CN1718612A - Inorganic oxide conductive powder/polyaniline conductive polymer composite material and its preparation method - Google Patents
Inorganic oxide conductive powder/polyaniline conductive polymer composite material and its preparation method Download PDFInfo
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Abstract
A process for preparing the electrically conductive inorganic oxide powder/electrically conductive high-molecular polyphenylamide compound includes such steps as proportionally mixing the aqueous solution of phenylamine with the aqueous solution of dopant acid, adding electrically conductive inorganic oxide, stirring,adding the aqueous solution of oxidant, reaction, and separating target product.
Description
Technical field
The present invention relates to conductive polymer composite, be specifically related to chemical oxidation in-situ polymerization synthetic inorganic oxide conductive powder/polyaniline conductive polymer matrix material and method.
Technical background
Last Nobel chemistry Prize in 20th century has been presented to three chemists that obtain distinguished service in the research of conducting high polymers thing in October, 2000: the Bai Chuanying tree of the black square of the U.S., mark's Diarmid and Japan.
Conducting polymer can be divided into two big classes by its electrical conduction mechanism: a class is a conductive polymeric composite, promptly adds various electroconductive stuffings in conventional macromolecular material, as metal-powder, graphitized carbon black particle or fiber etc.; Another kind of is the intrinsically conducting macromolecular material, is promptly formed after " doping " by the polymer with conjugated, makes its specific conductivity change conductor into by semi-conductor by " doping ".Conducting polymer described herein specially refers to the intrinsically conducting polymer.After conduction polyacetylene (PA) in 1977 discovery, people have developed a series of conducting polymer composites in succession, as polypyrrole (PPY, 1977), Polythiophene (PTH, 1981), polyparaphenylene (1979), poly-to vinylbenzene (1979), polyaniline (PANI, 1980) etc.
In numerous conducting polymer composites, polyaniline is a kind of intrinsically conducting polymer with conjugated electrons structure, its electrochemical properties is stable, the Doping Mechanism uniqueness, advantages such as the back conductivity that mixes is good, and raw material is easy to get, and preparation process is simple, be the conducting polymer composite of the easiest realization widespread use, so polyaniline has become the research focus of conducting high polymers thing.But the specific conductivity of polyaniline in numerous conducting polymer composites is more on the low side, and this shortcoming has limited the widespread use of polyaniline again greatly.Though domestic and international research personnel constantly make great efforts to attempt to improve the specific conductivity of doped polyaniline, for example adopt means such as p-poly-phenyl amino-group dopings such as mixing acid, polymer acid and secondary doping, also there is specific conductivity to be higher than the high conductivity polyaniline synthetic report of common several orders of magnitude of doped polyaniline frequently, but because it is a lot of to influence the factor of polyaniline specific conductivity, with general chemistry oxidation in-situ polymerization synthetic doped polyaniline, its specific conductivity can only reach the scope of 0.05-2S/cm usually.
Composite technology, especially composite organic-inorganic material technology have been opened up brand-new field for the research of exploring novel material.Organic and inorganic material by compound can be when keeping each composition material primary characteristic, produce the not available new capability of independent organic or inorganic material, therefore research and exploration novel organic-inorganic matrix material are subjected to scientific worker's extensive attention day by day.
(Mukul B, Suprakas S R.J Appl Polym Sci.2000,77:2948) (Wu Qiuju such as Wu Qiuju such as Biswas, Xue Zhijian, QiZongNeng etc. the polymer journal, 1999,5:551) all reported with the method for intercalation polymeric and synthesized high conductivity polyaniline/montmorillonite composite material.(Wan M X, Li W G.J Appl PolymSci 1997m73:2129) adopt solution blended process, blend coprecipitation method to synthesize the polyaniline Fe that has magnetic and electroconductibility simultaneously to Chinese Academy of Sciences's Beijing chemistry ten thousand plum perfume (or spice)
3O
4Matrix material, but Fe
3O
4The distribution of particulate in the polyaniline matrix is restive, and specific conductivity is lower, and the full specific magnetising moment of closing is little, and coercivity H ≈ 0.Polyaniline Fe is also arranged recently
2O
3The research report of nano composite membrane.The Deng Jianguo of the organic institute in Chinese Academy of Sciences Chengdu etc. has synthesized with nanometer Fe
3O
4Particulate is nuclear, and electrically conductive polyaniline is the polyaniline Fe with nucleocapsid structure of shell
3O
4Nano composite material, this material has electroconductibility and magnetic property simultaneously, is expected to obtaining actual application aspect absorption of electromagnetic wave, electromagnetic shielding and the electric demonstration.Other polyaniline function mixture such as polyaniline/CuO (Huang C L, Richard E, Matijevic E; J Colloid and interface Sci, (colloid and interface science journal) 1995,170:275), polyaniline/V
2O
5(WuC G, Degroot D C, Marcy H O, et al.Chem Mater, (chemical material) 1996,29:8277) grade all has report.The formation mechanism of report sheet mica/polyaniline composite materials such as W.Jia is that the oxidative polymerization of aniline preferentially carries out at the mica mica surface, thereby generated polyphenyl and coated micaceous nucleocapsid structure composite particles (Jia W, etal.Polymers forAdvanced Technologies, (polymkeric substance in the hi-tech) 2002,13 (1): 16-24.).It is nuclear that the new profit of well of Xi'an Communications University etc. has been synthesized with the silicon dioxide microparticle, silica dioxide composite particles (SD/PANI) (Jing Xinli, Wang Yangyong, Zhang Donghua that electrically conductive polyaniline PANI coats; Material engineering, 2004, (1): 20-24).But with the electroconductive oxide is nuclear, and electrically conductive polyaniline is that the inorganic oxide conductive powder/polyaniline conductive polymer composite study with nucleocapsid structure of shell is not appeared in the newspapers as yet, does not also have the application of related invention patent.
