CN101036198B

CN101036198B - Process for coating fine particles with conductive polymers

Info

Publication number: CN101036198B
Application number: CN200580033692.9A
Authority: CN
Inventors: W·普利思; U·拉默尔特; N·赫贝斯特雷特; M·斯特拉特曼; M·罗沃德; H·-J·阿德勒; K·波特杰-卡姆洛思; E·扬尼; A·皮克; H·多默斯; J·施奈德; G·帕利沃达-普罗贝斯卡
Original assignee: Chemetall GmbH
Current assignee: Chemetall GmbH
Priority date: 2004-08-03
Filing date: 2005-08-03
Publication date: 2013-04-17
Anticipated expiration: 2025-08-03
Also published as: CN101035630B; DE102004037542A1; CN101035631A; CN101035630A; CN101036198A

Abstract

The invention relates to process for coating fine particles, wherein the mixture comprises: at the least one monomer and/or one oligomer forming a aromatics of conductive oligomer/polymer/copolymer/block copolymer/graft copolymer and/or monomer/oligomer of unsaturate; at the least a type of anions, comprising 1) anions incorporated by an structure of conductive polymer as doped ion, and 2) releasing at least a part of anions for a potential variation (reduction), 3) substance in undistributed condition to the corrosion potential of the metallic surface; at the least a type of particles; at the least one kind of oxidant; water and/or at the least an another solvent forming the coating by the mixture in the particles surface, wherein the mixture is oxidized produced by the conductive polymer under the at the least one active anticorrosion anionic condition. In addition, the fine particles can be coated with a mixture of conductive polymer products.

Description

Method with coating fine particles with conductive polymers

The present invention relates to a kind of method of coated particle, be used for the mixture of coating, coating obtained by this method, this application that is coated with particle and this particle through applying of conductive coating.

Many materials are arranged in the conducting polymer, particularly based on those of polyaniline, known in recent years.Now many chemical systems that contain conducting polymer are studied, they need not to add other conductive materials and can use.And also have to show, it is inconsiderate to add the specific processing of various ingredients and enforcement, could obtain higher conductive capability.And, for example prove then aspect metal surface anticorrosive that the large volume coating or the thin seal coat that are made of conducting polymer all are inappropriate in some cases.

But, if do not mix those mix or wet processes in can not strengthen the mixing of conducting polymer in matrix and the particle of distribution by shearing (often being called grinding), then just be difficult to conducting polymer is blended in the organic matrix and go.Therefore, has prepared, the Powdered but agranular powder of the conducting polymer of the roughly the same performance of the coating that consists of with pure conducting polymer by those, need sky high cost to mix, and this mixing cause that also relatively poor degree of mixing is arranged when mixed mutually with the composition component of organic coating.Because these powder are made of fibrous viscosity structure usually, so they are easy to and will lump.

Basically show known have many kinds inorganic and organic particle, particularly pigment, they use with the coating state, for example are coated with the oxide shell, such as multiple pigment.

If with of the present invention contain the mixture that can react the monomer that generates conducting polymer and/or oligomer be coated with fluorine on the granular core and/or within, can bring problems, because many organic core materials can be dissolved by solvent, because very few particle can not flexibly be suitable for coating performance, for example glass transformation temperature T as organic particle _gWith the concentration in the mixture, can not be aspect surface property for example by crosslinked or grafting and chemically be optimized.In addition, the particle diameter of inorganic particle distributes can not marked change as organic particle, particularly aspect narrow distribution, and also aspect grain shape.In addition, usually can be better to be suitable for those aspect chemical be necessary organic binder bond for the organic binder bond matrix to organic granular sometimes.On the other hand, be purchased inorganic particle more generally platelet-like, linearity or needle-like.

And, usually to be chosen in selected solvent or the liquid as far as possible fully insoluble nuclear material, such as great majority particularly based on those of polyacrylate, Merlon, polyethylene, polyimides, polystyrene and/or polyurethane, perhaps all inorganic particle for example.Also can use other organic polymer particles in principle.Therefore, when applying organic granular, the selection of nuclear material or the selection of solvent for use all can be restricted.Because the hardness of organic core and shell thereof is all very little, so it should be noted that the particle through applying can not break under stronger shearing condition (so-called grinding).Mention again below when grinding that not distinguishing its wetting action that whether only relates to by shearing still is in fact with the abrasive action of pulverizing.

DE19919261A1 has put down in writing a kind of method, the surface of adopting the monomer solution of known formation conducting polymer to process oxide particle in the method, and come the oxidation monomer by the reaction with oxidant, thus so that monomer reaction generates conducting polymer.Preparation based on the monomer of aniline, pyrroles or thiophene has been described in these embodiments.After the powder preparation, also to filter at last, wash, use organic solvent extraction and drying.The purpose of method described here is to produce the coating that its conductive capability can be regulated at oxide particle.For this reason, the oxidizability that will regulate conducting polymer with collaborative redox solution.But do not add corrosion inhibitor.The anion that is contained in the oxidant can not play corrosion-resisting function.Relevant preparation conducting polymer, coating, Chemical composition that described in the DE19919261A1 and further process and the content used is all introduced among the application realizingly.

