CN101649111B - Molecular sieve polyaniline compound wave-absorbing material and preparation method thereof - Google Patents
Molecular sieve polyaniline compound wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a molecular sieve polyaniline compound wave-absorbing material and a preparation method thereof, belonging to the technical field of wave-absorbing material preparation. The preparation method comprises the following steps: wrapping polyaniline high-molecular compounds in a pore path and on the surfaces of molecular sieves, wherein; the molecular sieves is synthesized by a hydrothermal method with a surface active agent or a templating agent; and then preparing the molecular sieve polyaniline compound wave-absorbing material by polymerizing aniline monomers in a system containing the molecular sieves. The mass ratio of the molecular sieves to the polyaniline is 1 to 0.1- 10, the types of the molecular sieves are LTA, FDU-15, MFI, SBA-15, SBA-16, MCM-41 or MCM-48 porous molecular sieves which eliminate the surface active agent or the templating agent inside the pore path. The novel wave-absorbing material has wide wave frequency absorption range, good absorbing effect, light weight, and the like.
Description
Technical field
The invention belongs to the preparing technical field of absorbing material, be specifically related to a kind of molecular sieve polyaniline compound wave-absorbing material and preparation method thereof.
Technical background
Along with modern science and technology and rapid economy development, this functional materials that begins most to be used by the military of absorbing material has been widely used in civil area, as anti-electromagnetic radiation, and microwave attenuation device, electromagnetic compatibility equipment etc.But existing absorbing material exists quality heavier, and suction ripple scope is little, shortcomings such as stable mechanicalness difference, and this has restricted the potentiality of using greatly.
Molecular screen material has advantages such as high mechanical strength, resist chemical and biological corrosion, high temperature resistant, light weight.Simultaneously, different molecular sieves has different pore passage structures and pore size, the distribution of these duct rules, the conducting polymer composite that has absorbing property therein in the assembling, not only can improve the wave-absorbing effect of different-waveband, can also make it have wave-absorbing effect, simultaneously because the adding of molecular sieve in wideer frequency range, the physical strength of material, erosion resistance all can improve, and the quality of material then can reduce.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of molecular sieve polyaniline compound wave-absorbing material and this absorbing material, and its absorption of electromagnetic wave effect at different-waveband is tested.(1～18GHz, 18～26.5GHz, 26.5～40GHz) hertzian wave all have good assimilation effect to this absorbing material, and have the advantage of the little light weight of density with respect to traditional absorbing material to the wideband section.
Molecular sieve polyaniline compound wave-absorbing material of the present invention is characterized in that: the duct of molecular sieve and finishing polyaniline, the mass ratio of molecular sieve and polyaniline is 1: 0.1～10; Further, the mass ratio of molecular sieve and polyaniline is 1: 0.3～6, and molecular sieve type is LTA, FDU-15, MFI, SBA-15, SBA-16, MCM-41 or the MCM-48 porous molecular screen of tensio-active agent or template in the removal duct.
Molecular sieve is a kind of silico-aluminate compound, mainly connects to form spacious skeleton structure by sial by oxo bridge, and uniform duct, a lot of apertures and marshalling, hole that internal surface area is very big are arranged in structure, and pore size is 0.5～20 nanometer.That molecular sieve has is high temperature resistant, corrosion-resistant, physical strength big, light weight, characteristics that specific surface area is big.Absorbing material of the present invention is under acidity, synthetic in the system that contains molecular sieve and aniline monomer.
The method for preparing molecular sieve polyaniline compound wave-absorbing material of the present invention, its step is as follows:
A) preparation mesopore molecular sieve FDU-15, SBA-15, SBA-16, MCM-41 or MCM-48, and remove tensio-active agent in the duct, or preparation MFI type micro porous molecular sieve, and remove template;
Synthesizing of mesoporous molecular sieve SBA-15: in 25ml distilled water, add surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene 0.4～1.6g, add 4～10ml massfraction after stirring evenly again and be 36～38% concentrated hydrochloric acid HCl and the tetraethoxy of 1～5ml, 40～50 ℃ of following stirring in water bath after 12～24 hours, 100～150 ℃ of crystallization are 1～10 day in the stainless steel cauldron of packing into; Then with mesopore molecular sieve after the filtering and washing drying, in retort furnace, burnt sample 2～3 hours down prior to 300～350 ℃, be raised to 500～600 ℃ again and burnt sample 5～6 hours, thereby the tensio-active agent in the removal duct, obtain removing the SBA-15 molecular sieve of tensio-active agent, molecular sieve bore diameter is distributed in 7～9nm.