The monobasic oxide compound is as zinc oxide, stannic oxide, weisspiessglanz, Indium sesquioxide, Cadmium oxide etc., have lower resistivity at normal temperatures and belong to semi-conductor or low electric conductivity oxide compound, after these monobasic oxide compounds are handled through suitable doping process, its resistivity can reduce greatly, conductivity is significantly improved, Here it is the common conductive doped powder of the said binary oxide of people, as: weisspiessglanz doped stannum oxide (ATO), Indium sesquioxide doped stannum oxide (ITO), alumina doped zinc oxide (AZO), the magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide or the like.In addition, some binary or multicomponent composite oxide, as: zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, Cadmium oxide-Indium sesquioxide or the like also has electroconductibility preferably, and the proportionlity between these each compositions of binary composite oxides is different from doping, and mixing always has the branch of primary and secondary, and be regardless of primary and secondary between these each compositions of binary composite oxides, have the relation of integer mol ratio.These inorganic oxide conductive powders have following characteristics: certain electroconductibility is arranged, and static resistance, look shallow, good weathering resistance, high-specific surface area, good dispersiveness has functions such as radioprotective, infrared absorption simultaneously.But compare with doped polyaniline, the specific conductivity of these oxide compounds and the conductive doped powder of binary oxide is still lower, usually in the 0.01-0.1S/cm scope.
Summary of the invention
The purpose of this invention is to provide a kind of polyaniline/inorganic oxide conductive powder conductive polymer composite, this matrix material demonstrates than the higher specific conductivity of general chemistry oxidation in-situ polymerization synthesized polyaniline, also has the specific conductivity more much higher than inorganic oxide conductive powder; The present invention also provides the preparation method of this matrix material, and this preparation method is easy to operation, and yield is than simple in-situ oxidizing-polymerizing synthetic polyaniline height.
Have broad application prospects in fields such as novel high polymer composite conducting material, antistatic material, metal anti-corrosive paint, boats and ships factory antifouling paint and electrochromism, electroluminescent devices.
The inorganic oxide conductive powder/polyaniline conductive polymer matrix material that the present invention proposes has following raw material: the aqueous solution and the inorganic oxide conductive powder of the aqueous solution of aniline monomer, the dopant acid aqueous solution, oxygenant, the aniline monomer aqueous solution wherein: the dopant acid aqueous solution: the mol ratio of aqueous oxidizing agent solution is 1: 0.6～0.83: 0.25～1.2, aniline monomer: the mass ratio of inorganic oxide conductive powder is 1: 0.025～0.50.For suitable, the concentration of the aqueous solution of oxygenant is suitable with 5～25wt% to the concentration of the aqueous solution of aniline monomer with 1～15wt%.
Described inorganic oxide conductive powder refer to the monobasic oxide compound as: zinc oxide, stannic oxide, weisspiessglanz, Indium sesquioxide, Cadmium oxide etc. have lower resistivity to belong to semi-conductor or low electric conductivity oxide compound at normal temperatures; And the common conductive doped powder of the said binary oxide of people, as: weisspiessglanz doped stannum oxide (ATO), Indium sesquioxide doped stannum oxide (ITO), alumina doped zinc oxide (AZO), the magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide or the like.In addition, some binary or multicomponent composite oxide, as zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, Cadmium oxide-Indium sesquioxide or the like also have electroconductibility preferably, and their specific conductivity is usually in the scope of 0.01-0.1S/cm.
Described oxygenant refers to solubility persulphate or solubility dichromate etc., and particularly preferred oxygenant is ammonium persulphate, Sodium Persulfate, ammonium dichromate, potassium bichromate.Most preferred oxygenant is ammonium persulphate, potassium bichromate or ammonium dichromate.But the solubility persulphate is different with the consumption of solubility dichromate, common aniline monomer: the mol ratio of solubility persulfate oxidation agent is 1: 0.75～1.2, and in this amount ranges, the consumption of persulphate is not to the influence of the productive rate of synthetic inorganic oxide conductive powder/polyaniline conductive polymer matrix material and specific conductivity not clearly.And common aniline monomer: the mol ratio of solubility dichromate oxygenant is 1: 0.25～0.65.And the consumption of dichromate is very obvious to the influence of the productive rate of synthetic inorganic oxide conductive powder/polyaniline conductive polymer matrix material and specific conductivity.Therefore particularly preferred dichromate consumption is: aniline monomer: the mol ratio of dichromate oxygenant is 1: 0.30～0.55; Most preferred dichromate consumption is: aniline monomer: the mol ratio of dichromate oxygenant is 1: 0.35～0.45.