Patent application DE102004037542, DE102004037552 and come from its foreign application and submitted to by same Applicant in same Patent office simultaneously, theme as the application of " with the method for anticorrosive coating coating metal surfaces " and attached foreign application and all introduce clearly the present invention, particularly relevant Depotsubstanz, anion, cation, matrix material, raw material, the content of intermediate product and end product kind and other compositions that add or form and particularly relevant chemical reaction, preparation method and condition, each operating procedure, physical chemical phenomenon, electric conductivity, potential value, electrical potential difference, TV changes and other performances, definition, the claim content, accompanying drawing, icon and purposes, embodiment, the content of embodiment and comparative example aspect.

Which the anion of a smallest number also do not have according to the knowledge of the applicant to record in piece document even can carry out the variation of system in conjunction with conducting polymer yet.Because conducting polymer---in the polymer chemical compound lot all be not available commercially and therefore must oneself take a lot of trouble to prepare---preparation and the variation of preparation condition all be very expensive, so obviously just the system change of the raw material (Edukt), anion and the oxidant that are suitable for conducting polymer not have ever made research, particularly not for based on those of polypyrrole or polythiophene yet.

Prior art for the preparation of with the great majority test of using conducting polymer in, anion---so-called counter anion or doping anion---is because preparation condition but have to be included in the mixture, to keep the electroneutral of conducting polymer in forming process.But when using conducting polymer, also seldom know the protective effect of these anion.Seldom report the corrosion-resisting function that anion in the conducting polymer is arranged in the document.But select in some experiments in advance passivating metallic surfaces, wherein for example can only be formed the metal oxalate-passivation layer of an indissoluble by oxalates, then apply the chemical system that contains conducting polymer.When for example using polyaniline, usually to apply unadulterated polyaniline and then just for example mix with phosphoric acid with this system.When with electrochemical method coated with conductive polymer, always need in advance passivation.Used identical anion has to exist and be inserted into to guarantee electroneutral as counter ion counterionsl gegenions simultaneously when the conducting polymer polymerization during with passivation.

Have now found that the anion that will add not just guarantees required electroneutral when going in being inserted into the conducting polymer structure, and want to work as them and implement corrosion-resisting function in the metal surface when from conducting polymer, again moving out.Impaired by the overcoat that these selected anion move out from conducting polymer and move on the metal surface, corrosion-resisting function can occur when coating is subject to very little damage.At this moment, the metal surface of defective all can be passivated in many cases, particularly when its when not being excessive.

Also find in addition, at least a negative electrode lamination can occur when the metal surface is corroded when corroding.Find also that in addition this negative electrode lamination occurs in before the electromotive force decline phenomenon as release signal more.Usually release signal comes across in the impaired zone, because there, common common metal and the electromotive force on the alloy thereof almost have a value more negative than the redox potential of common conducting polymer without any exception.The latter is also therefore being reduced of negative polarization thus.

Interface unsticking effect actual in the negative electrode delaminating process will be prior to the decline of electromotive force.Wherein, at the interface electromotive force primary stage of unsticking namely from a this moment value that common conducting polymer exists with oxidation state drop to an at least part of value that causes reducing of lower meeting.In this process, aspect this wherein polymer bonding of going ahead of the rest still unbroken negative electrode, usually also the hydrogen reduction effect can occur at the interface, wherein can form and to destroy the free radical that bonds at the interface and then therefore cause unsticking.Also can form at least one bubble in layering place.

Have now found that this effect can be used to can suppress the anion of this reaction with 1 by discharging) prevention further layering and/or 2) suppress lamination at this commitment.When in this commitment inner boundary unsticking not also, so then because very little these anion of seldom measuring of only needing of complete at the interface free volume still to a great extent.

This chemical system is of great use for less defective, but but can not the excessive defective of passivation, and too high and when thus can be so that when for example containing the organic coating of conducting polymer reduction occuring rapidly when the cation transport rate in total system, even may cause danger.Because the corrosion that all amounts in this chemical system and performance all will coordinate to suppress the metal surface.But only having chromate is can not passivation excessive defective equally.

In many chemical systems that contain conducting polymer, all wishing or guessing has a kind of effect (release effects) that discharges based on anion, but but can only can authenticate under very rare individual cases.Conducting polymer is inserted into the effect of playing possibly the storage that is suitable for deactivation matter such as passivation anion in the coating.The anion overwhelming majority who puts down in writing in the document can not suppress to corrode.But it is very rare and do not elaborate to be used for release effects that anticorrosion uses, never must be checking and therefore just exist conjecture in the production time known to the applicant.But the release effects that triggers owing to electromotive force decline according to the knowledge of the applicant, is never to put down in writing.

But if etch-proof anion on the books in the prior art, corrosion-resisting function also just is confined to the passivation of local defect position to the full extent so, yet for the not record of zone that just is layering.For what conducting polymer need to be distinguished be, whether they are chemistry or electrochemical polymerization, because more inexpensive metal surface always was passivated before polymer precipitation in electrochemical polymerization process: the metal surface is at first with regard to passivation when for example using oxalates.According to the knowledge of the applicant, the open source literature that records the corrosion-inhibiting anion did not then always enlighten owing to electromotive force decline discharges these anion.

The known coating that only contains chromium VI is following except self-repair effect has: even the 1. metal surface at passivation fault location damaged location place (anode divides reaction); 2. in the zone of just layering and layering, suppress negative electrode and divide reaction (Reduction of oxygen reaction).But the chromate of known sexavalence is harmful to, so will strongly reduce chromate content with the protection metal surface for the reason of environmental protection.But chromic acid also can only passivation and is repaired less and can't passivation and repair the larger area defective.But also unknown so far have chemical system in fact to have other effects out of this self-repair effect in the situation lower time that does not have hexavalent chromate.

