CN1328074A - Composite aqueous latex containing electrically conducting polymer and insulating components and its preparing process and application - Google Patents
Composite aqueous latex containing electrically conducting polymer and insulating components and its preparing process and application Download PDFInfo
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- CN1328074A CN1328074A CN 00118356 CN00118356A CN1328074A CN 1328074 A CN1328074 A CN 1328074A CN 00118356 CN00118356 CN 00118356 CN 00118356 A CN00118356 A CN 00118356A CN 1328074 A CN1328074 A CN 1328074A
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Abstract
A compound aqueous latex with high dielectric constant and containing electrically conductive polymer and insulative component, its preparing process and its application are disclosed. Said latex is prepared through adding the unsaturated olefin monomer, emulsifier and water-soluble trigger for free radical reaction to the prepared electrically conductive polymer, and polymerizing reaction at 50-90 deg.C and pH value greater than 7 in inert gas atmosphere.
Description
The present invention relates to a kind of composite aqueous latex that contains electrically conducting polymer and insulating components, and relate to the preparation method and the application thereof of this composite aqueous latex with high-k low conductivity.The emulsion product that the invention particularly relates to conductive polymers such as polyaniline, polypyrrole, Polythiophene etc. or their derivative further with the electrically conducting polymer and insulating components composite aqueous latex of one or more other unsaturated monomers through the high-k of free-radical emulsion polymerization prepared in reaction, and relate to the preparation method of this composite aqueous latex and in the application of battery, electromagnetic wave shielding, electromagnetic interference, transmitter, precision capacitor, aspect such as antistatic.
For a long time, conductive polymerss such as polyaniline, polypyrrole, Polythiophene demonstrate its vital role and potentiality owing to its excellent conductivity in many Application Areass, receive great concern, as all having a wide range of applications at battery, electromagnetic interference, eliminostatic, transmitter and aspect such as anticorrosion.But how introduce these conductive polymerss in the polymkeric substance of routine, produce a kind of easy to produce and usely, and the combination product with excellent anti static and high-k then is technical problem demanding prompt solution.Make its requirement that reaches actual use as the technical method of modifying of once developing multiple polyaniline, as the method for aniline and N-substituted aniline or the copolymerization of ring substituted aniline; Use has the method for long-chain branch doping agent, as with organic acid such as Witco 1298 Soft Acid, camphorsulfonic acid or with the method for polymer acid such as polystyrolsulfon acid, polyacrylic acid; And such as forming the method for blend or matrix material with thermal plasticity high polymer.But these methods all can't obtain the stable latex and the copolymerization product of excellent anti static and high-k as mentioned above.
People's such as Yong Cao United States Patent (USP) 5 324 453 discloses a kind of emulsion polymerisation process of aniline, wherein use aniline, organic acid such as Witco 1298 Soft Acid (DBSA), organic solvent such as dimethylbenzene, chloroform to constitute organic phase, the aqueous solution initiated polymerization of dropping oxidizing agent gradually at low temperatures then, then the heavy-gravity emulsion is poured in the acetone to finish polyreaction, polyaniline-DBSA salt is precipitated out, and the polyaniline-DBSA that so obtains can be dissolved in chloroform, the toluene equal solvent.This method also can not get stable latex products.
Therefore, the present inventor is through going deep into extensive studies, a kind of composite aqueous latex that contains electrically conducting polymer and insulating components of high-k is provided and the preparation method of this matrix material latex is provided.In the electrically conducting polymer and insulating components matrix material latex of high-k low conductivity of the present invention, conductive component combines with the insulation component, usually conductive component is disperse phase in this matrix material, for example conductive component is insulated component and wraps up, and the two tangles mutually, grafting etc.; Wherein conducting polymer can be polyaniline, polypyrrole, Polythiophene etc. or corresponding derivative; Insulation component wherein is common superpolymer, for example polystyrene, polymethylmethacrylate, polyethyl methacrylate, Vinalac 5920, polyisobutyl methacrylate, polymethyl acrylate, polyethyl acrylate, the positive butyl ester of polyacrylic acid, polyisobutyl acrylate, polyvinyl chloride, polyhutadiene, polyvinyl acetate, polyacrylonitrile etc. or above-mentioned mixture of polymers.According to the present invention, a kind of microemulsion method with broad applicability is provided, microemulsion all keeps low viscosity in entire reaction course.The final copolymer emulsion that forms has wide practical use in fields such as antistatic, anticorrosion, transmitters, and can be used as printing ink, coating, paint etc.; Also can be used as fluid conductors or semi-conductor, be used for as devices such as gravity switch, liquid detection device, other electronic apparatus switches.
The purpose of this invention is to provide conductive polymers-insulation component composite material latex of a kind of high-k and its production and application; Provide a kind of electrically conductive aqueous latex of polyphnenylamine of new stable for extended periods of time, and the preparation method of this electrically conductive aqueous latex of polyphnenylamine to be provided and to use also be one object of the present invention.Other purpose of the present invention will obtain embodying from following further describing.
According to the present invention, a kind of composite aqueous latex that contains electrically conducting polymer and insulating components of high-k is provided, this aqueous latex comprises conductive polymer composition, insulation component, water, emulsifying agent and polymer and disperses auxiliary agent; Described conductive polymer composition normally is selected from least a polymeric part in polyaniline, polypyrrole, Polythiophene etc. or the corresponding derivative; Described insulation component is to be polymerized by ethylenically unsaturated monomer; Described ethylenically unsaturated monomer is selected from vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide etc. or their mixture at least a usually; Based on aqueous latex gross weight meter, the content of water is 60-99.5% in this aqueous latex; Described matrix material content is 0.4-34%; Wherein conductive polymer composition with respect to the insulation component weight fraction between 1%-200%; Emulsifying agent is 0-1% (weight) in the concentration of aqueous phase; It is 0.1-5% (weight) in the concentration of aqueous phase that polymer disperses auxiliary agent.
