CN104140642B - A kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex and preparation method thereof - Google Patents
A kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex and preparation method thereof Download PDFInfo
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- CN104140642B CN104140642B CN201410350623.1A CN201410350623A CN104140642B CN 104140642 B CN104140642 B CN 104140642B CN 201410350623 A CN201410350623 A CN 201410350623A CN 104140642 B CN104140642 B CN 104140642B
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Abstract
The present invention relates to a kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe with Microwave Absorption Properties3O4Complex and preparation method thereof, this preparation method includes preparing white emulsion, adds ferrous chloride, adds iron chloride, washing and drying and other steps. The absorption band of composite prepared by the present invention can be adjusted by change material thickness, and microwave absorption frequency band is substantially widened, and has good absorbing property. Can passing through to change temperature and change oxidizer in preparation process to regulate electromagnetic parameter, for widening Composite Microwave absorption band, to prepare novel wave-absorbing material significant.
Description
[technical field]
The invention belongs to novel wave-absorbing material technical field. More particularly it relates to an have poly-(pyrroles-ethylenedioxy thiophene)/Fe of Microwave Absorption Properties3O4Complex, further relates to gather (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation method of complex.
[background technology]
Microwave material refer to a kind of can absorb, incident electromagnetic wave of decaying, and convert its electromagnetic energy to material that heat energy dissipates or make electromagnetic wave to disappear because of interference. Absorbing material is the earliest for military purposes, it is called " stealth material ", however as electromagnetic extensive use, while improving human lives, the healthy infringement of the mankind is also produced by the electromagnetic radiation of its association therewith, so, absorbing material research in television broadcasting, electronic device and microwave radiation protecting etc. are civilian is also increasingly subject to pay attention to. Absorbing material is divided into tradition absorbing material and novel wave-absorbing material, and novel wave-absorbing material has features such as " thin, light, wide, strong ", and it rises and develop into the research and development of absorbing material and provides new path and direction.
In recent years, conducting polymer is considered as the New type microwave adsorption material of most prospect, compared with the microwave absorption based on metal and carbon-based material, conducting polymer have light weight, anticorrosive, be prone to processing and the advantage such as electrical conductivity is adjustable, especially the conducting polymer of function solenoid, because it has inorganic and organic material characteristic concurrently, cause the extensive concern of people. Research proves, the introducing of conducting polymer is conducive to improving the reflection loss of inorganic magnetic material, for instance polypyrrole/BaFe12O19, polypyrrole/nickel, polypyrrole/ZnFe2O4, polypyrrole/FeOOH, polypyrrole/Fe3O4, polyaniline/Fe3O4And polyaniline/BaTiO3The Microwave Absorption Properties of composite is better than corresponding single magnetic material;But, the microwave absorption frequency range of single conductive polymer-magnetic material complex is narrower, it is difficult to meet the demand of high performance applications. Poly-(aniline-pyrroles) copolymer/Fe prepared by Xiong Dongbai et al. (Xiong Dongbai, 2009, Hunan Normal University's Master's thesis, the Morphological control of conductive polymers based magnetic nanocomposites and electromagnetic property research thereof)3O4The microwave absorbing property of composite is substantially better than polyaniline/Fe3O4, polypyrrole/Fe3O4Composite, frequency bandwidth during lower than-10dB is 4.7GHz. But, the two-step synthetic method that Xiong Dongbai et al. adopts is relatively complicated, and magnetic particle dispersion is uneven. In order to improve above-mentioned technical problem, the present inventor adopts poly-(pyrroles-the EDOT)/Fe of " one-step synthesis " synthesis3O4Composite a, it is achieved that step of conducting polymer and magnetic particle generates, and method is simple, and effect is notable, has a extensive future.
[summary of the invention]
[solving the technical problem that]
It is an object of the invention to provide a kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe with Microwave Absorption Properties3O4Complex.
It is a further object to provide described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation method of complex.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe with Microwave Absorption Properties3O4The preparation method of complex.