The described dopant acid aqueous solution refers to the aqueous solution of mineral acid example hydrochloric acid, sulfuric acid (having left out nitric acid, phosphoric acid) etc., or the aqueous solution of organic acid such as camphorsulfonic acid, (leave out thionamic acid) alkylsulphonic acid (leaving out oxalic acid) etc., or the aqueous solution of mineral acid (above-mentioned)/organic acid (above-mentioned) nitration mixture.Particularly preferred is the aqueous solution of organic acid or mineral acid/organic acid nitration mixture, the most preferably aqueous solution of mineral acid/organic acid nitration mixture.
The inorganic oxide conductive powder that is adopted is the ultra micron powder of nano inorganic oxide conducting powder, submicro inorganic oxide conductive powder or inorganic oxide conductive powder.
Preparation method of the present invention comprises the steps:
The aqueous solution and the dopant acid aqueous solution of aniline monomer are mixed, and then inorganic oxide conductive powder added mix, aqueous solution adding said mixture with oxygenant reacts at last, temperature of reaction is-10～50 ℃, reaction times is that 4～24h. collects target product again from reaction product, also is synthetic inorganic oxide conductive powder/polyaniline conductive polymer composite products of the present invention.
According to the present invention, the aqueous solution and the dopant acid aqueous solution of aniline monomer can be mixed, and then inorganic oxide conductive powder added mix, aqueous solution adding said mixture with oxygenant reacts at last, or the aqueous solution and the dopant acid aqueous solution of aniline monomer mixed, and then inorganic oxide conductive powder added mix the aqueous solution that stirs at last oxygenant and add said mixture and react.
According to the present invention, oxidative polymerization carries out under constantly stirring. and stirring velocity per minute 500～3000 changes. and particularly preferred rotating speed interval is 750～2000 commentaries on classics/min, and most preferred rotating speed interval is 1000～1500 commentaries on classics/min.
In optimized technical scheme of the present invention, the mixing time of the aniline monomer aqueous solution and the dopant acid aqueous solution is 5～90 minutes, and the particularly preferred time period is 10～60 minutes, and the most preferred time period is 20～30 minutes.
As shown in the above, the present invention sets about from novel organic-inorganic matrix material angle, in the process of chemical in-situ polymerization polyaniline, add an amount of inorganic oxide conductive powder, the oxidative polymerization of aniline is preferentially carried out on the surface of inorganic oxide conductive powder particulate, thereby obtain with the inorganic oxide conductive powder is nuclear, electrically conductive polyaniline is the inorganic oxide conductive powder/polyaniline conductive polymer matrix material with nucleocapsid structure of shell, the inorganic oxide conductive powder/polyaniline conductive polymer composite products of gained, its specific conductivity can reach the scope of 0.2-25.0S/cm, have the higher specific conductivity of scope, also have the specific conductivity more much higher than inorganic oxide conductive powder 0.01-0.1S/cm than general chemistry oxidation in-situ polymerization synthesized polyaniline 0.05-2S/cm.And than general chemistry oxidation in-situ polymerization synthetic polyaniline higher yield is arranged by synthetic inorganic oxide conductive powder/polyaniline conductive polymer composite products of the present invention, thereby reduced the residual quantity of aniline and ultra-fine polyaniline in the filtered wastewater, thereby the contaminated wastewater of synthesized polyaniline conductive polymer composite product reduced greatly.In addition, because the oxidative polymerization of aniline preferentially carries out on the surface of inorganic oxide conductive powder particulate, polyaniline macromole or the arrangement of its segment on the surface of inorganic oxide conductive powder particulate trend towards more regular orderly, thereby demonstrate chloroform by synthetic inorganic oxide conductive powder/polyaniline conductive polymer composite products of the present invention, dimethylbenzene, meta-cresol, N-Methyl pyrrolidone, organic solvents such as acetonitrile have bigger solubleness, easier processing film forming or with the organic solvent suspension of inorganic oxide conductive powder/polyaniline conductive polymer matrix material modulation polyaniline conductive polymer coating and other polyaniline conductive polymer derived product.Therefore have broad application prospects in fields such as New Antistatic Materials, metal anti-corrosive paint, boats and ships factory antifouling paint and advanced composite materials by synthetic inorganic oxide conductive powder/polyaniline conductive polymer composite products of the present invention.
Therefore, synthesizing inorganic oxide conductive powder/polyaniline conductive polymer composite material good product performance of the present invention, quality height, method is simple, easy to operate, yield is high, pollution is little.