The preparation method of the electrically conducting polymer and insulating components composite aqueous latex of this high-k may further comprise the steps:
(1) prepared based on aqueous latex gross weight meter water-content be 60-99.5%, polymer to disperse auxiliary agent content be that 0.1-5%, conductive polymers content are to add inorganic salt in the conductive polymer precursor component aqueous latex of 0.4%-34%, the pH value of keeping aqueous latex is greater than 7;
(2) be warming up under the inert atmosphere under 50～90 ℃ of conditions and stir one or more ethylenically unsaturated monomers of 0.5～100 times that add with respect to the weight of conductive polymers, usually this ethylenically unsaturated monomer is to be selected from monomer at least a in the following material: vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide etc. or their mixture, and add emulsifying agent, the concentration that makes the aqueous phase emulsifying agent is 0～1% (weight);
(3) under inert atmosphere 50-90 ℃ add down with respect to adding monomer weight be to react 8-38 hour behind the water-soluble free radical reaction initiator of 0.05～0.8% (weight), promptly make the composite aqueous latex that contains electrically conducting polymer and insulating components of this high-k.
Wherein said conductive polymer precursor component should have been removed resistance polymers matter, and this resistance polymers produces in its polymerization process, and this resistance polymers can be removed with the known conventional method, and this is known in the art.
Described in the method conductive polymer precursor component is selected from polyaniline, polypyrrole, Polythiophene etc. or the corresponding derivative at least a.They are to use with the form of aqueous latex in reaction.Described water-soluble free radical reaction initiator is selected from (but being not limited to) peroxy acid salt, peroxidation two acyl classes, peroxy dicarbonates, peroxycarboxylic acid esters class, water-soluble azo class or the like.
Above-mentioned high-k provided by the invention contains the electrically conducting polymer and insulating components composite aqueous latex and is applied in many-sides such as antistatic, anticorrosion, transmitter, electromagnetic wave shielding, electronics or electric switches.As being used as printing ink, coating etc.Electrically conductive polyaniline water miscible liquid of the present invention is easy to storage and transport owing to stability is excellent, and use properties is reliable, and production technique is simple, and directly use does not need complicated separation forming step.Production and use have all embodied economical, convenient, stay-in-grade beneficial effect.
Fig. 1 and 2 is the photo of the transmission electron microscope of two kinds of conductive polymer precursor insulating components composite products obtaining in embodiment 1 and 2.
Fig. 3 is composite products ultraviolet-visible spectrum spectrogram before and after polymerization prepares the electrically conducting polymer and insulating components matrix material of embodiment 4.
Along with the development of making rapid progress of material science, many breakthroughs have also occured in conducting polymer compound field, have synthesized the conducting polymer compound of hundreds of different structures and type. On structure, they can be divided into conjugated polymer, electric charge shifts complex, polymer ions-free radical salt, metal-containing polymer etc. Wherein, the conducting polymer of conjugated structure is then representing the main flow of conducting polymer development. The conducting polymer of representational conjugated structure comprises polyaniline, polypyrrole, polythiophene etc. or corresponding derivative etc. General these conducting polymer composites are insoluble molten rigidity characteristic owing to its structural characteristics have, thereby is very limited in application because of poor processability. For these conducting polymer composites are fully utilized, enlarge as far as possible its application, the inventor has carried out long-term research in this field, develop a kind of new method of modifying, and take the method as the basis, synthesize the low conductivity electrically conducting polymer and insulating components composite with high-k.
The composite aqueous latex that contains electrically conducting polymer and insulating components of high-k prepared according to the methods of the invention comprises conductive polymer composition, insulation component, water, emulsifying agent and macromolecule and disperses auxiliary agent; Described insulation component is formed by ethylenically unsaturated monomer polymerisation under the condition that has the conductive polymer precursor component; Based on aqueous latex gross weight meter, the content of water is 60-99.5% in this aqueous latex; Described composite content is 0.4%-34%; Wherein conductive polymer composition, is preferably between the 20-170% between 1%-200% with respect to the weight fraction of insulation component; Emulsifying agent is 0-1% (weight) in the concentration of aqueous phase, is preferably 0.01-0.5% (weight), more preferably 0.08-0.3% (weight); Disperseing auxiliary agent with macromolecule is 0.1-5% (weight) in the concentration of aqueous phase, is preferably 0.8～3% (weight).
As the conducting polymer of conductive polymer precursor component, the conducting polymer of conjugated structure commonly used all can use in principle. General spendable comprise in polyaniline, polypyrrole, polythiophene or their the corresponding derivatives at least a. The preferred polyaniline or derivatives thereof that uses uses after also can directly becoming polymer water latex with emulsion form by monomer polymerization. Preferred this conductive polymer precursor is the doping type conducting polymer. Generally can use this area various emulsifying agents commonly used and macromolecule to disperse auxiliary agent, these emulsifying agents and macromolecule disperse selecting of auxiliary agent, can determine according to the specific requirement of different conducting polymers formation stable emulsions. As in the situation of polyaniline, preferably use anionic emulsifier, and preferred disperse auxiliary agent shared with macromolecule. In this conducting polymer aqueous latex, based on aqueous latex gross weight meter, water content is 60～99.5%, is preferably 70～85%, more preferably 72～80%; Anionic emulsifier content is 1-8%, is preferably 2-6%, more preferably 2.5～5.5%; It is 0.1～5% that macromolecule disperses auxiliary agent content, is preferably 0.3～4%, more preferably 0.5～3.5%; And conducting polymer content is 0.4～34%, is preferably 1～25%, more preferably 5～15%. And the particle diameter of made conducting polymer latex is between 60 to 700nm, preferably between 100～400nm.
Adapt therewith, the present invention preferably uses aqueous latex of polyphnenylamine as this conductive polymer precursor component. According to the present invention, a kind of electrically conductive aqueous latex of polyphnenylamine is provided, this latex comprises that water, doped polyaniline and macromolecule disperse auxiliary agent; Described polyaniline is the polymerizate of the aniline or derivatives thereof of chemical formula (1):
In the formula, R1、R
2、R
3、R
4、R
5Be respectively-H ,-CH3、-NO
2、-F、-Cl、
-OCH
3、-C
2H
5,-Br and/or-I; And this polyaniline is mixed by the anionicsite in the anionic emulsifier, and the content of water accounts for the 60-99.5 % of aqueous latex weight in this aqueous latex, is preferably 70～85% (weight); And electrically conductive polyaniline accounts for 0.4～34 % of this aqueous latex weight, is preferably 1～25%, more preferably 5～15%.
After the aqueous latex of conductive polymer precursor component is determined, also need to add therein inorganic salts, so that the pH value of reaction system, is beneficial to the polymerisation of ethylenically unsaturated hydrocarbons class monomer in system greater than 7. The inorganic salts of the general type that use this area all can be used for the present invention. The example of applicable inorganic salts comprises sodium carbonate, sodium acid carbonate, potash, saleratus, calcium carbonate, calcium bicarbonate, sodium acetate, potassium acetate etc. or their mixture. The use of these inorganic salts can add according to the process discontinuous of reaction or once all add. Its consumption is generally 1%～3% based on reaction system gross weight meter, can be come according to a conventional method to determine by those of ordinary skills.