The step of this preparation method is as follows:
A, prepare white emulsion
According to mol ratio 1:0.4��2.4 of pyrroles Yu ethylenedioxy thiophene, adding pyrroles and ethylenedioxy thiophene, mix homogeneously in 70��100ml ammonia spirit that concentration is 1��1.5mol/L, the mixture obtained obtains a kind of white emulsion under ultrasonic Treatment;
B, interpolation ferrous chloride
When temperature 20��40 DEG C, according to FeCl2��4H2O and mol ratio 1:1.3��2.0 of pyrroles, add 0.3��1.0mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2Mol ratio 1:31��92 of O, drip 2.2��9.0mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 8��12 hours when stirring and temperature 20��40 DEG C, it is then centrifuged for separating, obtains a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, vacuum drying, obtains described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
A preferred embodiment of the invention, in step, described ultrasonic Treatment is that 20��40KHz processes 2��5min in power 80��120w when.
Another kind of preferred implementation according to the present invention, in step, the mol ratio of pyrroles and ethylenedioxy thiophene is 1:1.2��1.6.
Another kind of preferred implementation according to the present invention, in stepb, FeCl2��4H2The mol ratio of O and pyrroles is 1:1.5��1.8.
Another kind of preferred implementation according to the present invention, in step C, has added FeCl in 15��30 minutes3.6H2O aqueous solution.
Another kind of preferred implementation according to the present invention, in step C, FeCl2.4H2O and FeCl3��6H2The mol ratio of O is 1:50��72.
Another kind of preferred implementation according to the present invention, in step D, the solid product of washing carries out vacuum drying 8��9h when temperature 40��50 and vacuum 0.2��0.3MPa.
The invention still further relates to poly-(pyrroles-ethylenedioxy thiophene)/Fe adopting described preparation method obtained3O4Complex.
A preferred embodiment of the invention, the maximum reflection loss when thickness 2mm of the described complex is-19.81��-49.10dB, the maximum microwave reflection rate frequency bandwidth lower than-10dB is 3.76��5.62GHz, and the frequency bandwidth that maximum microwave reflection rate is lower than-5dB is 8.52��9.25GHz.
The present invention is described in more detail below.
The present invention relates to a kind of poly-(pyrroles-ethylenedioxy thiophene)/Fe with Microwave Absorption Properties3O4The preparation method of complex.
The step of this preparation method is as follows:
A, prepare white emulsion
According to mol ratio 1:0.4��2.4 of pyrroles Yu ethylenedioxy thiophene, adding pyrroles and ethylenedioxy thiophene, mix homogeneously in 70��100ml ammonia spirit that concentration is 1��1.5mol/L, the mixture obtained obtains a kind of white emulsion under ultrasonic Treatment.
According to the present invention, pyrroles and ethylenedioxy thiophene carry out the purpose of supersound process in ammonia spirit and are in that to make pyrroles and ethylenedioxy thiophene be dissolved in better in ammonia, form emulsion.
Pyrroles and the ethylenedioxy thiophene that the present invention uses is product sold in the market, the pyrroles such as sold with trade name pyrroles along strong bio tech ltd by Shanghai, the ethylenedioxy thiophene sold with trade name 3,4-ethylenedioxy thiophene by subfamily chemical reagent company limited.
In this step, described ultrasonic Treatment be 20��40KHz in power 80��120w when process 2��5min.
The ultrasonic device that the present invention uses is the ultrasound products sold in the market, for instance by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit product sold.
In this step, when the mol ratio of pyrroles and ethylenedioxy thiophene is more than 1:0.4, then pyrroles's autohemagglutination, not easily copolymerization can be caused; If the mol ratio of pyrroles and ethylenedioxy thiophene is less than 1:2.4, then can the more difficult generation of copolyreaction. Therefore, the mol ratio of pyrroles and ethylenedioxy thiophene is 1:0.4��2.4 is rational. Preferably, pyrroles is 1:1.2��1.6 with the mol ratio of ethylenedioxy thiophene.
B, interpolation ferrous chloride
When temperature 20��40 DEG C, according to FeCl2��4H2O and mol ratio 1:1.3��2.0 of pyrroles, add 0.3��1.0mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
In this step, FeCl is used2��4H2The purpose of O is in that to provide the bivalence source of iron forming magnetic iron oxide;
The FeCl that the present invention uses2��4H2O is the ultrasound products sold in the market, for instance by Tianjin chemical reagents corporation of Jin Hui the Pacific-Asian with trade name ferrous chloride product sold.