Synthesizing of MFI type micro porous molecular sieve: with the TPAOH (TPAOH) of 0.16～1.6mol, the Al of 0.02～0.2mol
2(SO
4)
3.18H
2The tetraethoxy of O, 2～20mol, the H of 8～80mol
2O mixes to clarification, and crystallization is 12～18 hours under 120～140 ℃ of conditions; The removal of micro porous molecular sieve template: the dried molecular sieve of centrifuge washing in tube furnace or retort furnace 500～600 ℃ burnt sample 2～8 hours, obtain removing the molecular sieve of template, pore size distribution is at 0.6～0.7nm, granular size is at 100～200nm.
Mesopore molecular sieve SBA-16's is synthetic: add 0.3～0.6g surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene, 0.5～1.5g Repone K and 1～3g tetraethoxy in 30～35ml massfraction is 6～7% hydrochloric acid soln, stirred 20～30 hours under 35～40 ℃ of water-baths, 100～110 ℃ of crystallization are 12～36 hours in the stainless steel cauldron of packing into; Then with the mesopore molecular sieve that obtains after the filtering and washing drying, in retort furnace, burnt sample 2～3 hours down prior to 300～350 ℃, be raised to 500～600 ℃ again and burnt sample 5～6 hours, thereby the tensio-active agent in the removal duct, obtain removing the SBA-16 molecular sieve of tensio-active agent, molecular sieve bore diameter is distributed in 5～6nm;
Mesopore molecular sieve MCM-41's is synthetic: add hexadecyl brometo de amonio 1～2g in 15～30ml water, the adding massfraction is 24～26% ammoniacal liquor 8～15ml and tetraethoxy 3～6ml after stirring evenly, stirred at normal temperatures 5～6 hours, 100～150 ℃ of crystallization are 1～5 day in the stainless steel cauldron of packing into; Then with the mesopore molecular sieve that obtains after the filtering and washing drying, in retort furnace, burnt sample 2～3 hours down prior to 300～350 ℃, be raised to 500～600 ℃ again and burnt sample 5～6 hours, thereby the tensio-active agent in the removal duct, obtain removing the MCM-41 molecular sieve of tensio-active agent, molecular sieve bore diameter is distributed in 2～3nm;
Mesopore molecular sieve MCM-48's is synthetic: add hexadecyl brometo de amonio 3～5g and sodium hydroxide 0.1～0.5g in 10～30ml water, add tetraethoxy 4～6ml after the stirring and dissolving, after stirring 30～50 minutes at normal temperatures, 100～150 ℃ of crystallization are 2～5 days in the stainless steel cauldron of packing into; Then with the mesopore molecular sieve that obtains after the filtering and washing drying, in retort furnace, burnt sample 2～3 hours down prior to 300～350 ℃, be raised to 500～600 ℃ again and burnt sample 4～6 hours, thereby the tensio-active agent in the removal duct, obtain removing the MCM-48 molecular sieve of tensio-active agent, molecular sieve bore diameter is distributed in 2～3nm;
Mesopore molecular sieve FDU-15's is synthetic: the phenol that adds 0.5～1g in round-bottomed flask, heating in water bath to 40～45 ℃, add massfraction again and be sodium hydroxide solution 0.1～0.2g of 10～30%, stirring evenly the back, to add massfraction be formaldehyde solution 0.5～1.5g of 30～50%.Be warmed up to 65～75 ℃ and under this temperature, stirred 1～2 hour afterwards, be cooled to room temperature, regulate pH=6～8, steam moisture with Rotary Evaporators with the hydrochloric acid of massfraction 5～20%; Product 0.5～the 1.5g of previous step is joined in 10～30ml ethanol; add 0.5～1.5g surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene again; stirring at room 5～8 hours; change in the culture dish 100～120 ℃ 1～3 day down; product under nitrogen protection 350～700 ℃ burn the FDU-15 that sample obtained removing tensio-active agent in 2～6 hours, molecular sieve bore diameter is distributed in 5～7nm.