Carry out the required ethylenically unsaturated monomer of emulsion polymerization and generally be this area normally used those, generally be selected from styrene, methyl methacrylate, EMA, n-BMA, isobutyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, vinyl chloride, butadiene, vinyl acetate, acrylonitrile etc. or their mixture. The consumption of these ethylenically unsaturated monomers can change in wide range. General its weight fraction with respect to conducting polymer is 0.5-100 times. Those of ordinary skill in the art can make suitable adjustment according to the requirement of final use. When adding ethylenically unsaturated monomer, temperature can be under normal temperature or the Elevated Temperature Conditions carries out. Preferably under higher temperature, add. Especially preferred range is 50～90 ℃.
When adding ethylenically unsaturated monomer, also can in the emulsion reaction system, add an amount of emulsifying agent, but its consumption should be limited in and make its concentration less than the scope of its critical micelle concentration, to avoid further having the secondary karyomorphism to become in the reaction. This area emulsifying agent commonly used all can use, such as anionic emulsifier, cationic emulsifier, nonionic emulsifier etc., such as potassium oleate, potassium rosinate, potassium laurate, dodecyl sodium sulfate, neopelex, lauryl sodium sulfate, sldium lauryl sulfate, hexadecane trimethyl ammonium bromide, laurylamine hydrochloride, sorbitan laurate, octyl phenol polyglycol ether etc. General preferred use anionic emulsifier. Consumption is generally 0～1% (weight) with respect to adding monomer weight meter, is preferably 0.01～0.5% (weight), more preferably 0.08～0.3% (weight). The anionic emulsifier that is fit to generally is selected from dodecyl sodium sulfate, lauryl sodium sulfate, neopelex, odium stearate, potassium stearate, potassium oleate or enuatrol etc.
The radical initiator that uses in the methods of the invention must be water-soluble radical initiator, generates to guarantee emulsion polymeric product. The example that is fit to the water-soluble radical initiator of routine of the present invention comprises peracid salt, peroxidating two acyl classes, peroxy dicarbonates, peroxycarboxylic acid esters class, water-soluble azo compounds etc. Its consumption is generally 0.05～2% (weight) with respect to adding ethylenically unsaturated monomer weighing scale, is preferably 0.8～1.2% (weight).
Carry out emulsion polymerization after above reaction system stirred under 50-90 ℃ of temperature in inert atmosphere. Reaction time is generally at 8～38 hours. Namely make the composite aqueous latex that contains electrically conducting polymer and insulating components of high-k. According to the difference of final application target and certain requirement, also can in the finished product aqueous latex, add suitable quantity of water, make the content of water in the aqueous latex in 60～99.5% (weight) scope, do suitable adjustment.
In a preferred embodiment of the invention, be to make this electrically conductive aqueous latex of polyphnenylamine with the aniline or derivatives thereof through emulsion polymerisation. This electrically conductive aqueous latex of polyphnenylamine prepared according to the methods of the invention comprises that water, doped polyaniline and macromolecule disperse auxiliary agent; Described polyaniline is the polymerizate of the aniline or derivatives thereof of chemical formula (1):In the formula, R1、R
2、R
3、R
4、R
5Be respectively-H ,-CH3、-NO
2、-F、-Cl、
-OCH
3、-C
2H
5,-Br and/or-I; Wherein the content of water accounts for the 60-99.5% of aqueous emulsion weight, is preferably 70-85%.
The preparation method of this electrically conductive aqueous latex of polyphnenylamine may further comprise the steps:
(a) the aniline or derivatives thereof is dissolved in organic solvent and makes solution, making the concentration of aniline or derivatives thereof in organic solvent is 0.02～2.0 mol;
(b) add anionic emulsifier and polymer in water and disperse auxiliary agent to form solution, its concentration is based on water weight meter, and anionic emulsifier is 1-8% (weight), and it is 0.1-5% (weight) in the concentration of aqueous phase that polymer disperses auxiliary agent;
(c) mix above-mentioned two kinds of solution under vigorous stirring and form emulsion, its ratio is that water and organic solvent volume ratio are 0.1～8.0, is preferably 0.3～2.0;
(d) in this emulsion, slowly add protonic acid and make its pH value for being lower than 7, even can be 0 or negative value;
(e) the dropping oxidizing agent aqueous solution or protonic acid solution under 0～25 ℃ of condition, the oxidative polymerization of initiation aniline or derivatives thereof, the mol ratio of oxygenant and aniline or derivatives thereof is 0.1-4.0;
(f) finish reaction, organic solvent partly is the electrically conductive aqueous latex of polyphnenylamine product with aqueous latex layering, isolated aqueous latex; This product promptly can be used for follow-up emulsion polymerizing modification reaction after dialysis; Because this latex has permanent stability, it is easier to use.
(g) add inorganic salt in the electrically conductive polyaniline precursor component aqueous latex that this prepares, the pH value of keeping aqueous latex is greater than 7.
(h) being warming up to the weight fraction that adds under 50～90 ℃ of conditions with respect to the conductive polymer precursor component under the inert atmosphere is 0.5-100 one or more ethylenically unsaturated monomers doubly, this monomer is selected from: vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide or their mixture, and can add with respect to adding monomer weight be 0-1% (weight), be preferably the emulsifying agent of 0.01～0.5% (weight);
(i) under inert atmosphere 50～90 ℃ stir down add with respect to adding monomer weight be to react 8～38 hours behind the water-soluble free radical reaction initiator of 0.05～0.8% (weight), promptly make the composite aqueous latex that contains the electrically conductive polyaniline insulating components of high-k.
Wherein said conducting polyaniline amine precursor should be an electrically conductive polyaniline of having removed resistance polymers matter, and this resistance polymers matter produces in the polyaniline polymerization process, and available known conventional method is removed.
In this embodiment, the polymerization of aniline or derivatives thereof need be carried out under acidic conditions, and sour polyreaction for aniline provides hydrogen ion and improves the oxidative polymerization of aniline.But the aniline salt that aniline forms in acidic solution may be dissolved in the acidic aqueous solution, and this is disadvantageous to carry out emulsion polymerization in water medium.Therefore, should keep the acid-reaction condition, reduce the solubleness of aniline in acidic aqueous solution again, be to realize a problem to be solved by this invention.Acid simultaneously has destruction to the stable of emulsion again, thereby the dispersive emulsion particle is assembled breakdown of emulsion takes place.This has more increased the difficulty of implementing.