According to the present invention, FeCl2��4H2The concentration of O it is critical that, if its concentration is less than 0.3mol/L, then can affect the generation of magnetic iron oxide; If its concentration is higher than 1.0mol/L, then can affect the generation of magnetic iron oxide equally; Therefore, FeCl2��4H2The concentration of O is 0.3��1.0mol/L is appropriate, it is preferred that 0.5��0.8mol/L.
Preferably, FeCl2��4H2The mol ratio of O and pyrroles is 1:1.5��1.8.
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2Mol ratio 1:31��92 of O, drip 2.2��9.0mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 8��12 hours when stirring and temperature 20��40 DEG C, it is then centrifuged for separating, obtains a kind of solid product;
In this step, FeCl is added3��6H2The oxidant functioning as pyrroles and dioxy thiophene of O and the ferric iron source of formation magnetic iron oxide.
The FeCl that the present invention uses3��6H2O is the ultrasound products sold in the market, for instance by Tianjin chemical reagents corporation of Jin Hui the Pacific-Asian with trade name ferric chloride product sold.
According to the present invention, FeCl2.4H2O and FeCl3��6H2The mol ratio of O is 1:31��92, if this mol ratio is less than 1:31, is then unfavorable for the generation of conducting polymer; If this mol ratio is more than 1:92, then it is unfavorable for the generation of magnetisable material; Therefore, this mol ratio is 1:31��92 is suitable, it is preferred that 1:50��72, it is more preferred to be 1:56��66.
In step C, in 15��30 minutes, add FeCl3.6H2O aqueous solution.
Preferably, this reaction carries out 8.8��11.2 hours when temperature 26��35 DEG C, it is more preferred to, this reaction carries out 9.5��10.5 hours when temperature 28��32 DEG C.
In this step, the centrifuge used when being centrifuged is the centrifuge sold in the market, for instance by Anting Scientific Instrument Factory, Shanghai with trade name TDL-5 centrifuge product sold.
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, vacuum drying, obtains described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
In step D, the Main Function using distilled water, ethanol and washed with diethylether is to remove ferric chloride, ferrous chloride and other water-solubility impurities with distilled water wash; Low-molecular-weight conducting polymer is removed by washing with alcohol; Be conducive to the dry of sample with washed with diethylether, shorten drying time.
The solid product of washing carries out vacuum drying 8��9h when temperature 40��50 and vacuum 0.2��0.3MPa.
In this step, the equipment used during vacuum drying is product sold in the market, for instance by Nanjing martial prowess pharmaceutical equipment company limited with trade name DZF series vacuum drying oven product sold.
The present invention relates to poly-(pyrroles-ethylenedioxy thiophene)/Fe adopting described preparation method obtained3O4Complex.
To obtained poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex has carried out the mensuration of infrared spectrum (FTIR), X-ray diffraction analysis (XRD) and electric conductivity and magnetic.
Infrared spectrum (FTIR), X-ray diffraction analysis (XRD) and magnetic adopt conventional method of analysis to carry out, and its measurement result is listed in accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3.
The room-temperature conductivity of complex of the present invention is determined according to four electrode standard methods.
Described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4The complex maximum reflection loss when thickness 2mm is-19.81��-49.10dB, and it is 3.76��5.62GHz in the maximum microwave reflection rate frequency bandwidth lower than-10dB, and it is 8.52��9.25GHz in the maximum microwave reflection rate frequency bandwidth lower than-5dB.
Poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4Complex may be used for microwave absorption, is characterized in widening microwave absorption frequency band.
The present invention prepares poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4The method of complex has following feature:
Poly-(pyrroles-ethylenedioxy thiophene)/Fe prepared by the method3O4Composite, its absorption band can be regulated by the change of material thickness, and microwave absorption frequency band can substantially be widened, and has good absorbing property. Can regulating electromagnetic parameter by the change of the change of temperature and oxidizer in preparation process, for widening Composite Microwave absorption band, to prepare novel wave-absorbing material significant.