LTA type molecular sieve is produced by Tianjin recovery fine chemistry industry institute, and pore size is 0.39～0.4nm;
B) the high molecular assembling of polyaniline in the molecular sieve pore passage: by molecular sieve and aniline monomer mass ratio is 1: 6～0.3 to take by weighing respective sample, join quality and be 5～20 times of aniline monomers, massfraction and be in 4～5% the HCl solution, after the process ultrasonic agitation is uniformly dispersed, under the condition of ice bath, slowly add the oxygenant ammonium persulfate solution, the mass ratio of ammonium persulphate and aniline monomer is 1～5: 1, keeps the ice bath system to stir afterwards 6～10 hours;
C) will on the sample suction filtration, and, dry down at 60～100 ℃ with the alternately washing of acetone and water, obtain molecular sieve and polyaniline compound novel wave-absorbing material.
Wherein, adopt mesoporous molecular sieve SBA-15 with polyaniline compound absorbing material because the aperture of SBA-15 greatly (7～9nm), have the suction ripple scope of best wave-absorbing effect and broad.
Contain two kinds of cross one another pore canal system in the MFI type framework of molecular sieve, be parallel to axial ten Yuans S-type bendings in annular distance road of a, its turning is about 150 °, and this special structure makes hertzian wave be converted into more other energy.
Burning sample process described in the above-mentioned steps adopts temperature programming, 1～2 ℃ of heat-up rate per second;
What the present invention adopted is that the molecular sieve synthetic method is a hydrothermal synthesis method, and synthetic simple, energy consumption is low.
The present invention adopts is method at acidic conditions polymerization aniline monomer, and the polyaniline that obtains has the performance of conduction, and hertzian wave is produced electric consumption.
What the absorbing property test of NEW TYPE OF COMPOSITE absorbing material involved in the present invention was adopted is the arch bridge antenna method, in the hertzian wave darkroom, sample is tiled on the metal sheet of 200mmx200mm, thickness is 4mm, and (1～18GHz, 18～26.5GHz, 26.5～40GHz) carry out the absorption of electromagnetic wave measure of merit to it to divide three frequency ranges.
Description of drawings
Fig. 1: the x-ray diffraction pattern that synthetic SBA-15 molecular sieve is nanocrystalline;
Fig. 2: the scanning electron microscope diagram (a) of synthetic SBA-15 molecular sieve and transmission electron microscope figure (b);
Fig. 3: the nitrogen adsorption desorption curve (a) of synthetic SBA-15 molecular sieve and graph of pore diameter distribution (b);
Fig. 4: synthetic molecular sieve polyaniline matrix material absorbing property test.
Fig. 1 is the x-ray diffraction pattern of embodiment 1 synthetic SBA-15 molecular sieve, the series of features peak occurs occurring characteristic peak and about 1.5 ° near 0.8 ° as can be seen from the x-ray diffraction pattern peak of synthetic SBA-15 molecular sieve, this is typical SBA-15 pure phase;
Fig. 2 is the scanning electron microscope diagram (a) and the transmission electron microscope figure (b) of embodiment 1 synthetic synthetic SBA-15 molecular sieve, can obtain synthetic SBA-15 molecular sieve by figure (a) and become column, can obtain the two-dimentional hexagonal hole road that synthetic SBA-15 molecular sieve has rule by figure (b).
Fig. 3 is embodiment 1 synthetic SBA-15 molecular sieve nitrogen adsorption desorption curve and a graph of pore diameter distribution, can obtain mesoporous adsorption curve into standard by figure (a), is concentrated and is distributed in 9 nanometers in the aperture as can be known by figure (b);
Fig. 4 is the absorbing property figure of embodiment 3 synthetic molecular sieve polyaniline matrix materials, by figure can obtain this material in the attenuation by absorption of 6-16GHz, 18-40GHz all above-5dB, attenuation by absorption at 8-11GHz, 21-40GHz all reaches-more than the 10dB, and the maximum absorption decay can reach-18dB in the ripple frequency scope of 1-18GHz, illustrates that this material all has good assimilation effect to hertzian wave in the wideband section.
