CN103724854A - Nano-composite near-infrared absorbent and preparation method thereof - Google Patents
Nano-composite near-infrared absorbent and preparation method thereof Download PDFInfo
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- CN103724854A CN103724854A CN201310641661.8A CN201310641661A CN103724854A CN 103724854 A CN103724854 A CN 103724854A CN 201310641661 A CN201310641661 A CN 201310641661A CN 103724854 A CN103724854 A CN 103724854A
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Abstract
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a near-infrared absorbent and a preparation method thereof. According to the invention, an organic semi-conductor material of poly-(3, 4 ethylene PEDT) (PEDOT) is compounded with a nano metal oxide to prepare the near-infrared absorbent, the PEDOT and the nano metal oxide are dispersed in a solvent under the condition without additives such as a dispersant to obtain a stable existing dispersion liquid. The near-infrared absorbent has higher absorbability at a near-infrared region, and can be applied to a filtering material, a detection-preventing material, a laser protection material, an infrared fake-proof material and the like.
Description
Technical field
The invention belongs to absorbing material technical field, particularly a kind of near infrared absorbent and preparation method thereof.
Background technology
Near infrared absorbent is to the absorbent class material of near-infrared band hertzian wave tool, and it has a wide range of applications in military affairs and civil area, has now developed the near infrared absorbent of the different purposes of numerous kinds.Wherein, the compound near infrared absorbent of organic functional material and nano particle has become study hotspot now.
Nano particle is because of its special size, thereby produced the properties such as electricity, magnetics, optics, absorption.Nano material is made nano-scale as electromagnetic wave absorbent material by the material originally with wave-sucking performance, and the peculiar property that utilizes material to have when nanoscale, makes it to the receptivity of light wave, on original basis, be further improved.Nano particle has stronger absorption to short-wave band hertzian wave conventionally, and will make it in long-wave band, have absorption just need to carry out composite modified to it.Types of functionality material is carried out in microscopic dimensions to the hybrid material that hydridization is made, the function that can carry out single-material is compound, performance complement and optimization.Be different from traditional matrix material, organic materials is generally nanoscale with the phase microcell of nano material matrix material, sometimes even little compound to molecular level, and phase interface area is very large, and interfacial interaction is strong.Because the character of matrix material is not only relevant with the character of each component, and closely related with form and its interphase interface character of each component phase, wherein both play vital effect to the bulk property that determines material afterwards.Because organic materials and nano material matrix material may be in conjunction with desirable different precursor components character in one, and be not simply add and, under the synergy of component, even can produce the not available new property of some parents therein.
CN1435451A has described a kind of preparation method of nano combined shielding infrared coating, by by nano-metal-oxide respectively or combination add in paint vehicle, simply after sand mill grinds evenly, obtain the matrix material with infrared shielding performance.Its technique is comparatively simple.But be difficult to guarantee the dispersion stabilization of gained matrix material.CN1821315A has described a kind of polyaniline-coated nano-TiO
2and polyaniline-coated TiO
2the preparation method of metal whisker composite, makes TiO
2in UV-light region, there is new absorption peak, not only absorbed UV-light, can also well absorb visible and near infrared light.According to it, describe, prepared matrix material in UV-light region, all there is absorption visible region, near infrared light region, shows that it is not fine that made matrix material is selected absorptivity and the transparency.
Organic semiconductor material PEDOT(gathers (3,4-rthylene dioxythiophene)) be a kind of conductive polymers with pi-conjugated backbone, extremely extensive in photoelectric field application.But the PEDOT electroconductibility of eigenstate is very poor, and insoluble.
At present, near infrared absorbent has been widely used in military affairs and civil area.But because it relates to Sensitive Domain, be difficult to obtain the complete research idea of excellent performance near infrared absorbent from foreign literature.How comparatively complicated existing commercially available near infrared absorbent syntheti c route is.In nano material, prepare aspect absorbing material, conventionally use precious metal and oxide compound thereof, and be used for long wave and absorb, at near-infrared band, absorb application less.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, and near infrared absorbent syntheti c route complexity, preparation cost is high, and is used for long wave absorption, and what for shortwave, absorb is less.