Embodiment
Embodiment 1:
Take by weighing aniline 14g and be dissolved in the 140g water, the 42.5g Witco 1298 Soft Acid is dissolved in 100ml[HCL]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add 300～1200 order inorganic oxide conductive powder ATO (weisspiessglanz doped stannum oxide) 1.12g; Restir is after half an hour, and mixed solution is creamy white. and take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise in the reactor then, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation react 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filter, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtaining conducting powder ATO/ polyaniline conductive polymer composite material 75 ℃ of following vacuum-dryings. the productive rate of matrix material is 86wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 21.0S/cm.
Same quadrat method, the general chemistry oxidation in-situ polymerization polyaniline that under the situation that does not add ATO, synthesizes, its specific conductivity has only 1-2S/cm, and the productive rate of gained polyaniline is 74%.
Same quadrat method is dissolved in 100ml[H with Witco 1298 Soft Acid
2SO
4The mixed acid solution of]=1mol/L replaces Witco 1298 Soft Acid to be dissolved in 100ml[HCL]=mixed acid solution of 2mol/L carries out above-mentioned reaction, the conducting powder ATO/ polyaniline conductive polymer composite material that synthesizes, its productive rate is 88wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 15.0S/cm.As seen replace Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with Witco 1298 Soft Acid-sulfuric acid mixed acid solution, its productive rate of conducting powder ATO/ polyaniline conductive polymer composite material that synthesizes slightly increases, but it is many that specific conductivity is on the low side, so the mineral acid in mineral acid/organic acid nitration mixture dopant acid aqueous solution is best with hydrochloric acid, sulfuric acid takes second place, and other mineral acid or effect are more inferior or price is expensive.
Same quadrat method, the add-on of inorganic oxide conductive powder ATO reaches the conducting powder ATO/ polyaniline conductive polymer composite material that synthesizes under 2.5,5.0,7.5,10.0,12.5,15.0 and 17.5% the situation of aniline respectively, its specific conductivity is 2.4,9.4,18.6,24.5,9.6,5.6 respectively, 2.3S/cm, the specific conductivity that all is higher than the general chemistry oxidation in-situ polymerization polyaniline that synthesizes under the situation that does not add ATO, and the productive rate of the inorganic oxide conductive powder ATO/ polyaniline conductive polymer composite material of gained is 81-89%.Particle surface form with the inorganic oxide conductive powder ATO/ polyaniline conductive polymer composite material of scanning electron microscope analysis gained; the content of finding inorganic oxide conductive powder ATO is about 10% when following, and inorganic oxide conductive powder ATO particle is all wrapped up or covers by polyaniline basically.But along with the ATO addition is increased to when a certain amount of, polyaniline just can not or cover whole ATO particles parcels, thereby just has free ATO particle occur in the ATO/ polyaniline conductive polymer composite material.
Same quadrat method, the add-on of inorganic oxide conductive powder ATO reaches 20.0 of aniline respectively, 25.0,30.0,35.0,40.0 and the conducting powder ATO/ polyaniline conductive polymer composite material that synthesizes under 50.0% the situation, its specific conductivity is respectively 1.4,0.6,0.4,0.3,0.3,0.2S/cm, all be lower than the specific conductivity of the general chemistry oxidation in-situ polymerization polyaniline that synthesizes under the situation that does not add ATO, but the specific conductivity that all is higher than pure inorganic oxide conductive powder ATO, and the productive rate of the inorganic oxide conductive powder ATO/ polyaniline conductive polymer composite material of gained is 83-95%.Particle surface form with the inorganic oxide conductive powder ATO/ polyaniline conductive polymer composite material of scanning electron microscope analysis gained, discovery is along with the continuous increase of ATO addition, can not ATO particle parcel or the polyaniline that covers is more and more, ATO particle that is partly wrapped up or covered by polyaniline and the exposed or free ATO particle that is not wrapped up or cover by polyaniline substantially are also more and more.
Same quadrat method uses the Sodium Persulfate of identical mol ratio or Potassium Persulphate to replace ammonium persulphate not obvious to the influence of the conducting powder ATO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.Just the price of ammonium persulphate is relatively cheap, also removes easily in washing process.But be to use the potassium bichromate of most preferred amount or ammonium dichromate also not obvious to the influence of the conducting powder ATO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity for ammonium persulphate.
Same quadrat method, the inorganic oxide conductive powder ATO that uses is no matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, and is not obvious to the influence of the conducting powder ATO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.
Embodiment 2:
Take by weighing aniline 14g and be dissolved in the 140g water, the 35.4g camphorsulfonic acid is dissolved in the 100ml water and joins together in the reactor, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic oxide conductive powder ATO (antimony-doped tin oxide) 1.4g; Restir is after half an hour, and mixed solution is creamy white. and take by weighing the 32.9g ammonium persulphate and be dissolved in the 274g water, be added dropwise in the reactor then, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation react 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filter, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtain the adulterated polyaniline conductive polymer composite material of conducting powder ATO/ camphorsulfonic acid 75 ℃ of following vacuum-dryings.The productive rate of matrix material is 82.0wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 14.0S/cm.