Embodiment
Embodiment 1:
Synthesizing of molecular sieve SBA-15:
(1) .0.8 gram surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene (P123) joins in 25 milliliters the distilled water, 4 milliliters of concentrated hydrochloric acids (massfraction 37%) join in the top solution and mix, add 1.7 milliliters of tetraethoxys again, 40 ℃ of following stirred solutions are 24 hours in having the water-bath of magnetic stirring apparatus, and solution changes over to and contained in the teflon-lined stainless steel cauldron in 100 ℃ of baking ovens crystallization (heating) 3 days;
(2). the SBA-15 molecular sieve that will obtain after will reacting is through suction filtration, and with deionized water wash 3 to 4 times, 85 ℃ of oven dry down, the sample that obtains is put into the retort furnace heating, is raised to 300 ℃ in 150 minutes in air, 300 ℃ kept 2 hours down, be raised to 550 ℃ with 250 minutes again, 550 ℃ keep after 5 hours down, thereby remove the tensio-active agent in the duct, naturally cool to room temperature then, obtain 0.45 gram mesoporous molecular sieve SBA-15.Pore size is 9 nanometers, is cylindrical particle not of uniform size.
The assembling of polyaniline in the molecular sieve pore passage
Take by weighing previous step synthetic SBA-15 molecular sieve 2.5 grams, join 220 milliliters of massfractions and be in 4.625% the hydrochloric acid soln, after stirring, add 14.2 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 31.7 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately clean with acetone and deionized water, dry down at 85 ℃ afterwards, (molecular sieve is 1: 5.7 with the calculated mass ratio of polyaniline to obtain molecular sieve polyaniline compound wave-absorbing material 16.7 grams, calculate in the ratio that feeds intake, all water insoluble because of reactant, do not have loss substantially).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result show this material in the attenuation by absorption of 10-18GHz, 23-40GHz all above-5dB, and the ripple of 1-18GHz frequently in the scope maximum absorption decay can reach-8dB, illustrate that this material is not fine to hertzian wave assimilation effect all.
Embodiment 2:
Prepare the SBA-15 molecular sieve by embodiment 1 method.
The assembling of polyaniline in the molecular sieve pore passage:
Take by weighing previous step synthetic SBA-15 molecular sieve 5 grams, join 180 milliliters of massfractions and be in 4.625% the hydrochloric acid soln, after stirring, add 11.6 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 23.28 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain molecular sieve polyaniline compound wave-absorbing material 16.5 grams (molecular sieve is 1: 2.3 with the calculated mass ratio of polyaniline).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result show this material in the attenuation by absorption of 7-18GHz, 24-40GHz all above-5dB, attenuation by absorption at 10-14GHz, 27-34GHz all reaches-more than the 10dB, and the maximum absorption decay can reach-13dB in the ripple frequency scope of 1-18GHz, illustrates that this material all has assimilation effect preferably to hertzian wave in the wideband section.
Embodiment 3:
Prepare the SBA-15 molecular sieve by embodiment 1 method.
The assembling of polyaniline in the molecular sieve pore passage:
Take by weighing previous step synthetic SBA-15 molecular sieve 4.5 grams, join 90 milliliters of massfractions and be in 4.625% the hydrochloric acid soln, after stirring, add 5.5 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 12.1 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain molecular sieve polyaniline compound wave-absorbing material 10 grams (molecular sieve is 1: 1.2 with the calculated mass ratio of polyaniline).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result show this material in the attenuation by absorption of 6-16GHz, 18-40GHz all above-5dB, attenuation by absorption at 8-11GHz, 21-40GHz all reaches-more than the 10dB, and the maximum absorption decay can reach-18dB in the ripple frequency scope of 1-18GHz, illustrates that this material all has good assimilation effect to hertzian wave in the wideband section.
Comparative Examples 1:
Prepare the SBA-15 molecular sieve by embodiment 1 method.
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result does not show only to be had at 34～40GHz with polyaniline compound molecular sieve-attenuation by absorption more than the 5dB, and assimilation effect is far below embodiment 3.
