to claim 1, it is characterized in that: metal oxide tinting pigment nano particle is a kernel, shell is the collagen graft copolymer, and whole nucleocapsid particle diameter is less than 100nm, and outer field collagen graft copolymer thickness of the shell is less than 20nm.
4, a kind of preparation method of Collagon base nanometer infrared low-emissivity tinting pigment as claimed in claim 1, it is characterized in that: at first in water, tropocollagen molecule is adsorbed on metal oxide tinting pigment nano grain surface, promptly utilize the interface interaction between tropocollagen molecule and metal oxide nanoparticles surface, as hydrogen bond, the charge neutrality effect, surface adsorption one deck wetting ability collagen at metal oxide nanoparticles, the emulsion graft copolymerization that causes by initiator reacts on 50～60 ℃ in ethanol or methanol aqueous solution, grafting oleophylic side chain on the tropocollagen molecule on metal oxide nanoparticles surface then.
5, the preparation method of Collagon base nanometer infrared low-emissivity tinting pigment according to claim 4 is characterized in that in the emulsion graft copolymerization reaction that causes by initiator, and initiator is a kind of in ceric ammonium nitrate, Diisopropyl azodicarboxylate, the persulphate.
6, according to the preparation method of claim 4 or 5 described Collagon base nanometer infrared low-emissivity tinting pigments, it is characterized in that grafted oleophylic side chain is methyl methacrylate side chain, butyl methacrylate, N-vinyl pyrrolidone, Jia Jibingxisuanyizhi, methyl acrylate, ethyl propenoate, butyl acrylate, N on the tropocollagen molecule on metal oxide nanoparticles surface, the N-DMAA makes all had good dispersiveness by the metal oxide tinting pigment nano particle behind the collagen graft copolymer parcel in organic solvent and water.
7, the preparation method of Collagon base nanometer infrared low-emissivity tinting pigment according to claim 4, it is characterized in that the collagen content in the aqueous solution is 0.5～1%, pH value of aqueous solution is controlled at 3.5～7, and the tropocollagen molecule adsorption time is 24～48h, to reach adsorption equilibrium.
8,, it is characterized in that the aqueous solution is methanol aqueous solution or aqueous ethanolic solution, wherein methyl alcohol or ethanol: water=1: 1～3 according to the preparation method of claim 4 or 7 described Collagon base nanometer infrared low-emissivity tinting pigments.
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| CN 200310112734 CN1228398C (en) | 2003-12-24 | 2003-12-24 | Collagen base nano infrared low emissivity colouring pigment and preparing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008080908A2 (en) * | 2006-12-28 | 2008-07-10 | Nuplex Resins B.V. | Film forming composition comprising modified nanoparticles and modified nanoparticles for use in film forming compositions |
| CN103525363A (en) * | 2013-09-30 | 2014-01-22 | 东南大学 | Core-shell type infrared composite material and preparation method thereof |
| CN108748527A (en) * | 2018-05-03 | 2018-11-06 | 阜南县铭钰柳木工艺品有限公司 | A kind of preparation method for the paint vehicle additive promoting the knitting service life |
| CN108794970A (en) * | 2018-06-11 | 2018-11-13 | 安徽四季能源科技有限公司 | A kind of preparation method for the nano metal pigment master batch that coloring effect is good |
| CN108976688A (en) * | 2018-06-11 | 2018-12-11 | 安徽四季能源科技有限公司 | A kind of high-stability nano metallic pigments master batch |
| CN113683826A (en) * | 2020-05-16 | 2021-11-23 | 上海冠旗电子新材料股份有限公司 | Special color master batch modifier with migration resistance, high temperature resistance and reduced pigment and auxiliary agent consumption |
-
2003
- 2003-12-24 CN CN 200310112734 patent/CN1228398C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008080908A2 (en) * | 2006-12-28 | 2008-07-10 | Nuplex Resins B.V. | Film forming composition comprising modified nanoparticles and modified nanoparticles for use in film forming compositions |
| WO2008080908A3 (en) * | 2006-12-28 | 2008-08-21 | Nuplex Resins Bv | Film forming composition comprising modified nanoparticles and modified nanoparticles for use in film forming compositions |
| CN103525363A (en) * | 2013-09-30 | 2014-01-22 | 东南大学 | Core-shell type infrared composite material and preparation method thereof |
| CN108748527A (en) * | 2018-05-03 | 2018-11-06 | 阜南县铭钰柳木工艺品有限公司 | A kind of preparation method for the paint vehicle additive promoting the knitting service life |
| CN108794970A (en) * | 2018-06-11 | 2018-11-13 | 安徽四季能源科技有限公司 | A kind of preparation method for the nano metal pigment master batch that coloring effect is good |
| CN108976688A (en) * | 2018-06-11 | 2018-12-11 | 安徽四季能源科技有限公司 | A kind of high-stability nano metallic pigments master batch |
| CN113683826A (en) * | 2020-05-16 | 2021-11-23 | 上海冠旗电子新材料股份有限公司 | Special color master batch modifier with migration resistance, high temperature resistance and reduced pigment and auxiliary agent consumption |
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| CN1228398C (en) | 2005-11-23 |
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