Same quadrat method, the camphorsulfonic acid doped polyaniline of the general chemistry oxidation in-situ polymerization that under the situation that does not add ATO, synthesizes, its specific conductivity has only about 0.5-1S/cm, and the productive rate of gained polyaniline is 72-75%.
Same quadrat method, the add-on of inorganic oxide conductive powder ATO reaches the conducting powder ATO/ camphorsulfonic acid doped polyaniline conductive polymer composite that synthesizes under 2.5,5.0,7.5,12.5,15.0 and 17.5% the situation of aniline respectively, its specific conductivity is 1.5,2.7,5.1,4.6,2.8 respectively, 1.1S/cm, the specific conductivity that all is higher than the camphorsulfonic acid doped polyaniline of the general chemistry oxidation in-situ polymerization that synthesizes under the situation that does not add ATO, and the productive rate of the inorganic oxide conductive powder ATO/ polyaniline conductive polymer composite material of gained is 81-89%.
Same quadrat method, the add-on of inorganic oxide conductive powder ATO reach the adulterated polyaniline conductive polymer composite material of conducting powder ATO/ camphorsulfonic acid that synthesizes under 20.0,25.0,30.0,35.0,40.0 and 50.0% the situation of aniline respectively.Its specific conductivity is 0.8,0.4,0.3,0.3,0.2 respectively, 0.2S/cm, all be lower than the specific conductivity of the general chemistry oxidation in-situ polymerization camphorsulfonic acid doped polyaniline that synthesizes under the situation that does not add ATO, but the specific conductivity that all is higher than pure inorganic oxide conductive powder ATO, and the productive rate of the inorganic oxide conductive powder ATO/ camphorsulfonic acid doped polyaniline conductive polymer composite of gained is 82-94%.And the add-on of conducting powder ATO has similar Changing Pattern to specific conductivity, the productive rate of the adulterated ATO/ polyaniline conductive polymer composite material of camphorsulfonic acid to embodiment one.
Particle surface form with the inorganic oxide conductive powder ATO/ camphorsulfonic acid doped polyaniline conductive polymer composite of scanning electron microscope analysis gained has similar rule to embodiment one.
Embodiment 3:
Taking by weighing aniline 14g is dissolved in the 140g water, 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid are dissolved in 100ml[HCL]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic oxide conductive powder ITO (indium doped stannum oxide) 1.4g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtain conducting powder ITO/ polyaniline conductive polymer composite material 75 ℃ of following vacuum-dryings.The productive rate of matrix material is 80wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 15.0S/cm.
Same quadrat method, replace camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution, its productive rate of conducting powder ITO/ polyaniline conductive polymer composite material that synthesizes slightly increases, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method, the doped polyaniline of the general chemistry oxidation in-situ polymerization that under the situation that does not add ITO, synthesizes, its specific conductivity has only about 1.0-2.0S/cm, and the productive rate of gained polyaniline is 72-75%.And the add-on of inorganic oxide conductive powder ITO has similar Changing Pattern to embodiment one with embodiment two to specific conductivity, the productive rate of ITO/ polyaniline conductive polymer composite material.Usually the add-on of inorganic oxide conductive powder ITO is in the 8-12% of aniline scope, and the specific conductivity of mixture is the highest.When the add-on of ITO had surpassed about 16-20%, its specific conductivity was lower than the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes under the situation that does not add ITO.The Changing Pattern of productive rate is also similar with embodiment two to embodiment one.
With the particle surface form of the inorganic oxide conductive powder ITO/ doped polyaniline conductive polymer composite of scanning electron microscope analysis gained, also finding has similar rule to embodiment one with embodiment two.
Same quadrat method uses the Sodium Persulfate of identical mol ratio or Potassium Persulphate to replace ammonium persulphate not obvious to the influence of the conducting powder ITO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.But be to use the potassium bichromate of most preferred amount or ammonium dichromate also not obvious to the influence of the conducting powder ITO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity for ammonium persulphate.
Same quadrat method, the inorganic oxide conductive powder ITO that uses is no matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, and is not obvious to the influence of the conducting powder ITO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.
Embodiment 4:
Taking by weighing aniline 14g is dissolved in the 140g water, be dissolved in 100ml[HCL with 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic oxide conductive powder SnO
21.4g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtain conducting powder SnO 75 ℃ of following vacuum-dryings
2/ polyaniline conductive polymer composite material.The productive rate of matrix material is 80wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 21.5S/cm.
Similar with embodiment one, inorganic oxide conductive powder SnO
2Add-on and SnO
2The specific conductivity of/polyaniline conductive polymer composite material, productive rate have similar Changing Pattern.Common inorganic oxide conductive powder SnO
2Add-on in the 8-12% of aniline scope, the specific conductivity of mixture is the highest.Work as SnO
2Add-on when having surpassed about 16-20%, its specific conductivity is lower than and does not add SnO
2Situation under the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes.The Changing Pattern of productive rate is also similar with embodiment two to embodiment one.