[beneficial effect]
The invention has the beneficial effects as follows:
Compared with prior art, the present invention adopts poly-(pyrroles-ethylenedioxy thiophene)/Fe prepared by " one-step synthesis "3O4Electric conductivity and the magnetic of composite are adjustable, and preparation method is simple, and energy consumption is low, reproducible, it may be achieved product continuous, quickly prepare, it is easy to industrialized production. The method achieve magnetic particle and conducting polymer can be simultaneously generated under FeCl3.6H2O effect, ensure magnetic particle being uniformly distributed in conducting polymer well, and simplify reactions steps, overcome the complex process that existing " two-step synthesis method " exists, the defect that magnetic particle dispersion is uneven. The absorption band of composite prepared by the present invention can be adjusted by change material thickness, and microwave absorption frequency band is substantially widened, and has good absorbing property. Can passing through to change temperature and change oxidizer in preparation process to regulate electromagnetic parameter, for widening Composite Microwave absorption band, to prepare novel wave-absorbing material significant.
[accompanying drawing explanation]
Fig. 1 is poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4The infrared spectrogram of complex;
Fig. 2 is poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4The XRD figure of complex;
Fig. 3 is poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4The hysteresis curve of complex;
Fig. 4 is poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4Complex is at the reflection loss curve that thickness of sample is 2.5mm.
Fig. 5 is poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present invention3O4Complex is at the reflection loss curve of different thickness of sample.
[detailed description of the invention]
The present invention will be better understood when by following embodiment.
Embodiment 1: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:1.2 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 80ml ammonia spirit that concentration is 1.4mol/L, mix homogeneously, use the ultrasonic device sold by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 3min when 20KHz. and power 80w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 32 DEG C, according to FeCl2��4H2O and the mol ratio 1:2.0 of pyrroles, adds 1.0mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:31 of O, drips 6.8mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 10 hours when stirring and temperature 34 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, temperature 40 DEG C with vacuum 0.2MPa when carry out vacuum drying 8.8h, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
Poly-(pyrroles-ethylenedioxy thiophene)/Fe prepared by the present embodiment3O4Complex has carried out infrared spectrum analysis, and its infrared spectrum is listed in accompanying drawing 1.By accompanying drawing 1 it can be seen that at wave number 572,688,788,848,928,976,1052,1200,1400,1540 and 1636cm-1Place's existing characteristics absworption peak, it was demonstrated that pyrroles and ethylenedioxy thiophene (EDOT) copolymerization.
Poly-(pyrroles-ethylenedioxy thiophene)/Fe of the present embodiment 1 preparation3O4Complex has also carried out X-ray diffraction analysis, and its XRD figure is listed in accompanying drawing 2. By accompanying drawing 2 it can be seen that except the characteristic absorption peak of pyrroles's-EDOT copolymer occurs in 2 ��=25.6 ��, also in 2 ��=30.1,35.6,43.1,53.5,57.1 and 62.7 �� of places multiple diffraction maximums, these diffraction maximums and Fe occur3O4Standard diffraction peak is consistent, thus proving that the method adopting the present invention prepares poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
Poly-(pyrroles-ethylenedioxy thiophene)/Fe prepared by the present embodiment is measured according to four electrode standard methods3O4The room-temperature conductivity of complex, its room-temperature conductivity is 1.06S/cm. Gaussmeter is adopted to determine poly-(pyrroles-ethylenedioxy thiophene)/Fe prepared by the present embodiment3O4The hysteresis curve of complex, its result is shown in accompanying drawing 3, and its saturated magnetic intensity is 6.99A2m/kg��
The product obtained by the present embodiment mixes according to mass ratio 3:7 with paraffin, is pressed into the annulus of external diameter 7mm, internal diameter 3mm and thickness 2mm with grinding tool. Then use the vector network analyzer sold with trade name vector network analyzer by Agilent company, measure its electromagnetic parameter within the scope of 1-18GHz: pcrmeability real part (�� '), pcrmeability imaginary part (�� "), real part of permittivity (�� '), imaginary part of dielectric constant (�� ").
By complex permeability ��=�� '-j �� " with complex dielectric permittivity ��=�� '-j �� ", finally simulating the maximum microwave reflection rate R of sample, its result is shown in accompanying drawing 4 and accompanying drawing 5. The present embodiment prepares Product samples when thickness 2mm, and its frequency bandwidth when maximum microwave reflection rate-10dB is 5.62GHz, and its frequency bandwidth when maximum microwave reflection rate-5dB is 8.63GHz; Its maximum reflection loss at 13.6GHz place is-31.59dB.