Task of the present invention is to provide the method for and/or organic granular inorganic with conductive polymer coated, and it is in principle also applicable to the corrosion protection of metal surface.Can carry out if preparation and painting method can as far as possible simply and need not special device, then just have very large advantage.

In addition, if in fact when coating occuring damage, contain not only can change owing to the electromotive force along with electric-force gradient in the coating of each chemical system on metallic substrates of conducting polymer and reveal (the release of anion; Release effects), but also can have recovery dynatron effect (repairing effect), then this point can be particularly advantageous.But the recovery dynatron effect that delamination area can be repaired again can only be at some chemical systems and could expect under given conditions to occur.

The solution of this task is a kind of method that applies organic and/or inorganic particle, wherein said particle is present in the mixture and/or when initial and is formed at wherein, and described mixture is dispersion liquid, has material, colloidal sol and/or a gel that fluid ability or shell are mediated, it is characterized in that, contain as the mixture of raw mix:

It is selected from monomer and/or the oligomer of aromatic compounds and/or unsaturated hydrocarbon compound for-at least a monomer and/or at least a oligomer---below be called " raw material of conducting polymer " or just be called " raw material "---, such as alkynes, heterocycle, carbocyclic ring, their derivative and/or their composition, particularly preferably from the heterocycle of X=N and/or S, they are suitable for forming the oligomer/polymer/copolymer of conduction/block copolymer/graft copolymer, particularly preferably from based on imidazoles, naphthalene, luxuriant and rich with fragrance, the pyrroles, the compound that does not replace and/or replace of thiophene and/or benzenethiol;

-at least a anion---optional at least a salt, ester and/or at least a acid are as the carrier of this anion---and at least a anion 1 in the conducting polymer) can be used as in the structure that the doping ion is inserted into conducting polymer and go 2) if conducting polymer has potential drop (reduction) also can again discharge and 3 from this structure again) if exist the metal surface just can play corrosion-resisting function---below be called " the anticorrosion anion of activity ";

-at least a be selected from bunch, nano particle, nanotube, the particle of fibrous, spherical and/or loose structure, average grain diameter the particle of 10nm to 10mm and their aggregate such as aggregation block and/or agglutination body and

-water and/or another kind of at least polar solvent and optional another kind of at least solvent, be selected from especially the solvent of polar solvent, nonpolar or low pole and be selected from room temperature can not exist with liquid state, but under higher temperature, can play the solvent thing of solvent action;

And form the coating that thickness is at least an individual layer by this raw mix at least a portion particle surface, and described coating particularly preferably is comprised of monomer and/or oligomer in fact or also contain at least monomer and/or the oligomer of real mass except the another kind of at least composition of optional raw mix

And, at dispersion liquid, body, in colloidal sol or the gel or---optional at least after part removes liquid---under aerosol state, by adopting at least a oxidant and all having under the anticorrosion anion existence condition of at least a activity, utilize the voltage effect electrochemical method and/or the photochemical method of electromagnetic radiation carry out the oxidation reaction of chemistry and make at least a portion monomer and/or oligomer contain in the mixture of water and/or another kind of at least polar solvent at least in part reaction generates at least a oligomer and/or optional part or fully generates respectively at least a polymer, copolymer, block copolymer and/or graft copolymer (" product ")

And here formed oligomer, polymer, copolymer, block copolymer and/or graft copolymer---below be called " conducting polymer "---have conductive capability and/or conduction comparatively at least in part.

Here, preferably will select at least a raw material to make at least a conducting polymer according to following principle, namely its oxidation potential be less than or equals water in used mixture and/or the decomposition potential of at least a other polar solvent.

Here, movable anticorrosion anion and optional also have bonding promote the property anion preferably not and/or just time strategic point and mainly and/or fully discharge from polymer formed conduction, with anion via reduction reaction via taking off proton reaction.

Here, these anion also can be particularly preferably from based on alkanoic acid, aromatic acid, boronic acid containing, fluoric-containing acid, heteropoly acid, isopolyacid, contain acid iodide, silicic acid, lewis acid, mineral acid, contain molybdic acid, peracid, phosphoric acid, contain metatitanic acid, contain vanadic acid, contain wolframic acid, contain zirconic acid, their salt, ester and composition thereof those.

Contain at least a oxidant in the optional mixture of the present invention, and especially when there being at least a anion also to play the oxidant effect and/or when carrying out electrochemistry and/or photochemical polymerization, can completely or partially save this at least a oxidant simultaneously.

The solution of this task also depends on the method for a kind of coating inorganic and/or organic granular, wherein said particle is present in the mixture and/or namely is formed at wherein at the beginning, and a kind of suspension of mixture history, have agglomerate, colloidal sol and/or gel that fluid ability maybe can be mediated, it is characterized in that mixture is product mixture and contains:

-at least a " conducting polymer " based on oligomer/polymer/copolymer/block copolymer/graft copolymer,

-at least a anion---optional at least a salt, ester and/or at least a acid are as the carrier of this anion---and at least a anion 1 in the conducting polymer) can be used as in the structure that the doping ion was inserted into and/or was inserted at least in part conducting polymer and go 2) if conducting polymer has potential drop (reduction) also can again discharge and 3 from this structure again) if exist the metal surface just can play corrosion-resisting function---below be called " the anticorrosion anion of activity ";

-optional oxidant, water and/or another kind of at least solvent,

And form the coating that thickness is at least an individual layer by this product mixture at least a portion particle surface,

And formed oligomer, polymer, copolymer, block copolymer and/or graft copolymer---below be called " conducting polymer "---have conductive capability and/or conduction comparatively at least in part.