In order to address the above problem, before water miscible liquid is made in the emulsification of aniline or derivatives thereof, elder generation is dissolved in the aniline monomer raw material and can makes in its dissolved organic solvent, with form emulsification formation monomer water miscible liquid in the water miscible liquid that is added with anionic emulsifier and polymer dispersion auxiliary agent of its organic solvent solution.Through this dissolution process in advance, reached the purpose that reduces the solubleness of aniline in acidic aqueous solution, thereby in the presence of emulsifying agent and dispersing auxiliary, obtain needed emulsion, and in polymerization process, form oil phase as the emulsion of aniline source of supply.General organic solvent all can use.The example of the organic solvent that is suitable for has (but being not limited thereto) chloroform, toluene, benzene, methylene dichloride, hexane, hexanaphthene and/or their mixture.These organic solvents all have the low characteristics of solubleness in water.The solubleness of organic solvent in water is low more, and is favourable more to reaching the requirement that reduces the solubleness of aniline in acidic aqueous solution.
During preparation organic solution, the concentration of aniline or derivatives thereof in organic solvent is advisable between 0.02～2.0 mol, is preferably between 0.3～0.6 mol.And water and organic solvent volume ratio are advisable between 0.1～8.0 in the emulsion, preferably between 0.3～2.0.
Under acidic conditions, carry out the emulsion polymerization of aniline or derivatives thereof, require to have stable emulsion dispersion system.Therefore need lot of experiments work to determine emulsifier system.In the present invention, disperseing auxiliary agent to be used with anionic emulsifier and polymer is advisable.Wherein, anionic emulsifier also plays the effect of the doping agent of polyaniline except that playing emulsifying effect.The example of described anionic emulsifier (but being not limited thereto) has sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate, sodium oleate etc.This anionic emulsifier, is 1-8% (weight) based on water weight meter in the concentration of aqueous phase; And the mol ratio of aniline or derivatives thereof is advisable between 0.1-1.0, is preferably between the 0.1-0.8, more preferably between the 0.3-0.6.If this ratio is excessive, the organic phase drop is dispersed to very little in the emulsion system, surface-area increases, thereby the rate of diffusion of aniline monomer is accelerated, cause reaction to be accelerated, and, make the polyaniline molecule interchain generation accumulative trend that increases sharply obviously strengthen owing to intensive hydrogen bond action between the NH group of polyaniline, make polymer particle strengthen the system bad stability.And if this ratio is too low, the emulsifying agent quantity not sufficient does not have due emulsifying effect, is unfavorable for the requirement of system stability equally.And the emulsifying agent consumption is too low, can not satisfy the needs of its doping effect.Described polymer disperses auxiliary agent to play crucial effects too to stablizing this emulsion system.This polymer disperses the example (but being not limited thereto) of auxiliary agent that polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose gum, derivatived cellulose, starch, gelatin etc. are arranged.It counts 0.1-5% (weight) in the concentration of aqueous phase based on water weight, is preferably 0.3～1% (weight).
Is 0.1～8.0 with aniline or derivatives thereof solution that forms in organic solvent and the water miscible liquid system that is added with anionic emulsifier and polymer dispersion auxiliary agent by water and organic solvent volume ratio, 0.3～2.0 the ratio of being preferably is mixed mutually, and vigorous stirring, be made into monomer water miscible liquid system.In the water miscible liquid system that this is made into, also need add protonic acid and regulate its pH value to being lower than 7, even be 0 or negative value, thereby help the oxidative polymerization of aniline.The conventional protonic acid that uses in general this area all can be used for the present invention.But the amount ranges of acid should be limited in and can not make within the consumption that emulsion system stability is damaged.Because the affiliation that adds of acid makes the bad stability of emulsification system, make oil phase drop instability, be gathered into big drop, and be unfavorable for that stable reaction carries out smoothly, until the situation that uncontrollable reaction takes place.But too little as fruit acid concentration, oxidative polymerization there is not the use of promotion, when oxygenant adds in the emulsion, react not begin immediately, so the equally also oxidized dose destruction of emulsion.Therefore, protonic acid is advisable between 0.1 to 10 mol in the concentration of aqueous phase, preferably in 0.3-2.0 mol scope.The example (but being not limited thereto) of the protonic acid that is suitable for has toluene sulfonic acide, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, methylsulphonic acid, hydrofluoric acid, perchloric acid, acetate, trifluoroacetic acid etc.
The oxidative polymerization of realizing the aniline or derivatives thereof needs to carry out under the oxygenizement condition of oxygenant, and this is known in the art.Oxygenant commonly used known in the art all can be used for the present invention.The example (but being not limited thereto) of the oxygenant that is suitable for has ammonium persulphate, Potassium Persulphate, potassium bichromate, potassium permanganate, Potcrate, plumbous oxide, iron(ic) chloride, cupric chloride, hydrogen peroxide etc.These oxygenant initiators can add separately in the reaction system in use, also can add with the protonic acid wiring solution-forming.The amount ranges of oxygenant should be controlled in the scope of mol ratio between 0.1-4.0 of oxygenant and aniline or derivatives thereof, is preferably 0.5-2.0.When this oxygenant added reaction system with the protonic acid wiring solution-forming, the concentration range of protonic acid was that 0 to 10 mol is advisable in the oxidizing agent solution, is preferably the 0.3-2.0 mol.
The emulsion polymerization of aniline or derivatives thereof of the present invention all can well carry out under 0～25 ℃ and condition of normal pressure, but preferably carries out under 0-5 ℃.Its reaction times was generally 8 minutes-8 hours, was preferably 20 minutes-3 hours.After reaction is finished, because anionic emulsifier also plays the Polyaniline Doped agent, all be consumed owing to the doping effect, there has not been unnecessary emulsifying agent in the emulsion system, reaction system will be layered as aqueous phase layer and organic solvent mutually layer significantly this moment, thereby can easily isolate organic solvent.The polymer water latex that obtains promptly can be used as the polyaniline product emulsion and directly uses after dialysis.In this aqueous latex product, the mol ratio of doping anionicsite and aniline is generally 0.1～0.8 in the doped polyaniline, is preferably 0.3～0.6.Thereby obtain by the aqueous latex of the adulterated polyaniline of anionicsite in the anionic emulsifier.Through polymeric polyaniline solids product is carried out conductance measurement (four point probe method), its specific conductivity is generally greater than 1 to 15S/cm.