Embodiment 2: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:0.4 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 100ml ammonia spirit that concentration is 1.0mol/L, mix homogeneously, use the ultrasonic device that Gou Wei Science and Technology Ltd. sells with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 2min when 25KHz and power 120w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 20 DEG C, according to FeCl2��4H2O and the mol ratio 1:1.3 of pyrroles, adds 0.3mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:92 of O, drips 7.6mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 8 hours when stirring and temperature 20 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, temperature 46 DEG C with vacuum 0.3MPa when carry out vacuum drying 8.0h, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
The maximum microwave reflection rate R of Product samples is prepared: when thickness 2mm according to obtaining the present embodiment with the simulation of embodiment 1 same way, its frequency bandwidth when maximum microwave reflection rate is less than-10dB is 3.76GHz, and its frequency bandwidth when maximum microwave reflection rate is less than-5dB is 9.06GHz; Its maximum reflection loss at 10GHz place is-19.81dB.
Embodiment 3: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:0.8 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 90ml ammonia spirit that concentration is 1.2mol/L, mix homogeneously, use the ultrasonic device sold by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 3min when 30KHz. and power 120w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 28 DEG C, according to FeCl2��4H2O and the mol ratio 1:1.5 of pyrroles, adds 0.8mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:50 of O, drips 2.2mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 9 hours when stirring and temperature 28 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, carry out vacuum drying 8.2h when temperature 50 C and vacuum 0.2MPa, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
The maximum microwave reflection rate R of Product samples is prepared: when thickness 2mm according to obtaining the present embodiment with the simulation of embodiment 1 same way, its frequency bandwidth when maximum microwave reflection rate is less than-10dB is 3.81GHz, and its frequency bandwidth when maximum microwave reflection rate is less than-5dB is 8.52GHz; Its maximum reflection loss at 10GHz place is-20.30dB.
Embodiment 4: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:2.0 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 80ml ammonia spirit that concentration is 1.4mol/L, mix homogeneously, use the ultrasonic device sold by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 4min when 20KHz and power 80w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 36 DEG C, according to FeCl2��4H2O and the mol ratio 1:1.8 of pyrroles, adds 0.5mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:72 of O, drips 5.4mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 10 hours when stirring and temperature 34 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, temperature 40 DEG C with vacuum 0.3MPa when carry out vacuum drying 9.0h, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
The maximum microwave reflection rate R of Product samples is prepared: when thickness 2mm according to obtaining the present embodiment with the simulation of embodiment 1 same way, its frequency bandwidth when maximum microwave reflection rate is less than-10dB is 5.02GHz, and its frequency bandwidth when maximum microwave reflection rate is less than-5dB is 9.25GHz; Its maximum reflection loss at 10GHz place is-49.10dB.
Embodiment 5: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:1.6 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 70ml ammonia spirit that concentration is 1.5mol/L, mix homogeneously, use the ultrasonic device sold by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 5min when 25KHz and power 120w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 24 DEG C, according to FeCl2��4H2O and the mol ratio 1:1.8 of pyrroles, adds 0.8mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:56 of O, drips 3.8mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 11 hours when stirring and temperature 40 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, carry out vacuum drying 8.4h when temperature 45 C and vacuum 0.2MPa, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
The maximum microwave reflection rate R of Product samples is prepared: when thickness 2mm according to obtaining the present embodiment with the simulation of embodiment 1 same way, its frequency bandwidth when maximum microwave reflection rate is less than-10dB is 4.32GHz, and its frequency bandwidth when maximum microwave reflection rate is less than-5dB is 8.84GHz; Its maximum reflection loss at 10GHz place is-37.50dB.