Inorganic oxide conductive powder SnO with the scanning electron microscope analysis gained
2The particle surface form of/doped polyaniline conductive polymer composite, also finding has similar rule to embodiment 1 with embodiment 2.
Same quadrat method replaces camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution, the conducting powder SnO that synthesizes with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution
2Its productive rate of/polyaniline conductive polymer composite material slightly increases, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method uses the Sodium Persulfate of identical mol ratio or Potassium Persulphate to replace the conducting powder SnO of ammonium persulphate to synthesizing
2The influence of/polyaniline conductive polymer composite material productive rate and specific conductivity is not obvious.But be to use the potassium bichromate of most preferred amount or ammonium dichromate to replace the conducting powder SnO of ammonium persulphate to synthesizing
2The influence of/polyaniline conductive polymer composite material productive rate and specific conductivity is also not obvious.
Same quadrat method, the inorganic oxide conductive powder SnO of use
2No matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, to the conducting powder SnO that synthesizes
2The influence of/polyaniline conductive polymer composite material productive rate and specific conductivity is not obvious.
Embodiment 5:
Taking by weighing aniline 14g is dissolved in the 140g water, be dissolved in 100ml[HCL with 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic oxide conductive powder zinc oxide, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide) 1.4g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtain inorganic oxide conductive powder zinc oxide, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/polyaniline conductive polymer composite material 75 ℃ of following vacuum-dryings.The productive rate of matrix material is 80wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 8.0-17.0S/cm.
Similar to Example 1, the add-on of inorganic oxide conductive powder zinc oxide (or weisspiessglanz, Indium sesquioxide, Cadmium oxide) and inorganic oxide conductive powder zinc oxide (or weisspiessglanz, Indium sesquioxide, the Cadmium oxide)/specific conductivity of polyaniline conductive polymer composite material, productive rate have similar Changing Pattern.Usually the add-on of inorganic oxide conductive powder zinc oxide (or weisspiessglanz, Indium sesquioxide, Cadmium oxide) is in the 8-12% of aniline scope, and the specific conductivity of mixture is the highest.When the add-on of inorganic oxide conductive powder zinc oxide (or weisspiessglanz, Indium sesquioxide, Cadmium oxide) had surpassed about 16-20%, its specific conductivity was lower than the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes under the situation that does not add inorganic oxide conductive powder zinc oxide (or weisspiessglanz, Indium sesquioxide, Cadmium oxide).The Changing Pattern of productive rate is also similar with embodiment two to embodiment one.
With the particle surface form of the inorganic oxide conductive powder zinc oxide of scanning electron microscope analysis gained (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/doped polyaniline conductive polymer composite, also finding has similar rule to embodiment one with embodiment two.
Same quadrat method, replace camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution, the conducting powder zinc oxide that synthesizes, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/its productive rate of polyaniline conductive polymer composite material slightly increase, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method uses the Sodium Persulfate of identical mol ratio or Potassium Persulphate to replace ammonium persulphate not obvious to the influence of the conducting powder zinc oxide that synthesizes, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/polyaniline conductive polymer composite material productive rate and specific conductivity.But be to use the potassium bichromate of most preferred amount or ammonium dichromate also not obvious to the influence of the conducting powder zinc oxide that synthesizes, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/polyaniline conductive polymer composite material productive rate and specific conductivity for ammonium persulphate.
Same quadrat method, the inorganic oxide conductive powder zinc oxide that uses, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide) are no matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, and is not obvious to the influence of the conducting powder zinc oxide that synthesizes, (or weisspiessglanz, Indium sesquioxide, Cadmium oxide)/polyaniline conductive polymer composite material productive rate and specific conductivity.
Embodiment 6:
Taking by weighing aniline 14g is dissolved in the 140g water, be dissolved in 100ml[HCL with 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add the alumina doped zinc oxide of inorganic oxide conductive powder (AZO) (or magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.) 1.4g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and do not detect sulfate radical for extremely; To constant weight, promptly obtain inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.)/polyaniline conductive polymer composite material 75 ℃ of following vacuum-dryings.The productive rate of matrix material is 80wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 16.0-25.0S/cm.
Similar to Example 1, inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, the bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.) add-on and inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.)/specific conductivity of polyaniline conductive polymer composite material, productive rate have similar Changing Pattern.Usually the add-on of inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.) is in the 8-12% of aniline scope, and the specific conductivity of mixture is the highest.When inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, the bismuth oxide doping zinc-oxide, when add-on gallium oxide doping zinc-oxide etc.) has surpassed about 16-20%, its specific conductivity is lower than and does not add inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.) the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes under the situation.The Changing Pattern of productive rate is also similar with embodiment two to embodiment one.
Inorganic oxide conductive powder AZO (or magnesium oxide doping zinc-oxide with the scanning electron microscope analysis gained, the bismuth oxide doping zinc-oxide, gallium oxide doping zinc-oxide etc.)/and the particle surface form of doped polyaniline conductive polymer composite, also finding has similar rule to embodiment 1 with embodiment 2.