As above the electrically conductive aqueous latex of polyphnenylamine for preparing like this can be used for the monomeric emulsion polymerization of the present invention and ethylenically unsaturated hydrocarbons without any processing.Even after placing 5-12 month, still can normally use.
At first in having removed the electrically conductive aqueous latex of polyphnenylamine that hinders the polymeric material, stir and add inorganic salt, as yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, lime carbonate, Calcium hydrogen carbonate, sodium-acetate, Potassium ethanoate etc. or their mixture (but being not limited thereto), make to be weakly acidic this polyaniline latex pH value and to be tending towards neutral greater than 7 to weakly alkaline.Usually the consumption of these inorganic salt counts 0.5～3% based on electrically conductive aqueous latex of polyphnenylamine weight for this reason, is preferably 1～2%.
This electrically conductive aqueous latex of polyphnenylamine pH value be adjusted to tend towards stability greater than 7 after, be warming up to stir under 50～90 ℃ of conditions and add ethylenically unsaturated monomer and add small amounts of emulsifiers.Conventional this area is used for the polymeric ethylenically unsaturated monomer and all can uses.This monomer generally comprises (but being not limited thereto) vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide etc. or their mixture.These monomers should be removed wherein contained compositions such as stopper by means known in the art earlier before using.This monomeric consumption is counted 0.5～100 times with respect to electrically conductive aqueous latex of polyphnenylamine weight.According to the monomer that is added, can use different emulsifying agents, so that reaction system keeps the stable emulsion form.This area emulsifying agent commonly used all can use.Used emulsifying agent can be identical or different with the emulsifying agent that uses in the electrically conductive aqueous latex of polyphnenylamine.The preferred anionic emulsifier that uses.The emulsifying agent that is suitable for is selected from (but being not limited thereto) sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate, sodium oleate etc.Its consumption is generally 0～1% with respect to adding monomer weight meter, preferred 0.01-0.5% (weight), more preferably 0.3～3% (weight).
Stir this reaction system evenly after, add water-soluble radical initiator, and continue to stir.This initiator generally is selected from the peracid salt, peroxidation two acyl classes, peroxy dicarbonates, peroxycarboxylic acid esters class and water-soluble azo class etc.Its consumption is generally 0.05～2% (weight) with respect to adding monomer weight meter, is preferably 0.8～1.2% (weight).Sustained reaction adds the terminator stopped reaction after 8～38 hours under 50～90 ℃ of temperature.This product is promptly made polyaniline/ethylenically unsaturated monomer polymer composites.The color of this final latex product is blackish green shallow than polyaniline obviously, illustrates that original polyaniline precursor particles interacts with ethylenically unsaturated monomer reaction product that the back adds and combines, and forms electrically conductive polyaniline insulating components matrix material.Good consistency has guaranteed not have in the emulsion polymerization stage generation of secondary nuclear between the two.
Below the present invention is described in detail, further specify the present invention below in conjunction with embodiment.But these embodiment can not think the present invention there is any restriction.
Embodiment:
Use following raw materials according among the embodiment:
Aniline (Aldrich company) is through distillation, be stored in the low temperature environment, ammonium persulphate (Aldrich company), hydrochloric acid (Merck company), chloroform (Aldrich company), Sodium dodecylbenzene sulfonate (Aldrich company), benzene (Merck company) and toluene (Aldrich company) all directly use.The molecular weight of polyvinyl alcohol (PVA) (Aldrich company) is 25,000,88% degree of hydrolysis.Initiator is 2,2 '-azo (2-diamino methane-propane) hydrochloride (Wake pure chemistry Industrial Co., Ltd) directly uses, and the stopper in the vinylbenzene is removed.
Relevant test and testing method are described as follows in the experiment.
Specific conductivity: polyaniline latex is placed in 70 ℃ the baking oven, evaporate water and promptly obtain the powder of polyaniline, the four point probe method that the mensuration of the specific conductivity of polyaniline powder adopts Van Der Pauw to propose, finish under the room temperature: the mensuration of resistivity is to apply continuous current on therein two electrodes, and the potential difference of measuring in addition between two electrodes can obtain resistivity.
Latex particle diameter: DLS is determined on the Malvern 4700SM particle-size analyzer and finishes, and adopts the Ar ion laser, wavelength 488nm, power 50mW.Laser light scattering (PCS) diameter adopts the Stokes-Einstein Equation for Calculating to obtain.
Transmission electron microscope: transmission electron microscope photo obtains on Philips EM400, and acceleration voltage is 100KV.
Uv-visible absorption spectroscopy: the ultraviolet ray-visible absorption spectrum of polyaniline latex and polyaniline/styrene polymer matrix material is finished on Varian CARY-4E ultraviolet-visible spectrometer, and scanning speed is 600nm/min.
Specific inductivity: adopt Hewlett-Packard HP4285A Precision LCR to measure the specific inductivity of product powder, measure range of frequency 50KHz to 1MHz.
Embodiment 1
(1) preparation of polyaniline latex
Prepare the toluene solution 70ml (concentration of aniline in toluene is 0.357mol/L) that contains 2.33g (0.025mol) aniline in advance, add to above-mentioned toluene solution and to contain 0.75g polyvinyl alcohol (polymer dispersion auxiliary agent) and 3.50g (0.01mol) Sodium dodecylbenzene sulfonate is the water miscible liquid of the 150ml of anionic emulsifier, under violent stirring, form white emulsion, slowly add the hydrochloric acid soln of 20ml5mol/L again.
Drip the 0.5mol/L HCl60ml of the ammonium persulphate that contains 5.70g (0.025mol) in above-mentioned solution, polyreaction is carried out in 0 to 5 ℃ temperature range.
React after 1-2 hour and finish, stop to stir, owing to there is not unnecessary Sodium dodecylbenzene sulfonate to exist in solution, reaction system is separated, and organic solvent can be separated at an easy rate.
The polyaniline latex that obtains is at room temperature dialysed to remove inorganic salt and the acid in the latex, changes distilled water every day three times, dialyses 4 days.
The particle dia of the polyaniline latex that obtains is 160nm, solid content 0.93%.