Embodiment 6: the present invention gathers (pyrroles-ethylenedioxy thiophene)/Fe3O4The preparation of complex
The enforcement step of this embodiment is as follows:
A, prepare white emulsion
Mol ratio 1:2.4 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in the 90ml ammonia spirit that concentration is 1.2mol/L, mix homogeneously, use the ultrasonic device sold by Gou Wei Science and Technology Ltd. with trade name ultrasonic washing unit, the mixture obtained is carried out ultrasonic Treatment 4min when 30KHz and power 120w/cm, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 40 DEG C, according to FeCl2��4H2O and the mol ratio 1:1.5 of pyrroles, adds 0.4mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1:66 of O, drips 9.0mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 12 hours when stirring and temperature 28 DEG C, then use and be centrifuged separating with the centrifuge that trade name TDL-5 centrifuge is sold by Anting Scientific Instrument Factory, Shanghai, obtain a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, then in the vacuum desiccator sold with trade name DZF series vacuum drying oven by Nanjing martial prowess pharmaceutical equipment company limited, carry out vacuum drying 8.5h when temperature 50 C and vacuum 0.3MPa, obtain described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
The maximum microwave reflection rate R of Product samples is prepared: when thickness 2mm according to obtaining the present embodiment with the simulation of embodiment 1 same way, its frequency bandwidth when maximum microwave reflection rate is less than-10dB is 4.85GHz, and its frequency bandwidth when maximum microwave reflection rate is less than-5dB is 8.45GHz; Its maximum reflection loss at 10GHz place is-41.20dB.
By above-described embodiment it can be clearly seen that " one-step synthesis " of the present invention successfully prepares poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex, when thickness of sample is 2mm, the maximum reflection loss of this complex reaches-19.81��-49.10dB, frequency bandwidth when maximum microwave reflection rate is lower than-10dB is 3.76��5.62GHz, frequency bandwidth when maximum microwave reflection rate is lower than-5dB is 8.52��9.25GHz, illustrate that it possesses good Microwave Absorption Properties, meet novel microwave absorbent requirement, it is possible to be applied to association area.
Claims (8)
1. poly-(pyrroles-ethylenedioxy thiophene)/Fe with Microwave Absorption Properties3O4The preparation method of complex, it is characterised in that the step of this preparation method is as follows:
A, prepare white emulsion
Mol ratio 1: 0.4��2.4 according to pyrroles Yu ethylenedioxy thiophene, pyrroles and ethylenedioxy thiophene is added in 70��100ml ammonia spirit that concentration is 1��1.5mol/L, mix homogeneously, the mixture obtained is ultrasonic Treatment 2��5min when 20��40KHz and power 80��120w, obtains a kind of white emulsion;
B, interpolation ferrous chloride
When temperature 20��40 DEG C, according to FeCl2��4H2O and the mol ratio 1: 1.3��2.0 of pyrroles, add 0.3��1.0mol/LFeCl in the step A white emulsion obtained2��4H2O aqueous solution, obtains the solution that chloride containing is ferrous;
C, interpolation iron chloride
According to FeCl2.4H2O and FeCl3��6H2The mol ratio 1: 31��92 of O, drips 2.2��9.0mol/LFeCl in the step B chloride containing ferrous iron solution obtained3.6H2O aqueous solution, the stirring reaction 8��12 hours when stirring and temperature 20��40 DEG C, it is then centrifuged for separating, obtains a kind of solid product;
D, washing with dry
The solid product that step C obtains washs with distilled water, ethanol and ether respectively, vacuum drying, obtains described poly-(pyrroles-ethylenedioxy thiophene)/Fe3O4Complex.
2. the mol ratio of preparation method according to claim 1, it is characterised in that in step, pyrroles and ethylenedioxy thiophene is 1: 1.2��1.6.
3. preparation method according to claim 1, it is characterised in that in stepb, FeCl2��4H2The mol ratio of O and pyrroles is 1: 1.5��1.8.
4. preparation method according to claim 1, it is characterised in that in step C, has added FeCl in 15��30 minutes3.6H2O aqueous solution.
5. preparation method according to claim 1, it is characterised in that in step C, FeCl2.4H2O and FeCl3��6H2The mol ratio of O is 1: 50��72.
6. preparation method according to claim 1, it is characterised in that in step D, the solid product of washing temperature 40��50 DEG C with vacuum 0.2��0.3MPa when carry out vacuum drying 8��9h.
7. poly-(pyrroles-ethylenedioxy thiophene)/Fe that preparation method described in claim any one of claim 1-6 obtains3O4Complex.
8. poly-(pyrroles-ethylenedioxy thiophene)/Fe according to claim 73O4Complex, it is characterized in that the maximum reflection loss when thickness 2mm of the described complex is-19.81��-49.10dB, the maximum microwave reflection rate frequency bandwidth lower than-10dB is 3.76��5.62GHz, and the frequency bandwidth that maximum microwave reflection rate is lower than-5dB is 8.52��9.25GHz.
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