According to the knowledge of the applicant, the aniline, polyaniline or their derivative that also do not play a role as the present invention at present.Particularly preferably movable anticorrosion anion also can 4) have an at least hydrogen reduction effect and/or 5 in the destroyed area on minute aspect of termination) also can play the bonding facilitation, so that can partly again seal layering (recovery dynatron effect) at least.

For polyaniline, movable anticorrosion anion does not discharge from conducting polymer via reduction reaction.Because polyaniline to go back original product unstable, so in category of the present invention selective reduction not.To select hydrogenation reaction to substitute reduction reaction to discharge anion more.According to the knowledge of the applicant, the conducting polymer based on polyaniline that those can carry out by hydrogenation reaction this release is not disclosed.

When the oxidation potential of raw material is less than or equal to water and/or here during the decomposition potential of the another kind of at least polar solvent in the used mixture, then will cause the oxidation reaction (=polymerization) of conducting polymer to finish, for example can or then just can not occuring again simultaneously, the decomposition of water also for example discharges hydrogen.

Term " dispersion " not only comprises suspension in the application's category, and also has solution and emulsion.

Confirm that now particularly molybdate anion is understood owing to the potential drop at the conducting polymer that is arranged in damaged zone is released, and directly migrates to fault location.Other flyways can be got rid of in this experimentation.Then on the metal surface, can form the passivation layer that contains molybdate at the damaged location place, and can record by XPS measuring method (X-ray spectrum).

In addition, utilize now grating-Kelvin probe (SKP) also can authenticate to recovery dynatron effect.Fig. 2 of DE102004037542 and in conjunction with the measurement result of embodiment 1 there has reproduced the significant passivation effect of affected area.Omitted but there are some to measure curves in Fig. 2, these curves are to obtain between the first measured value under the very low corrosion potential and each come from the measurement curve of measurement series central point.The electromotive force that exists very significant about 0.3V therebetween raises, and this has also just hinted, has stopped at least in part in the locational lamination of layering.As a comparison, Fig. 1 has shown those effects that usually can occur.

Also determine now, owing to begun corrosion process in metal/coating interface position, the electromotive force change situation of electric-force gradient will occur having.And the release of anion (release effects) only can just can be carried out when this electromotive force change occurs.If coating is not damaged, on coating, do not have other disturbing factors yet or do not have other defect such as impurity at metal-coating interface, be inserted in then that anion in the conducting polymer will store and electromotive force is constant.

Before metal surface and the coating unsticking and between, for example such when coating occur to be damaged, electrode potential namely obviously descends.

The decline of this electromotive force can cause near especially conducting polymer generation reduction reaction defective, and discharge simultaneously have anticorrosion, anion that passivation and/or bonding promote property.

Here, potential drop can preferably have redox potential and the fault location less than the storage substance under at least a impaired attitude, the value of the difference of the corrosion potential of the metal surface on the face with at first unsticking that electromotive force changes situation particularly, thereby so that can be at least part of in advance or in early days, before faint or significant layering occurring, just suppress formation or the development of layering.

The redox potential of conducting polymer preferably be higher than each should be able to be by suitable coating the passivation potential of etch-proof metal material.Redox potential is a kind of under normal condition, and itself can have the electromotive force that obtains under the right condition of corrosive oxidation reduction with simultaneous different doping levels.

Redox potential can mainly via doping level, also namely be regulated according to anion species and its consumption.Can on purpose regulate for particle of the present invention or in coating electrical potential difference thus.The preferred redox potential of regulating conducting polymer is so that it is higher than through the electromotive force of the metal surface of passivation and is significantly higher than the electromotive force of corrosion surface.

Passivation potential is the potential value on the interface of metal surface and water, and the metal surface can form the passivation coating of a closed stablity under this potential value, thereby can further suppress melting of metal.

Particularly preferably the oxidation potential of anion is higher than the oxidation potential of raw material, because follow the effect that anion can play oxidant simultaneously.

Other preferred at least a storage substance also, be that at least a conducting polymer has and can realize the early stage redox potential that discharges of anion, and at least a storage substance have relatively low cation from the electrolyte cation transport speed out of defective and/or metal surface particularly.

Preferred cationic out enters at least a storage substance from the electrolyte of defective and/or metal surface particularly cation transport speed is for less than 10 ^-8Cm ²/ s, preferably less than 10 ^-10Cm ²/ s, extremely preferably less than 10 ^-12Cm ²/ s, particularly preferably less than 10 ^-14Cm ²/ s.

Term " damaged zone " expression defective neighboring area, the optional defective that comprises wherein, i.e. damaged location also has the in advance face of potential change, also namely wherein chemical system change has appearred." damaged location " refers to comprise the defective of the layering that may occur.Faint layering comes across in the cathode plane zone that is moved forward, and wherein polymer bonding does not still go to pot, but also usually can begin the hydrogen reduction effect on the interface.Bond if formed again there many can destruction on the interface, also namely cause the free radical of layering, then significant layering will occur.

In all cases, anion and coating, particularly at least a storage substance and/or at least a matrix material all should have specific ionic size or aperture, so that anion selected to be discharged can or can in migration by coating, not be suppressed during namely particularly by storage substance with by other compositions such as matrix substantially yet.So-called matrix material is a kind of material that consists of or substantially can consist of at least in part coated substrate, such as organic polymer/copolymer, and wherein has smooth transition region between matrix and other compositions, as after film forming.