(2) preparation of polyaniline-styrene polymer matrix material latex
Vinylbenzene directly filters with alkali alumina, promptly removes resistance polymers matter wherein.Resistance polymers matter in the polyaniline latex can be removed as follows: add alkali alumina by the consumption that adds the alkali alumina about 20g in every 100ml polyaniline latex, stirred 15 hours, filter the removal alkali alumina and get final product; Use 130ml polyaniline latex then, the pH value that the sodium bicarbonate that adds 0.05g under nitrogen atmosphere is therein kept reaction system is slightly larger than 7; Under nitrogen protection, be warming up to 65 ℃, in polyaniline latex, add the vinylbenzene of 7.80g, stirred 2 hours, make the abundant swelling polyaniline of vinylbenzene latex particle; Add the sodium lauryl sulphate of 0.10g in above-mentioned solution, the concentration of sodium lauryl sulphate is less than its micelle-forming concentration; Add initiator 2,2 '-azo (2-aminomethane-propane) hydrochloride, this initiator concentration is 3mmol/L; Be reflected at and carried out under 65 ℃ 20 hours, along with the carrying out of reaction, the color of reaction system shoals, and obtains 170ml matrix material latex.The conducing composite material that obtains can carry out performance test, and the diameter of matrix material latex particle is 422nm.Fig. 1 is its transmission electron microscope photo, and the result shows the formation that does not have secondary nuclear, and the specific inductivity under different frequencies is listed in the table 1, and conduction copolymerization conductivity of electrolyte materials is less than 10
-9S/cm.
The specific inductivity of table 1 matrix material under different frequency
| Frequency (KHz) | 0.03 | ?0.1 | ?0.5 | ?1 | ?2 | ?5 | ?10 | ?20 | ?50 |
| Specific inductivity | 18.0 | ?14.5 | ?10.6 | ?9.3 | ?7.2 | ?6.4 | ?5.7 | ?5.7 | ?4.8 |
| Frequency (MHz) | 0.1 | ?0.2 | ?0.3 | ?0.4 | ?0.5 | ?0.6 | ?0.8 | ?1.0 | |
| Specific inductivity | 4.2 | ?3.8 | ?3.5 | ?3.4 | ?3.3 | ?3.2 | ?3.1 | ?3.1 |
Embodiment 2-4
The preparation method is with embodiment 1, institute's difference is to change the cinnamic add-on different conducing composite material latex of component concentration that obtains insulating, the diameter and the corresponding specific conductivity of latex particle are listed in the table 2 before and after the polymerization, and the specific inductivity of conducing composite material particle under different frequency listed in the table 3.
Latex particle diameter variation and specific conductivity before and after table 2 Composite Preparation
| Solid content % before the latex polymerization | Polyaniline volume (ml) | The vinylbenzene add-on | Before the styrene polymerization (nm) | Behind the styrene polymerization (nm) | Solid content % after the polymerization | Latex volume (ml) | Specific conductivity behind the styrene polymerization (S/cm) | |
| Embodiment 2 | ????0.79 | ?120 | ?9.09g | ?215 | ????478 | ????4.7 | ????160 | ????＜10 -9 |
| Embodiment 3 | ????0.93 | ?120 | ?1.95g | ?129 | ????155 | ????1.5 | ????150 | ????8×10 -7 |
| Embodiment 4 | ????0.93 | ?120 | ?4.65g | ?139 | ????207 | ????1.1 | ????155 | ????5×10 -9 |
In sreen analysis before and after the above embodiment 1-4 polymerization, comparison sheet 2, the result of Fig. 1 and Fig. 2 as can be seen, the particle dia value that the diameter of the transmission electron microscope of embodiment 1 and 2 product particle obtains near laser light scattering (PCS) method.
Table 3 matrix material is at the specific inductivity of different frequency
| Frequency (KHz) | ?0.03 | ?0.1 | ?0.5 | ????1 | ??2 | ??5 | ??10 | ?20 | ??50 |
| Embodiment 2 | ?12.2 | ?10.0 | ?7.1 | ?6.0 | ?5.1 | ?4.2 | ?3.7 | ?3.4 | ?3.0 |
| Embodiment 3 | ?1923 | ?1009 | ?585 | ?468 | ?398 | ?323 | ?272 | ?217 | ?144 |
| Embodiment 4 | ?650 | ?316 | ?140 | ?102 | ?75.5 | ?50.4 | ?37.0 | ?27.3 | ?19.0 |
| Frequency (MHz) | ?0.1 | ?0.2 | ?0.3 | ?0.4 | ?0.5 | ?0.6 | ?0.8 | ?1.0 | |
| Embodiment 2 | ?2.8 | ?2.7 | ?2.6 | ?2.6 | ?2.6 | ?2.5 | ?2.5 | ?2.5 | |
| Embodiment 3 | ?98.7 | ?67.1 | ?54.7 | ?47.9 | ?43.6 | ?40.6 | ?36.5 | ?33.9 | |
| Embodiment 4 | ?15.1 | ?12.5 | ?11.1 | ?10.5 | ?10.0 | ?9.7 | ?9.2 | ?8.9 |
Specific conductivity in the above-mentioned table and specific inductivity data presentation combine conductive polymer precursor with the common superpolymer of insulation, can obtain the matrix material of low conductivity and specific inductivity, and the specific inductivity of polystyrene is 10
3To 10
8Be 2.55 between the Hz, and be almost constant that the specific inductivity of the conducing composite material that the present invention obtains will be higher than the dielectric constant values of polystyrene in whole range of frequency, increase with the reduction of frequency.
The PCS diameter variation of table 4 polyaniline/styrene polymer matrix material latex before and after dialysis
| Before the dialysis | After the dialysis | |
| PCS diameter (nm) | ????478 | ????473 |
Polyaniline/styrene polymer matrix material latex with embodiment 2 is at room temperature dialysed, change water every day three times, dialysed four days, disperse auxiliary agent and inorganic salt to remove emulsifying agent, polymer, the diameter of polyaniline/styrene polymer latex particle redeterminates, listed experimental result in the table 4, the PCS diameter of polyaniline/styrene polymer matrix material has good repeatability as can be seen, and this shows that polyaniline/styrene polymer matrix material latex at room temperature is stable.
Fig. 3 is the spectrogram that the polyaniline/styrene polymer matrix material to embodiment 4 carries out the uv-visible absorption spectrum test, this absorption spectrum figure shows that the position of polyaniline and the vinylbenzene absorption peak of polyaniline/styrene polymer matrix material after polymerization does not change because form matrix material, thereby thinks that the conjugated structure of polyaniline does not have destroyed.