Same quadrat method, replace camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution, its productive rate of conducting powder AZO/ polyaniline conductive polymer composite material that synthesizes slightly increases, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method uses the Sodium Persulfate of identical mol ratio or Potassium Persulphate to replace ammonium persulphate not obvious to the influence of the conducting powder AZO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.But be to use the potassium bichromate of most preferred amount or ammonium dichromate also not obvious to the influence of the conducting powder AZO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity for ammonium persulphate.
Same quadrat method, the inorganic oxide conductive powder AZO that uses is no matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, and is not obvious to the influence of the conducting powder AZO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.
Embodiment 7:
Taking by weighing aniline 14g is dissolved in the 140g water, be dissolved in 100ml[HCL with 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic binary composite oxides, as: zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, Cadmium oxide-Indium sesquioxide conducting powder 1.4g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 27.4g ammonium persulphate and be dissolved in the 274g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 24h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and can't check sulfate radical for extremely; To constant weight, promptly obtain inorganic oxide conductive powder zinc oxide-stannic oxide 75 ℃ of following vacuum-dryings, magnesium oxide-Indium sesquioxide, Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material.The productive rate of matrix material is 80wt%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 8.0-17.5S/cm.
Similar to Example 1, inorganic binary composite oxides, zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, the add-on of Cadmium oxide-Indium sesquioxide and inorganic oxide conductive powder zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, the specific conductivity of Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material, productive rate have similar Changing Pattern.Common inorganic binary composite oxides, zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, the add-on of Cadmium oxide-Indium sesquioxide is in the 8-12% of aniline scope, and the specific conductivity of mixture is the highest.When inorganic binary composite oxides, zinc oxide-stannic oxide, when magnesium oxide-Indium sesquioxide, the add-on of Cadmium oxide-Indium sesquioxide had surpassed about 16-20%, its specific conductivity was lower than the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes under the situation that does not add inorganic oxide conductive powder.The Changing Pattern of productive rate is also similar with embodiment two to embodiment one.
Inorganic binary composite oxides with the scanning electron microscope analysis gained, zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, the particle surface form of Cadmium oxide-Indium sesquioxide/doped polyaniline conductive polymer composite, also finding has similar rule to embodiment one with embodiment two.
Same quadrat method, replace camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution, conducting powder zinc oxide-the stannic oxide that synthesizes, magnesium oxide-Indium sesquioxide, its productive rate of Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material slightly increases, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method, use the Sodium Persulfate or the Potassium Persulphate of identical mol ratio to replace the conducting powder zinc oxide-stannic oxide of ammonium persulphate to synthesizing, magnesium oxide-Indium sesquioxide, the influence of Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material productive rate and specific conductivity is not obvious.But be to use the potassium bichromate of most preferred amount or ammonium dichromate to replace the conducting powder zinc oxide-stannic oxide of ammonium persulphate to synthesizing, magnesium oxide-Indium sesquioxide, the influence of Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material productive rate and specific conductivity is also not obvious.
Same quadrat method, the inorganic binary composite oxides that use, zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide, Cadmium oxide-Indium sesquioxide is no matter be nano level, submicron order or ultra micron powder, and its globule size is compared with add-on, to the conducting powder zinc oxide-stannic oxide that synthesizes, magnesium oxide-Indium sesquioxide, the influence of Cadmium oxide-Indium sesquioxide/polyaniline conductive polymer composite material productive rate and specific conductivity is not obvious.
Embodiment 8:
Taking by weighing aniline 14g is dissolved in the 140g water, be dissolved in 100ml[HCL with 35.4g camphorsulfonic acid or 42.5g Witco 1298 Soft Acid]=mixed acid solution of 2mol/L joins in the reactor together, on electric blender, stir (the rotating speed interval be 1000～1500 change/min); After emulsification half an hour, add inorganic oxide conductive powder AZO (alumina doped zinc oxide) 1.6g; Restir is after half an hour, and mixed solution is creamy white.Take by weighing the 13.9g potassium bichromate and be dissolved in the 200g water, be added dropwise to then in the reactor, 0～10 ℃ of ice-water bath control reaction temperature, reaction takes place immediately, after 1h dropwises, under agitation reacts 12h, reaction solution becomes yellow-green colour by oyster white, and is light blue, blueness, blue-greenish colour, green, last solution is blackish green latax, filters, separate, be washed with distilled water to filtrate and do not detect till the sulfate radical; To constant weight, promptly obtain inorganic oxide conductive powder AZO/ polyaniline conductive polymer composite material 75 ℃ of following vacuum-dryings.The productive rate of matrix material is 85wt%, and AZO content is about 10%, and recording specific conductivity with Suzhou telecommunication instrument plant four point probe digital electric conductance testing tool is 8.0～10.0S/cm.