In order to solve this technical problem, the technical solution used in the present invention is:
The invention provides a kind of nano combined near infrared absorbent, calculate by weight, described absorption agent comprises
Wherein, PEDOT is dispersed in solution,
Doping agent can be selected following material:
Sodium polystyrene sulfonate (PSS, Mn=20000～200000),
Sodium styrene sulfonate-Propylene glycol monoacrylate multipolymer (mol ratio of Sodium styrene sulfonate and HPA is 3～30:1 for PSS-HPA, Mn=20000～200000 of PSS-HPA),
Sodium styrene sulfonate-glycidyl methacrylate copolymer (mol ratio of Sodium styrene sulfonate and GMA is 3～30:1 for PSS-GMA, Mn=20000～200000 of PSS-GMA),
Sodium styrene sulfonate-butyl acrylate copolymer (mol ratio of Sodium styrene sulfonate and BA is 3～30:1 for PSS-BA, Mn=20000～200000 of PSS-BA)
PSS-HPA, PSS-GMA, the preparation of PSS-BA is by HPA, GMA, BA is mixed to join stirring and dissolving in appropriate amount of deionized water with Sodium styrene sulfonate according to certain mol proportion respectively, vacuumize logical nitrogen, 80 ℃ of left and right of temperature of reaction, add initiator ammonium persulfate, reaction 2～6h stopped reaction, aftertreatment obtains the PSS-HPA of corresponding copolymerization ratio, PSS-GMA, PSS-BA multipolymer.
Sodium sulfanilate, p-methyl benzenesulfonic acid, thionamic acid, Witco 1298 Soft Acid or camphorsulfonic acid;
Above-mentioned nano-metal-oxide is selected from ZnO, TiO
2, ITO or Al
2o
3, median size is 1～200nm, dispersion medium is selected water.
The present invention also provides a kind of preparation method of above-mentioned nano combined near infrared absorbent, is by PEDOT aqueous dispersions is mixed and made with nano-metal-oxide, is specially:
(1) preparation of PEDOT aqueous dispersions by the doping agent stirring and dissolving that is added to the water, adds EDOT(3,4-ethene dioxythiophene under agitation condition in system), catalyzer and oxygenant, after reaction for some time, obtain PEDOT aqueous dispersions,
Oxygenant is selected Sodium Persulfate, ammonium persulphate, Potassium Persulphate or the arbitrary proportion mixture between them, and the mass ratio of oxygenant and EDOT is 0.5～2.5:1,
Catalyzer is selected iron(ic) chloride, iron nitrate, ferric sulfate or the arbitrary proportion mixture between them, and the mass ratio of catalyzer and EDOT is 0.001～0.02:1,
In addition, the part by weight of EDOT and doping agent is 1:1～20, and the part by weight of EDOT and water is 1:10～1000, and the reaction times of step (1) is 0.5～48h;
(2) preparation of near infrared absorbent, in the PEDOT aqueous dispersions making in step (1), adds nano-metal-oxide or its aqueous dispersions, and be uniformly dispersed and obtain PEDOT and the compound near infrared absorbent of metal oxide nanoparticles,
Nano-metal-oxide weight, with the weight ratio of the EDOT adding in step (1) be 0.05～2:1.
The compound near infrared absorbent of the PEDOT that the present invention obtains by simple process flow and nano-metal-oxide, without the dispersion liquid that can obtain stable existence under the auxiliary agent conditions such as dispersion agent, and adopt water be solvent, environmental protection, applicable suitability for industrialized production can.The prepared absorption agent of the present invention can have good absorption to hertzian wave within the scope of 500～1000nm, can be used for filtering material, detection-proof material, laser protective material, infrared anti-forging material etc.