The following examples change the influence of solvent, polymer dispersion auxiliary agent, emulsifying agent and the preparation of their condition p-poly-phenyl amine latexes such as consumption in order to explanation.
Embodiment 5-8
Condition is with embodiment 1, and organic solvent is a benzene, the concentration difference of polyvinyl alcohol, the particle dia difference of the polyaniline latex that obtains.
Embodiment 9-10
Synthesis condition adopts different solvents with embodiment 1, and the diameter of the polyaniline particle that obtains is also different.
Embodiment 11
Make solvent with benzene, the concentration of aniline in this organic solvent doubles, and is 0.714Mol/L; Keeping the mol ratio of ammonium persulphate/aniline is 1/1, all the other conditions are all with embodiment 1, and the diameter of the polyaniline particle that obtains is 246nm, and the specific conductivity of the polyaniline powder that obtains of latex is 10.6S/cm thus, the specific inductivity of polyaniline is respectively under the different frequency: 50KHz, 169; 100KHz, 146; 200KHz, 128; 300KHz, 121; 400KHz, 116; 500KHz, 113; 600KHz, 109; 800KHz, 105; 1MHz, 101.
Embodiment 12
Ammonium persulphate/aniline mol ratio is 1/2, other synthesis conditions are with embodiment 11, and the diameter of the polyaniline latex particle that obtains is 250nm, and the specific conductivity of the polyaniline powder that obtains of latex is 3.6S/cm thus, the specific inductivity of polyaniline is respectively under the different frequency: 50KHz, 144; 100KHz, 133; 200KHz, 123; 300KHz, 119; 400KHz, 116; 500KHz, 113; 600KHz, 110; 800KHz, 105; 1MHz, 101.
Embodiment 13-14
Synthesis condition is with embodiment 1, and keeping the mol ratio of anionic emulsifier (Sodium dodecylbenzene sulfonate)/aniline is 0.4, and keeping the mol ratio of oxygenant (ammonium persulphate)/aniline is 1/1, further reduces the concentration of aniline in toluene, and the result is as follows:
Embodiment 15-18
Synthesis condition is with embodiment 1, keeping the mol ratio of anionic emulsifier (Sodium dodecylbenzene sulfonate)/aniline is 0.4, and keeping the mol ratio of oxygenant (ammonium persulphate)/aniline is 1/1, adopts the solvent of benzene as aniline, change the concentration of aniline in benzene, the result is as follows:
Embodiment 19
Synthesis condition is with embodiment 1, and anionic emulsifier adopts sodium lauryl sulphate, and the particle dia of the polyaniline latex that obtains is 420nm.
Embodiment 20-23
Synthesis condition adopts the chloroform give solvent with embodiment 1, changes the consumption of anionic emulsifier Sodium dodecylbenzene sulfonate, obtains the polyaniline latex particle of different diameter.
Embodiment 24
Synthesis condition is with embodiment 1, and the employing Potassium Persulphate is an oxygenant, and keeping the mol ratio of oxygenant/aniline is 1/1.With benzene is solvent, and the polyaniline latex particle diameter that obtains is 155nm.
Embodiment 25
Synthesis condition adopts the protonic acid of nitric acid as the aniline oxidative polymerization with embodiment 1, and used concentration of nitric acid is with embodiment 1, and the polyaniline latex particle diameter that obtains is 265nm.
Embodiment 26
Synthesis condition is with embodiment 1, and adopting Polyvinylpyrolidone (PVP) is that polymer disperses auxiliary agent, and the polyaniline latex particle diameter that obtains is 232nm.
In conjunction with above explanation and embodiment, draw as drawing a conclusion:
(1) changes polymerizing condition and can change polyaniline or derivatives thereof latex particle diameter;
(2) polyaniline or derivatives thereof latex is more stable under room temperature state;
(3) polyaniline or derivatives thereof latex can form stable mixture latex with common polymer latex.
Claims (30)
1. the composite aqueous latex that contains electrically conducting polymer and insulating components of a high-k, this aqueous latex comprise conductive polymer composition, insulation component, water, emulsifying agent and polymer and disperse auxiliary agent; Described insulation component is polymerized by ethylenically unsaturated monomer; Based on aqueous latex gross weight meter, the content of water is 60-99.5% in this aqueous latex; Described matrix material content is 0.4-34%; Wherein conductive polymer composition with respect to the insulation component weight fraction between 1%-200% (weight); Emulsifying agent is that 0-1% (weight) polymer dispersion auxiliary agent is 0.1～5% (weight) in the concentration of aqueous phase in the concentration of aqueous phase.
2. according to the aqueous latex of claim 1, it is characterized in that this emulsifying agent is an anionic emulsifier.
3. according to the aqueous latex of claim 1, it is characterized in that anionic emulsifier is selected from sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate or sodium oleate.
4. according to the aqueous latex of claim 1, it is characterized in that described conductive polymer composition be selected from polyaniline, polypyrrole, Polythiophene or the corresponding derivative at least a.
5. according to the aqueous latex of claim 1, it is characterized in that described ethylenically unsaturated monomer is selected from vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide or their mixture.
6. according to the aqueous latex of claim 1, it is characterized in that described conductive polymer composition is a doped polyaniline, described polyaniline is the polymerisate of the aniline or derivatives thereof of chemical formula (1):
In the formula, R
1, R
2, R
3, R
4, R
5Be respectively-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br and/or-I; And this polyaniline is adulterated by the anionicsite in the anionic emulsifier.
7. according to the aqueous latex of claim 6, it is characterized in that the mol ratio of doping anionicsite and aniline is 0.1～0.8 in the doped polyaniline.
8. according to the aqueous latex of claim 7, it is characterized in that the mol ratio of doping anionicsite and aniline is 0.3～0.6 in the described doped polyaniline.
9. according to the aqueous latex of claim 1, it is characterized in that described polymer disperses auxiliary agent to be selected from polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose gum, derivatived cellulose, starch or gelatin.
10. according to the aqueous latex of claim 1, it is characterized in that the specific inductivity of the matrix material that obtained by this aqueous latex is higher than the specific inductivity of corresponding insulation component.