Comparative Examples 2:
90 milliliters of massfractions of adding are 4.625% hydrochloric acid soln in the 250ml flask, add 5.5 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, other gets 12.1 gram ammonium persulphates and joins in 100 ml deionized water, dropwise join in the top solution with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain polyaniline wave absorbing material 5.3 grams
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result does not show and only reaches-5dB with molecular sieve compound polyaniline attenuation by absorption maximum, far below embodiment 3.
Embodiment 4:
Prepare the SBA-15 molecular sieve by embodiment 1 method.
The assembling of polyaniline in the molecular sieve pore passage:
Take by weighing previous step synthetic SBA-15 molecular sieve 15 grams, join massfraction and be in 110 milliliters of hydrochloric acid solns of 4.625%, after stirring, add 6.66 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 15 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain molecular sieve polyaniline compound wave-absorbing material 21.5 grams (molecular sieve is 1: 0.45 with the calculated mass ratio of polyaniline).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result show this material in the attenuation by absorption of 7-17GHz, 24-40GHz all above-5dB, attenuation by absorption at 26-32GHz all reaches-more than the 10dB, and the ripple of 1-18GHz frequently in the scope maximum absorption decay can reach-9dB, illustrate this material in each frequency range especially high frequency region hertzian wave is all had assimilation effect preferably.
Embodiment 5:
Prepare the SBA-15 molecular sieve by embodiment 1 method.
The assembling of polyaniline in the molecular sieve pore passage:
Take by weighing previous step synthetic SBA-15 molecular sieve 7.5 grams, join massfraction and be in 40 milliliters of hydrochloric acid solns of 4.625%, after stirring, add 2.5 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 5 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain molecular sieve polyaniline compound wave-absorbing material 10 grams (molecular sieve is 3: 1 with the calculated mass ratio of polyaniline).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.Measuring result show this material in the attenuation by absorption of 12-17GHz all above-5dB, this material only has some assimilation effects to hertzian wave, far below embodiment 3, but still is better than the assimilation effect of Comparative Examples 1,2.
Embodiment 6:
Synthesizing of molecular sieve:
In 100 milliliters beaker, add 10 gram TPAOH (TPAOH massfraction 40%) and 13 ml deionized water, stir the clarification back and add 0.68 gram Tai-Ace S 150, add 12.3 milliliters of TEOS (tetraethoxy) after the dissolving again, stir more than 2 hours, crystallization is 12 hours in the inherent 120 ℃ of baking ovens of the stainless steel cauldron of packing into, descended centrifugal 5 minutes at 7000 revolutions per seconds afterwards, and with deionized water wash 3 to 4 times, obtain sample and put into 85 ℃ of oven dryings, dry intact sample 550 ℃ of burning samples in retort furnace were removed template in 5.5 hours.The MFI type molecular sieve that obtains nanocrystalline (3.1 gram) is rectangular, and volume is about 100nmx150nm, has the duct of 0.6～0.7nm of homogeneous.
The assembling of molecular sieve and polyaniline
Take by weighing previous step synthetic MFI type molecular sieve 4.5 grams, join 90 milliliters of massfractions and be in 4.625% the hydrochloric acid soln, after stirring, add 5.5 gram aniline monomers therein again, ultrasonic agitation is more than 10 minutes, and other gets 12.1 gram ammonium persulphates and joins in 100 ml deionized water, dropwise joins in the mixing solutions of top molecular sieve and polyaniline with dropping funnel after the stirring and dissolving, keep temperature of reaction at zero degree, and continue to stir 6 hours.The product that has reacted is through suction filtration, and alternately cleans with acetone and deionized water, and is dry down at 85 ℃ afterwards.Obtain molecular sieve polyaniline compound wave-absorbing material 10 grams (molecular sieve is 1: 1.2 with the calculated mass ratio of polyaniline).
The test of absorbing property:
Adopt the arch bridge antenna method respectively 1-18GHz, 18-26.5GHz, three frequency range absorption of electromagnetic wave of 26.5-40GHz effect to be measured.The result who records shows that the maximum absorption decay in 1～18GHz scope of magnetic material can reach-27dB, and not add the matrix material of SBA-15 molecular sieve wide but absorb width.