The size that movable anticorrosion anion and/or the optional bonding that also exists promote the property anion preferably to have is wanted so that it can be when electromotive force descends move from conducting polymer with higher activity out enters into affected area and also particularly will move along the defective direction.By the directional migration of anion at the damaged location place, in containing each chemical system of conducting polymer, can suppress passivation and the optional effect (repairing effect) that damaged location is repaired that metal (further) melts with it with regard to obtaining.The precondition of this migration is, optionally comprises that also duct its solvate shell, that be suitable for moving anion wants enough greatly.In the chemical reaction at damaged location place, when melting, metal can form the cation that can in the scope of damaged position, form partly with anion passivation layer.

But the production practices so far show, the real chemical system that contains conducting polymer almost can only guarantee bar none lower electric conductivity and can not confirm so far recovery dynatron effect or this effect very faint and can not be used for industrial production.Therefore particularly preferably select a kind of chemical system, also recovery dynatron effect can occur in this system, but this effect can only could be utilized in some embodiments and under given conditions obviously again.To be devoted in addition potential gradient (starting of release effects) and the optional in addition formation condition of healing effect (recovery dynatron effect) are carried out optimization, can be used for industry.In addition, the interface of unsticking also should be able to be subject to by this chemical system (further) anti-corrosion protection.

The advantage that use contains the particle of partially conductive polymer is, for the coating of metal surface or any kind arbitrarily, the application of particle has diversity.

Coatings many complete or main organic compositions and that also have other chemical composition types can improve by adding conducting polymer: when the content of conductive component is very little, special aspect the antistatic behaviour of coating, with when particularly having this constituent content that can regulate electric conductivity when higher, this point with regard to for the precipitation of japanning composition in the electric field for example or optional also have coated with the electric welding of the sheet material of this type coating extremely important.In a lot of the application, even the metal surface can obtain higher better corrosion protection.

Here, the particle that is formed by conducting polymer in fact, contain the particle of conducting polymer and/or as particle nuclear and that have thin, thinner, the thick or very thick housing (core-shell particles) that is consisted of by conducting polymer, can both help very much conducting polymer is incorporated in body agglomerate, dispersion liquid or the solution of particle, thin liquid or high sticking form.

The composition of raw mix or product mixture:

In addition, the solution of this task also depends on and a kind ofly has raw mix or product mixture such as the particle of composition as described in the claim 49 for coating.

Transition between raw mix and the product mixture is normally very smooth.The component that therefore can form the conducting polymer of suitable content in raw mix and/or still contain a great deal of in product mixture is with further formation conducting polymer.

Preferably according to aftermentioned according to selecting at least a raw material, namely its can be in water polymerization and/or its oxidation potential be less than or equal in containing the solvent mixture of water or the decomposition potential of the water when only only having water as solvent.

The feature of this raw mix can be that it comprises

-optional material content is 0.001 to 25 or at least a monomer and/or at least a oligomer to the 20 % by weight scopes,

The anticorrosion anion of-at least a activity and/or at least a salt, ester and/or at least a acid is as the carrier of anion, and the content of movable anticorrosion anion calculates with anion in the scope of 0.05 to 50 % by weight,

-optional at least a oxidant, and oxygenate content is in the scope of 0.05 to 50 % by weight,

-at least a inorganic and/or organic particle and granule content is 1 to 95 or to the scope of 96 % by weight,

-wherein all these content and the additive of choosing other wantonly, do not mention herein---but not comprising solvent---satisfy altogether 100 % by weight, and

-at least a the solvent that is suitable for raw material, anion and/or oxidant, and solvent outwards surpassed 100 % by weight in the scope of 1 to 5000 % by weight,

-and when---after optional---when having added monomer/oligomer or oxidant, the summation of solid satisfies 100 % by weight.

In the production decision segment, relate to some interpolation schemes for monomer/oligomer or oxidant especially.Because after monomer/oligomer, anion and oxidant meet, usually will begin reaction and generate conducting polymer.

Especially reliably, particularly for organic granular, the raw mix with following composition is particularly suitable for coated particle:

-optional 0.001 to 0.5Mol/L at least a monomer and/or the oligomer of at least a raw mix, only otherwise can cause very high concentration so that coated particle is assembled gets final product, preferred 0.01 to 0.2Mol/L, 0.001 to 0.5 % by weight particularly preferably,

The anticorrosion anion of-0.01 to 1Mol/L at least a activity, optional at least a salt, ester or at least a acid are as the carrier of this anion, and preferred 0.1 to 0.8Mol/L, 0.05 to 3 % by weight particularly, all in anion,

-choose wantonly and add at least a oxidant with one times of amount to five times of material quantities (summation of=monomer and oligomer), it also is preferred 0.01 to 2.5Mol/L, more preferably 0.05 to 1.5Mol/L, particularly preferably 0.1 to 3 % by weight, wherein, the preferred in some embodiments content of at least a oxidant is one times to five times monomer and oligomer amount

Inorganic and/or the organic granular of the preferred at least a compound of-1 to 96 % by weight, wherein be noted that, raw mix and the product mixture that forms thus also can keep stable under higher particle density, namely can or can not assemble very significantly yet, preferred 1.5 to 60 % by weight, 2 to 50 % by weight particularly preferably, and for organic granular, the concentration in raw material and/or the product mixture is usually only for being no more than 20 % by weight

-wherein, when---also optional after---when having added monomer/oligomer or oxidant, all these content and optional some other, at this additive of not mentioning---but not comprising solvent---satisfy summation 100 % by weight, and