11. the preparation method of the composite aqueous latex that contains electrically conducting polymer and insulating components of a high-k may further comprise the steps:
(1) prepared based on gross weight meter water-content be 60-99.5%, polymer to disperse auxiliary agent content be that 0.1-5% and conductive polymer precursor content are to add inorganic salt in 0.4%～34% the conductive polymer precursor component aqueous latex, the pH value of keeping aqueous latex is greater than 7;
(2) be warming up to one or more ethylenically unsaturated monomers of 0.5～100 times that add under 50～90 ℃ of agitation conditions with respect to the weight of conductive polymer precursor component aqueous latex under the inert atmosphere, can add emulsifying agent, the concentration that makes the aqueous phase emulsifying agent is 0-1% (weight);
(3) under inert atmosphere, add under 50-90 ℃ of temperature with respect to adding monomer weight be to react 8-38 hour behind the water-soluble free radical reaction initiator of 0.05～0.8% (weight), promptly make the composite aqueous latex that contains electrically conducting polymer and insulating components of this high-k.
12. method according to claim 11 is characterized in that described ethylenically unsaturated monomer is to be selected from monomer at least a in the following material: vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide or their mixture.
13. method according to claim 11, it is at least a to it is characterized in that described conductive polymer precursor component is selected from polyaniline, polypyrrole, Polythiophene etc. or the corresponding derivative.
14. method according to claim 11 is characterized in that described conductive polymer precursor component aqueous latex is an electrically conductive aqueous latex of polyphnenylamine, this latex comprises water, doped polyaniline and polymer and disperses auxiliary agent; Described polyaniline is the polymerisate of the aniline or derivatives thereof of chemical formula (1):
In the formula, R
1, R
2, R
3, R
4, R
5Be respectively-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br and/or-I; And this polyaniline is adulterated by the anionicsite in a kind of anionic emulsifier.
15., it is characterized in that anionic emulsifier is selected from sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate or sodium oleate according to the method for claim 14.
16., it is characterized in that described polymer disperses auxiliary agent to be selected from polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose gum, derivatived cellulose, starch or gelatin according to the method for claim 11.
17., it is characterized in that it is 0.1～5% (weight) in the concentration of aqueous phase that described polymer disperses auxiliary agent according to the method for claim 11.
18., it is characterized in that wherein said emulsifying agent is an anionic emulsifier, is selected from sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate or sodium oleate according to the method for claim 11.
19., it is characterized in that the specific conductivity of the polyaniline that obtained by this aqueous latex is 1-15S/cm according to the method for claim 14.
20., it is characterized in that the mol ratio of doping anionicsite and aniline is 0.1～0.8 in the doped polyaniline according to the method for claim 14.
21. the method according to claim 14 is characterized in that, the mol ratio of doping anionicsite and aniline is 0.3～0.6 in the described doped polyaniline.
22. one kind prepares the method that high-k contains the composite aqueous latex of electrically conductive polyaniline insulating components, it is characterized in that this method comprises:
(a) the aniline or derivatives thereof is dissolved in organic solvent and makes solution; Making the concentration of aniline or derivatives thereof in organic solvent is 0.02～2.0 mol;
(b) add anionic emulsifier and polymer in water and disperse auxiliary agent to form solution, its concentration is based on water weight meter, and anionic emulsifier is 1-8% (weight), and it is 0.1-5% in the concentration of aqueous phase that polymer disperses auxiliary agent;
(c) vigorous stirring is mixed above-mentioned two kinds of solution formation emulsion, and its ratio is that water and organic solvent volume ratio are 0.1-8.0;
(d) slowly adding protonic acid solution in this emulsion makes its pH value for being lower than 7;
(e) the dropping oxidizing agent aqueous solution or protonic acid solution under 0-25 ℃ of condition, the oxidative polymerization of initiation aniline or derivatives thereof, the mol ratio of oxygenant and aniline or derivatives thereof is 0.1～4.0;
(f) finish reaction, organic solvent phase and aqueous latex layering are mutually isolated the aqueous latex that aqueous latex partly is the electrically conductive polyaniline precursor component;
Wherein said aniline is the aniline or derivatives thereof of chemical formula (1):
In the formula, R
1, R
2, R
3, R
4, R
5Be respectively-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br and/or-I; The content that it is 0.3%-33% and water that electrically conductive polyaniline accounts for this water miscible liquid weight accounts for the 60-99.5% of water miscible liquid weight;
(g) add inorganic salt in the electrically conductive polyaniline precursor component aqueous latex that this prepares, the pH value of keeping aqueous latex is greater than 7;
(h) be warming up to weight 0.5-100 one or more ethylenically unsaturated monomers doubly that add under 50～90 ℃ of conditions with respect to the conductive polymer precursor component under the inert atmosphere, this monomer is selected from: vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylchlorid, divinyl, vinyl-acetic ester, vinyl cyanide or their mixture, and add with respect to adding monomer weight be the emulsifying agent of 0～1% (weight);
(i) under inert atmosphere, add under 50～90 ℃ of temperature with respect to adding monomer weight be to react 8～38 hours behind the water-soluble free radical reaction initiator of 0.05～0.8% (weight), promptly make the composite aqueous latex that contains the electrically conductive polyaniline insulating components of high-k.
23., it is characterized in that described emulsifying agent is an anionic emulsifier according to the method for claim 22.
24., it is characterized in that anionic emulsifier is selected from sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate, potassium oleate or sodium oleate according to the method for claim 23; Polymer disperses auxiliary agent to be selected from polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose gum, derivatived cellulose, starch or gelatin.
25., it is characterized in that described organic solvent is selected from chloroform, toluene, benzene, methylene dichloride, hexane, hexanaphthene and/or their mixture according to the method for claim 22.
26. the method for claim 22 is characterized in that protonic acid is selected from toluenesulphonic acids, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, methylsulphonic acid, hydrofluoric acid, perchloric acid, acetate, trifluoroacetic acid.
27. method according to claim 22 is characterized in that described oxygenant is selected from ammonium persulphate, Potassium Persulphate, potassium bichromate, potassium permanganate, Potcrate, plumbous oxide, iron(ic) chloride, cupric chloride and hydrogen peroxide.
28., it is characterized in that described water-soluble radical initiator is selected from peroxy acid salt, peroxidation two acyl classes, peroxy dicarbonates, peroxycarboxylic acid esters class and water-soluble azo compounds class according to each described method of claim 11-27.
29. the composite aqueous latex that contains electrically conducting polymer and insulating components of the described high-k of claim 1-10 is as the application of anti-electrostatic and protective system.
30. the application of the composite aqueous latex that contains electrically conducting polymer and insulating components in battery, electromagnetic interference, transmitter and electrical condenser of the described high-k of claim 1-10.
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