Claims (4)
1. molecular sieve polyaniline compound wave-absorbing material is characterized in that: the duct of molecular sieve and finishing polyaniline material, the mass ratio of molecular sieve and polyaniline is 1: 0.1～10, molecular sieve type is SBA-15.
2. the preparation method of the described molecular sieve polyaniline compound wave-absorbing material of claim 1, its step is as follows:
A) preparation mesoporous molecular sieve SBA-15, and remove tensio-active agent in the duct;
B) the high molecular assembling of polyaniline in the molecular sieve pore passage: by molecular sieve and aniline monomer mass ratio is 1: 6～0.3 to take by weighing respective sample, join quality and be 5～20 times of polyaniline monomers, massfraction and be in 4～5% the HCl solution, after the process ultrasonic agitation is uniformly dispersed, under the condition of ice bath, slowly add the oxygenant ammonium persulfate solution, the mass ratio of ammonium persulphate and aniline monomer is 1～5: 1, keeps the ice bath system to stir afterwards 6～10 hours;
C) will on the sample suction filtration, and, dry down at 60～100 ℃ with the alternately washing of acetone and water, obtain molecular sieve and polyaniline compound absorbing material.
3. the preparation method of molecular sieve polyaniline compound wave-absorbing material as claimed in claim 2, it is characterized in that: the preparation mesoporous molecular sieve SBA-15 also removes that tensio-active agent is to add surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene 0.4～1.6g in 25ml distilled water in the duct, add 4～10ml massfraction after stirring evenly again and be 36～38% concentrated hydrochloric acid HCl and the tetraethoxy of 1～5ml, 40～50 ℃ of following stirring in water bath after 12～24 hours, 100～150 ℃ of crystallization are 1～10 day in the stainless steel cauldron of packing into; Then with mesopore molecular sieve after the filtering and washing drying, in retort furnace, burnt sample 2～3 hours down prior to 300～350 ℃, be raised to 500～600 ℃ again and burnt sample 5～6 hours, thereby the tensio-active agent in the removal duct, obtain removing the SBA-15 molecular sieve of tensio-active agent, molecular sieve bore diameter is distributed in 7～9nm.
4. the preparation method of molecular sieve polyaniline compound wave-absorbing material as claimed in claim 3 is characterized in that: burn the sample process and adopt temperature programming, 1～2 ℃ of heat-up rate per second.
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| CN102643592B (en) * | 2012-04-16 | 2014-07-02 | 沈阳化工大学 | Preparation method of anticorrosive paint of polyaniline modified mesoporous molecular sieve |
| CN106750283A (en) * | 2016-12-25 | 2017-05-31 | 常州创索新材料科技有限公司 | A kind of preparation method of foamed aluminium modified polyaniline composite wave-suction material |
| CN106750284B (en) * | 2017-01-19 | 2020-05-19 | 北京工商大学 | Foamed metal doped polyaniline electromagnetic shielding material and preparation method thereof |
| CN108914244B (en) * | 2018-06-19 | 2021-05-11 | 江苏迪胺新材料科技有限公司 | Preparation method for synthesizing conductive polymer polyaniline nano-fiber by taking molecular sieve as seed crystal in guiding manner |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186750A (en) * | 2007-11-16 | 2008-05-28 | 辽宁大学 | Method for preparing polyaniline/MCM-48 mesoporous molecular screen composition |
| CN101191017A (en) * | 2007-11-20 | 2008-06-04 | 沈阳化工学院 | Preparation for polyaniline mesoporous molecular screen composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186750A (en) * | 2007-11-16 | 2008-05-28 | 辽宁大学 | Method for preparing polyaniline/MCM-48 mesoporous molecular screen composition |
| CN101191017A (en) * | 2007-11-20 | 2008-06-04 | 沈阳化工学院 | Preparation for polyaniline mesoporous molecular screen composite |
Non-Patent Citations (2)
| Title |
|---|
| 孟桂花等.聚苯胺/MCM241 介孔分子筛导电复合材料的制备及其表征.《化工新型材料》.2006,第34卷(第1期),42-44. * |
| 罗根祥等.分子筛孔道内聚苯胺的微波合成.《石油化工高等学校学报》.2000,第13卷(第3期),5-8. * |
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