-at least a the solvent that is suitable for raw material, anion and/or oxidant, and solvent outwards surpassed 100 % by weight in the scope of 2 to 4000 % by weight,

In certain embodiment, particularly for inorganic particle, raw mix preferably contains,

-choose at least a monomer and/or at least a oligomer and material content wantonly in 1 to 25 % by weight scope,

The anticorrosion anion of-at least a activity and/or at least a salt, at least a ester and/or at least a acid is as the carrier of anion, and it all calculates with anion, and movable anticorrosion anion is in the scope of 1 to 35 % by weight,

-optional at least a oxidant, and oxygenate content is in the scope of 1 to 40 % by weight, and

-at least a content inorganic and/or organic granular and particularly inorganic particle is 35 to 95 % by weight.

Then preferably especially for organic granular, raw mix contains in another embodiment,

-choose at least a monomer and/or at least a oligomer and material content wantonly in 0.5 to 18 % by weight scope,

The anticorrosion anion of-at least a activity and its content in 0.5 to 35 % by weight scope,

-optional at least a oxidant and its content in 0.2 to 30 % by weight scope, and

-at least a content inorganic and/or organic granular and particularly inorganic particle is 10 to 40 % by weight.

Raw mix preferably contains

-choose at least a monomer and/or at least a oligomer and material content wantonly in 2 to 20 % by weight scopes,

The anticorrosion anion of-at least a activity and its content in the scope of 2 to 30 % by weight,

-optional the oxidant of at least a content in 2 to 25 % by weight scopes, and

-at least a content inorganic and/or organic granular and particularly inorganic particle is 15 to 65 % by weight.

Consist of on the particle and/or mixture that particle contains the coating of conducting polymer preferably contains:

The content of-minute other at least a oligomer, polymer, copolymer, block copolymer and/or graft copolymer and conducting polymer is in 0.1 to 30 % by weight scope, and mainly, the to a great extent or fully polymerization in water of described conducting polymer,

The anticorrosion anion of-at least a activity and its content are in the scope of 0.1 to 40 % by weight, and wherein said these anion can discharge from conducting polymer via reduction reaction,

-optional at least a content is at the oxidant of 0.1 to 30 % by weight, and if have at least a anion to play simultaneously oxidant to do the time spent, described this at least a oxidant can completely or partially save,

-at least a content inorganic and/or organic granular and inorganic particle is 30 to 98 % by weight, and it can be coated with conducting polymer,

-all these content and optional some other, at this additive of not mentioning---but not comprising solvent---satisfy summation 100 % by weight, and

-at least a the solvent that is suitable for raw material, at least a anion and/or at least a oxidant, and solvent has outwards surpassed 100 % by weight in the scope of 0.1 to 4000 % by weight.

The content of preferred feedstock is respectively about 0,1,2,4,6,8,10,12,14,16,18,20 or 22 % by weight.The content of the anticorrosion anion of preferred activity is respectively about 2,4,6,8,10,12,14,16,18,20,22,24,26,28,30 or 32 % by weight.It is about 2,4,6,8,10,12,14,16,18,20,22,24,26,28,30,32 that the content of preferred oxidant is respectively, 34,36 or 38 % by weight.The content of preferred particulates is respectively about 6,8,10,12,14,16,18,20,22,24,26,28,30,32,34,36,38,40,42,44,46,48,50,52,54,56,58,60,62,64,66,68,70,72,74,76,78,80,82,84,86,88,90 or 92 % by weight.

The content of preferred feedstock is respectively about 0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4 or 0.45Mol/L.It is about 0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95 that the content of preferred movable anticorrosion anion is respectively, or 0.85Mol/L.The content of preferred oxidant is respectively about 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1 or 2.2Mol/L.

The content of preferred feedstock is in 0.1 to 24 % by weight, 0.001 to 0.5 % by weight, 1 to 25 % by weight, 0.5 to 18 % by weight, 2 to 20 % by weight, 8 to 22 % by weight or 0.8 to 18 % by weight, particularly preferably in 0.1 to 15 % by weight, 2 to 12 % by weight or 4 to 16 % by weight, extremely preferably in 0.3 to 8 % by weight, 5 to 14 % by weight or 6 to 12 % by weight.

Preferably OxidantContent be 0.1 to 45 % by weight, 0.001 to 0.5 % by weight, 0.1 to 3 % by weight, 1 to 40 % by weight, 0.2 to 30 % by weight, 2 to 25 % by weight or 0.01 to 38 % by weight, particularly preferably in 0.1 to 15 % by weight, 0.2 to 32 % by weight or 2 to 26 % by weight, extremely preferably in 0.3 to 28 % by weight, 4 to 24 % by weight or 5 to 38 % by weight.

Preferred movable anticorrosion AnionAnd/or as the content of at least a salt of these anion carriers, at least a ester and/or at least a acid, calculate with anion respectively, be 0.05 to 3 % by weight, 1 to 35 % by weight, 10 to 40 % by weight, 0.1 to 30 % by weight, 5 to 38 % by weight, 12 to 42 % by weight or 0.1 to 45 % by weight, particularly preferably 0.2 to 26 % by weight, 0.4 to 42 % by weight or 2 to 30 % by weight, extremely preferred 3 to 38 % by weight, 5 to 25 % by weight or 14 to 36 % by weight.More recommend, add excessive anion or roughly insert in the content stoichiometric with respect to the anion-content in the theoretic insertion conducting polymer.