Similar to Example 1, the add-on of inorganic oxide conductive powder AZO has similar Changing Pattern to specific conductivity, the productive rate of AZO/ polyaniline conductive polymer composite material.Usually the add-on of inorganic oxide conductive powder AZO is in the scope of 8-10%, and the specific conductivity of mixture is the highest.When the add-on of AZO had surpassed about 16-20%, its specific conductivity was lower than the general chemistry oxidation in-situ polymerization doped polyaniline that synthesizes under the situation that does not add AZO.The Changing Pattern of productive rate is also similar to embodiment one.
With the particle surface form of the inorganic oxide conductive powder AZO/ doped polyaniline conductive polymer composite of scanning electron microscope analysis gained, also finding has similar rule to embodiment one.
Same quadrat method, replace camphorsulfonic acid or Witco 1298 Soft Acid-hydrochloric acid mixed acid solution with camphorsulfonic acid or Witco 1298 Soft Acid-sulfuric acid mixed acid solution, its productive rate of conducting powder AZO/ polyaniline conductive polymer composite material that synthesizes slightly increases, but specific conductivity is on the low side, and is similar to embodiment 1.
Same quadrat method uses the ammonium dichromate of identical mol ratio to replace potassium bichromate not obvious to the influence of the conducting powder AZO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.
Same quadrat method, the inorganic oxide conductive powder AZO that uses is no matter be nano level, submicron order or ultra micron powder, its globule size is compared with add-on, and is not obvious to the influence of the conducting powder AZO/ polyaniline conductive polymer composite material productive rate that synthesizes and specific conductivity.
Claims (10)
1. inorganic oxide conductive powder/polyaniline conductive polymer matrix material, it is characterized in that it has following raw material: the aqueous solution and the inorganic oxide conductive powder of the aqueous solution of aniline monomer, the dopant acid aqueous solution, oxygenant, the aniline monomer aqueous solution wherein: the dopant acid aqueous solution: the mol ratio of aqueous oxidizing agent solution is 1: 0.6～0.83: 0.25～1.2, aniline monomer: the mass ratio of inorganic oxide conductive powder is 1: 0.025～0.50;
Described inorganic oxide conductive powder is selected the monobasic oxide powder material with semi-conductor or low electric conductivity energy for use, has the doping oxide powder body material of conductivity, i.e. the conductive doped powder of binary oxide, or binary oxide composite conductive powder;
Described oxygenant is selected solubility persulphate, solubility dichromate for use;
Described dopant acid is selected mineral acid, organic acid or mineral acid/organic acid nitration mixture for use.
2, inorganic oxide conductive powder/polyaniline conductive polymer matrix material according to claim 1 is characterized in that: described monobasic oxide powder material is zinc oxide, stannic oxide, weisspiessglanz, Indium sesquioxide or Cadmium oxide; The conductive doped powder of described binary oxide is weisspiessglanz doped stannum oxide ATO, Indium sesquioxide doped stannum oxide ITO, alumina doped zinc oxide AZO, magnesium oxide doping zinc-oxide, bismuth oxide doping zinc-oxide, or gallium oxide doping zinc-oxide; Described binary oxide composite conductive powder is zinc oxide-stannic oxide, magnesium oxide-Indium sesquioxide or Cadmium oxide-Indium sesquioxide.
3, inorganic oxide conductive powder/polyaniline conductive polymer matrix material according to claim 1 is characterized in that: the inorganic oxide conductive powder that is adopted is the ultra micron powder of nano inorganic oxide conducting powder, submicro inorganic oxide conductive powder or inorganic oxide conductive powder.
4, inorganic oxide conductive powder/polyaniline conductive polymer matrix material according to claim 1 is characterized in that: the concentration of the aqueous solution of aniline monomer is 1～15wt%, and the concentration of the aqueous solution of oxygenant is 5～25wt%.
5, inorganic oxide conductive powder/polyaniline conductive polymer matrix material according to claim 1 is characterized in that: aniline monomer: the mass ratio of inorganic oxide conductive powder is 1: 0.025～0.20.
6, prepare the method for claim 1,2,3,4 or 5 described inorganic oxide conductive powder/polyaniline conductive polymer matrix materials, step is as follows:
The aqueous solution and the dopant acid aqueous solution of aniline monomer are mixed, then inorganic oxide conductive powder is added and mix, carry out oxidative polymerization in the aqueous solution adding said mixture with oxygenant again, from reaction product, collect target product at last, i.e. the inorganic oxide conductive powder/polyaniline conductive polymer matrix material.
7. method according to claim 6 is characterized in that the temperature of reaction for preparing the inorganic oxide conductive powder/polyaniline conductive polymer matrix material is-10～50 ℃, and the reaction times is 4～24h.
8. method according to claim 6, the mixing time that it is characterized in that the aniline monomer aqueous solution and the dopant acid aqueous solution is 5～90 minutes.
9. method according to claim 6 is characterized in that the time of mixing of inorganic oxide conductive powder adding aniline monomer and dopant acid mixed aqueous solution is 1～30 minute.
10. method according to claim 6 is characterized in that oxidative polymerization carries out under constantly stirring, stirring velocity per minute 500～3000 changes.
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