Accompanying drawing explanation
Fig. 1 is gained near infrared absorbent in case study on implementation 1, by ultraviolet-visible-near-infrared absorption spectrogram of glassy membrane frame institute film forming;
Fig. 2 is the ultraviolet-visible-near infrared light reflection spectrogram of two identical material cottons, and wherein one is infiltrated in case study on implementation 1 and after gained absorption agent 1h, takes out 70 ℃ of oven dry, does not do any processing for latter one.
Embodiment
Embodiment 1
(1) 6g PSS is joined contain 350g deionized water reaction vessel in, stirring and dissolving, under agitation condition, slowly drip 1g EDOT, after add 2.42g ammonium persulphate and 0.0056g ferric sulfate, under room temperature, continue to stir 12h, by gas chromatograph (GC1690) monitoring EDOT residual volume, judge reaction end therebetween, solution from the colourless blueness that becomes, obtains PEDOT/PSS aqueous dispersions gradually.
(2) 0.87g nano-ZnO solid particulate is slowly joined in 42.63g deionized water under agitation condition, with ultrasonic cleaner ultrasonic concussion 30min, being uniformly dispersed and obtaining solid content is 2% nano-ZnO aqueous dispersions.
(3) by step 2) solid content that obtains is 2% nano-ZnO aqueous dispersions slowly joins in step 1) gained PEDOT/PSS dispersion liquid under agitation condition, with the ultrasonic concussion of ultrasonic cleaner 30min, be uniformly dispersed and can obtain PEDOT and the compound near infrared absorbent of nano-ZnO.
Gained absorption agent is watered to drying and forming-film in glassy membrane frame in right amount, thickness is 0.02mm, by ultraviolet-visible spectrophotometer (UV-2450), in 200～1000nm wavelength region, test its absorptive character, it can have good absorption to the hertzian wave of 600～900nm.Maximum absorption wavelength is 855nm.
Embodiment 2
(1) by the mol ratio of 1gPSS-GMA(Sodium styrene sulfonate and GMA, be 3:1) join contain 10g deionized water reaction vessel in, stirring and dissolving, under agitation condition, slowly drip 1g EDOT, after add 2.35g Sodium Persulfate and 0.02g iron(ic) chloride, under room temperature, continue to stir 0.5h, by gas chromatograph (GC1690) monitoring EDOT residual volume, judge reaction end therebetween, solution from the colourless blueness that becomes, obtains PEDOT/PSS-GMA aqueous dispersions gradually.
(2) 0.05g nano-ITO solid particulate is slowly joined in 0.05g deionized water under agitation condition, with ultrasonic cleaner ultrasonic concussion 10min, being uniformly dispersed and obtaining solid content is 50% nano-ITO aqueous dispersions.
(3) by step 2) solid content that obtains is 50% nano-ITO aqueous dispersions slowly joins in step 1) gained PEDOT/PSS-GMA dispersion liquid under agitation condition, with the ultrasonic concussion of ultrasonic cleaner 20min, be uniformly dispersed and can obtain PEDOT and the compound near infrared absorbent of nano-ITO.
Gained absorption agent is watered to drying and forming-film in glassy membrane frame in right amount, thickness is 0.02mm, by ultraviolet-visible spectrophotometer (UV-2450), in 200～1000nm wavelength region, test its absorptive character, it can have good absorption to the hertzian wave of 700～1000nm.Maximum absorption wavelength is 900nm.
Embodiment 3
(1) by the mol ratio of 20gPSS-BA(Sodium styrene sulfonate and BA, be 8:1) join contain 500g deionized water reaction vessel in, stirring and dissolving, under agitation condition, slowly drip 1g EDOT, after add 0.95g Potassium Persulphate and 0.0028g iron nitrate, under room temperature, continue to stir 48h, by gas chromatograph (GC1690) monitoring EDOT residual volume, judge reaction end therebetween, solution from the colourless blueness that becomes, obtains PEDOT/PSS-BA aqueous dispersions gradually.