At least a inorganic and/or organic granularContent be preferably 1 to 96 % by weight, 35 to 95 % by weight, 10 to 40 % by weight, 15 to 65 % by weight, 2 to 80 % by weight, 5 to 65 % by weight or 1.5 to 48 % by weight, particularly preferably in 0.8 to 15 % by weight, 1.2 to 32 % by weight or 2 to 46 % by weight, extremely preferred 1.3 to 18 % by weight, 4 to 24 % by weight or 5 to 28 % by weight, first-selected 6 to 16 % by weight.

Preferably SolventContent be, solids content=100 % by weight have been surpassed, 2 to 4000 % by weight, 1 to 2500 % by weight, 5 to 3000 % by weight, 10 to 800 % by weight, 2 to 300 % by weight, 20 to 2500 % by weight or 30 to 600 % by weight, be particularly preferably 1 to 1500 % by weight, 2 to 1200 % by weight or 50 to 600 % by weight, extremely preferred 30 to 400 % by weight, 5 to 160 % by weight or 5 to 80 % by weight.

In addition, also can add a certain amount of at least a bonding promotion property anion, for example based on phosphorous negative oxygen ion such as phosphonate, silane, siloxanes, polysiloxanes and/or surfactant, and preferred content is to 20 % by weight, particularly preferably content be 1.5 to 18 % by weight or 2 to 12 % by weight and/or particularly preferably these anion content so that all anion sums in 1 to 80mol% scope, preferred 10 to 50mol%.But not adding in many embodiments bonding and promoting property anion or can only be to exist in a small amount.

The weight ratio of component in the mixture, be raw material: movable anticorrosion and optional in addition bonding promotion property anion: oxidant: the ratio of inorganic particle is preferably 1 in some embodiments: (0.5 to 30): (0.5 to 10): (0.5 to 8), and be particularly preferably 1: (1 to 25): (1 to 8): (1 to 7), wherein under these ratios, also can choose wantonly and save discontinuously raw material or oxidant.

The content of these components can change in wider scope.The thickness of coating is depended in this variation especially: can apply and obtain ultra-thin, thin, thick or very thick coating, it for example has 0.1 to 10nm,＞1 to 100nm,＞10 to 1000nm (1 μ m),＞100nm to 10 μ m or＞layer thickness of 0.5 μ m to 50 μ m.Also can select to have very little or very highdensity component.In addition, the specific area of inorganic particle also can play very strong influence, such as the SiO that makes by the calcination hydrolysis ₂Powder.

In addition, raw mix and the optional product mixture that forms thus that also has also all contain at least a surfactant, protecting colloid, sour agent for capturing and/or complexing formation agent.Can add at least a additive in the mixture; optional at least a surfactant is such as difference at least a nonionic, anion and/or amphoteric surfactant; at least a protecting colloid such as polyvinyl alcohol, at least a sour agent for capturing such as ammoniacal liquor or weak base such as acetate and/or at least a complexing form agent such as ammonia, citric acid, EDTA or lactic acid.The content of at least a surfactant is preferably 0.01 to 1.5 % by weight.The content that at least a protecting colloid, at least a sour agent for capturing and/or at least a complexing form agent all is preferably 0.01 to 0.8 % by weight.

Particularly owing to coated particle, raw mix lacks the composition of the raw mix of dissolving.The concentration of the solvent components that therefore, forms in the product mixture is corresponding lower.

The conducting polymer that is formed by chemical reaction in the raw mix is present in the described product mixture.

Reaction generates conducting polymer and the process technology scheme during with conductive polymer coated:

If needed, can or add to before disperseing the raw mix crowd go before drying and/or heated particle.As solvent, preferred use the mixture with high water content more or just make water.But in a series of schemes, need or necessary a small amount of organic solvent, particularly at least a alcohol, at least a alcohol such as ethanol, propyl alcohol and/or the isopropyl alcohol of first-selected 1 to 10 % by weight of adding.

With solution, dispersion liquid, colloidal sol and/or the gel of inert gas such as argon gas and/or nitrogen hydro-peening raw material, remove thus air oxygen, obtain better thoroughly to obtain specific atmosphere in mixture, the gas phase above mixture and/or drying is fallen nonaqueous solvents before preferably in adding raw mix to, going.

Being used for coated particle, when for example the composition of the raw mix of solution or dispersion is mixed together, confirmed all in a plurality of embodiments that all components except oxidant all will add in the situation of mixture movement.

Usually, when raw mix mixes mutually, at first to insert in advance inorganic and/or organic particle and at least a liquid and also have at least a raw material with choosing wantonly.Preferably adding in the mixture is respectively all components of solution and/or dispersion.

In a preferred embodiment, when mixing mutually, component wants long-time so that the agent of oxygen-freeization of raw mix, until form at least individual layer of one deck raw material at least a portion surface of inorganic and/or organic granular, could at first form especially at least one individual layer by absorption method with this.This point is very useful for inorganic particle particularly.Then, individual layer mainly or fully contains raw material and movable anticorrosion anion, does not wherein consider it also can is the accumulation of very a large amount of liquid in principle.Can continue at least one second until form the time period of at least one individual layer, sometimes also at least one minute.Then, preferably after having formed at least one individual layer, just be added into the particularly oxidant of solution form.Thus, at least a raw material at first is deposited on the particle with the anticorrosion anion of at least a activity, thereby so that compare with other a series of Blending Processes, obtaining comparatively uniformly, coating structure also partly also makes the coating that contains the conducting polymer that forms after a while obtain higher coating electric conductivity.At least part of raw material is deposited on the gram force surface, then is anion.During this time, the stand-by period can be particularly preferably in 0.5 to 10 minute the scope.Preferably in this process, mixture always is in the motion.