(2) by 2g nanometer Al
2o
3solid particulate slowly joins in 398g deionized water under agitation condition, and with ultrasonic cleaner ultrasonic concussion 40min, being uniformly dispersed and obtaining solid content is 0.5% nanometer Al
2o
3aqueous dispersions.
(3) by step 2) solid content that the obtains nanometer Al that is 0.5%
2o
3aqueous dispersions slowly joins in step 1) gained PEDOT/PSS-BA dispersion liquid under agitation condition, with the ultrasonic concussion of ultrasonic cleaner 60min, is uniformly dispersed and can obtains PEDOT and nanometer Al
2o
3compound near infrared absorbent.
Gained absorption agent is watered to drying and forming-film in glassy membrane frame in right amount, thickness is 0.02mm, by ultraviolet-visible spectrophotometer (UV-2450), in 200～1000nm wavelength region, test its absorptive character, it can have good absorption to the hertzian wave of 700～900nm.Maximum absorption wavelength is 860nm.
Embodiment 4
(1) by the mol ratio of 4gPSS-HPA(Sodium styrene sulfonate and HPA, be 15:1) join contain 200g deionized water reaction vessel in, stirring and dissolving, under agitation condition, slowly drip 1g EDOT, after add 2.5g ammonium persulphate and 0.0084g ferric sulfate, under room temperature, continue to stir 10h, by gas chromatograph (GC1690) monitoring EDOT residual volume, judge reaction end therebetween, obtain PEDOT/PSS-HPA aqueous dispersions.
(2) by commercially available 26g solid content, be 4%(massfraction) nano-TiO
2aqueous dispersions slowly joins in step 1) gained PEDOT/PSS-HPA dispersion liquid under agitation condition, with the ultrasonic concussion of ultrasonic cleaner 30min, is uniformly dispersed and can obtains PEDOT and nanometer Al
2o
3compound near infrared absorbent.
Gained absorption agent is watered to drying and forming-film in glassy membrane frame in right amount, thickness is 0.02mm, by ultraviolet-visible spectrophotometer (UV-2450), in 200～1000nm wavelength region, test its absorptive character, it can have good absorption to the hertzian wave of 800～1000nm.Maximum absorption wavelength is 920nm.
Embodiment 5
(1) 8g p-methyl benzenesulfonic acid is joined contain 400g deionized water reaction vessel in, stirring and dissolving, under agitation condition, slowly drip 1g EDOT, after add 2.40g Sodium Persulfate and 0.012g iron(ic) chloride, under room temperature, continue to stir 4h, by gas chromatograph (GC1690) monitoring EDOT residual volume, judge reaction end therebetween, obtain PEDOT/ p-methyl benzenesulfonic acid aqueous dispersions.
(2) 2g nano-ZnO solid nano particle is slowly joined under agitation condition in step 1) gained PEDOT/ p-methyl benzenesulfonic acid dispersion liquid, with the ultrasonic concussion of ultrasonic cleaner 40min, be uniformly dispersed and can obtain PEDOT and the compound near infrared absorbent of nano-ZnO.
Gained absorption agent is diluted to 10 with deionized water
-4g/ml, tests its absorptive character by ultraviolet-visible spectrophotometer (UV-2450) in 200～1000nm wavelength region, and it can have good absorption to the hertzian wave of 600～900nm.Maximum absorption wavelength is 840nm.
Claims (7)
1. a nano combined near infrared absorbent, is characterized in that: calculate by weight, described absorption agent comprises
2. nano combined near infrared absorbent as claimed in claim 1, it is characterized in that: described doping agent is selected from PSS, PSS-HPA, PSS-GMA, PSS-BA, Sodium sulfanilate, p-methyl benzenesulfonic acid, thionamic acid, Witco 1298 Soft Acid or camphorsulfonic acid.
3. nano combined near infrared absorbent as claimed in claim 1, is characterized in that: described nano-metal-oxide is selected from ZnO, TiO
2, ITO or Al
2o
3, median size is 1～200nm.
4. the preparation method of the nano combined near infrared absorbent as described in claims 1 to 3 any one, is characterized in that: described method is, by PEDOT aqueous dispersions, to mix with nano-metal-oxide.
5. the preparation method of nano combined near infrared absorbent as claimed in claim 4, is characterized in that: step is
(1) preparation of PEDOT aqueous dispersions by the doping agent stirring and dissolving that is added to the water, adds EDOT, catalyzer and oxygenant under agitation condition in system, after reaction for some time, obtains PEDOT aqueous dispersions;
(2) preparation of near infrared absorbent, in the PEDOT aqueous dispersions making in step (1), adds nano-metal-oxide or its aqueous dispersions, is uniformly dispersed and obtains PEDOT and the compound near infrared absorbent of metal oxide nanoparticles.
6. the preparation method of nano combined near infrared absorbent as claimed in claim 5, it is characterized in that: the oxygenant described in step (1) is selected from, Sodium Persulfate, ammonium persulphate, Potassium Persulphate or its mixture, the mass ratio of oxygenant and EDOT is 0.5～2.5:1.
7. the preparation method of nano combined near infrared absorbent as claimed in claim 5, it is characterized in that: the catalyzer described in step (1) is selected from, iron(ic) chloride, iron nitrate, ferric sulfate or its mixture, the mass ratio of catalyzer and EDOT is 0.001～0.02:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104193972A (en) * | 2014-09-04 | 2014-12-10 | 常州大学 | Preparation method for PEDOT (polymer ethylenedioxy thiophene)/nano titanium dioxide aqueous dispersion |
| CN112980030A (en) * | 2021-02-07 | 2021-06-18 | 电子科技大学 | Organic composite material for personal infrared thermal management and preparation method thereof |
| CN113248138A (en) * | 2021-06-03 | 2021-08-13 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
| CN113419401A (en) * | 2021-06-09 | 2021-09-21 | 安徽强邦新材料股份有限公司 | Photosensitive emulsion for heat-sensitive positive image CTP plate and preparation method thereof |
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| CN102108271A (en) * | 2010-12-23 | 2011-06-29 | 陕西科技大学 | Method for preparing water transferring glue |
| CN103131254A (en) * | 2013-02-05 | 2013-06-05 | 陕西科技大学 | Zinc-oxide-containing dual-wavelength light-absorption aquosity anti-forgery ink easer preparation technology |
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Patent Citations (3)
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| CN101407575A (en) * | 2008-12-08 | 2009-04-15 | 北京服装学院 | High dispersibility nano-scale poly (3,4-ehtylene dioxythiophene), preparation and use thereof |
| CN102108271A (en) * | 2010-12-23 | 2011-06-29 | 陕西科技大学 | Method for preparing water transferring glue |
| CN103131254A (en) * | 2013-02-05 | 2013-06-05 | 陕西科技大学 | Zinc-oxide-containing dual-wavelength light-absorption aquosity anti-forgery ink easer preparation technology |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193972A (en) * | 2014-09-04 | 2014-12-10 | 常州大学 | Preparation method for PEDOT (polymer ethylenedioxy thiophene)/nano titanium dioxide aqueous dispersion |
| CN104193972B (en) * | 2014-09-04 | 2016-05-18 | 常州大学 | A kind of preparation method of PEDOT/ nano titanium oxide aqueous dispersion |
| CN112980030A (en) * | 2021-02-07 | 2021-06-18 | 电子科技大学 | Organic composite material for personal infrared thermal management and preparation method thereof |
| CN112980030B (en) * | 2021-02-07 | 2022-01-25 | 电子科技大学 | Organic composite material for personal infrared thermal management and preparation method thereof |
| CN113248138A (en) * | 2021-06-03 | 2021-08-13 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
| CN113248138B (en) * | 2021-06-03 | 2021-10-15 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
| CN113419401A (en) * | 2021-06-09 | 2021-09-21 | 安徽强邦新材料股份有限公司 | Photosensitive emulsion for heat-sensitive positive image CTP plate and preparation method thereof |
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