In another embodiment, when component is mixed mutually, also can keep for a long time making mixture not contain the raw material of conducting polymer, until form main or fully by anticorrosion anion and optional at least one individual layer that also has oxidant to form of at least a activity at least a portion on inorganic particle surface particularly.The advantage of doing like this is that individual layer mainly or fully contains anion and/or oxidant, and does not wherein consider the accumulation of liquid.Preferably after having formed the individual layer that one deck at least is made of these anion in fact, just add at least a raw material of solution particularly or dispersion in the raw mix.Thus usually can be on coating green onion skin structure formed more or have the coating of gradient.

But the anticorrosion anion of at least a activity should preferably add before oxidant adds or before the raw material interpolation.

In addition can also be at least a electrolyte of raw mix interpolation that reaction generates conducting polymer that is used for that is consisted of by oxidant and monomer/oligomer, for example at least a salt and/or at least a acid, and their anion is inserted in the conducting polymer as the doping ion and it has corrosion-resisting function as anion.In this process, can be before particle forms individual layer or raw material layer or in mixture, add at least a electrolyte that does not play the oxidant effect.

If but in raw mix, contain all the components except particle and when particle added as last composition, the oxidation reaction of raw material namely began or further develops.Then just damage coating possibly, for example cause hiding by halves or not hiding particle.

Preferably make raw mix---also will before adding every other component---and optionally also have the product mixture that forms thus to be in the motion, and wherein said mixed process can in laminar flow and/or turbulent flow, will be undertaken by mediating, spray and/or atomizing under static and/or dynamic mixing condition and/or also.

As a rule, if mixture does not move, for example stir and/or the ultrasonic wave processing, will produce non-uniform phenomenon.Preferably made mixture movement 1 to 40 minute, particularly preferably 5 to 30 minutes.Before the inorganic particle that adds through applying, be recommended in and add front they being distributed in liquid or the mixture again by the motion such as long-time stirring, with the Uniform Dispersion particle.Then also can mainly be that motion by mixture makes their keep disperseing.

Want in many situations preferably pH value to be adjusted in 0.5 to 8 the scope, preferred 1 to 7, be 2 to 6 or 4 to 8 in some situation, wherein, the type of anion and stability have decisive significance at this for the concrete pH value of selection.But particularly some oxidant such as molybdate and/or tungstates need higher temperature in specific pH value scope.But for specific inorganic particle such as carbonate and sulfide, preferably can not in the strong acid scope, operate, not destroy particle, particularly can not be under the pH value outside 5 to 7 scopes.Also be noted that on the other hand greater than 6 or during greater than 7 pH value in some situation conducting polymer also can go wrong, such as peroxidating.The decline of mixture pH value also has following advantage, namely can improve thus the electric conductivity of mixture.The pH value of mixture is dropped to be no more than 3 numerical value.But in pH value adjustment process, also be noted that for conducting polymer preparation and whether the pH value of selecting is suitable for or the particle that is conducive to apply and optional also whether be suitable for or be conducive to particle through coating in coating such as the application in painting.

Especially for mix, the formation of interpolation, chemical reaction and/or the coating of the present invention of oxidant, operating temperature is usually at 0 to 60 ℃, preferred 10 to 50 ℃.Usually can and recommend at room temperature to operate.But in certain embodiments, each mix stages and optional also thereafter until the temperature that forms conductive coating---during especially at coating inorganic particle---raw mix preferably at 0 ℃ to boiling point in the boiling spread of minimum liquid, perhaps just arrive the temperature that forms azeotropic mixture, preferably in 0 to 200 ℃, particularly preferably 5 to 120 ℃, extremely preferred 10 to 70 ℃ temperature range.From mixing until finally particle forms the process of coating, all will roughly contain valuably selected temperature.

The process of coated particle is preferably 1 to 5 hour in order to the raw material/product mixture that forms nucleocapsid particles, and more preferably 5 minutes to 4 hours, extremely preferred 10 minutes to 3 hours, particularly preferably 15 to 2 hours.

Movable anticorrosion anion:

In raw mix and the composition at product coating, the task of movable anticorrosion anion provides the electrophilic center that essential electric charge forms in polymer chain in oxidation with charge compensation, and the corrosion-resisting function that is transmitted on the metal surface owing to adsorbing is provided.

When not adding anion in the raw mix, conducting polymer returns in its lattice and embeds any anion that is present in the dispersion liquid, but does not have with that movable anticorrosion anion to have inserted.If really so, then usually can form and compare to the inventive method more porous, thinner and worse conductive layer.

When all adding anion with preparation in the overwhelming majority's test in prior art and using conducting polymer, usually when forming, also can make conducting polymer reach electroneutral.In addition, some character of conducting polymer also can be received the impact of anion, such as electric conductivity or ionic conductivity and form and work function (oxidation potential).Have now found that, also can obtain corrosion-resisting function by anion.

At least a anion preferably has at least 110 at least a polar solvent or solvent mixture ^-3Water-soluble or the solubility of Mol/L because otherwise anion also just no longer can be inserted in the conducting polymer (=salt).

Wherein, do not play the anticorrosion anion of at least a activity of oxidant effect can be before particle forms individual layer or coating or among add in the mixture and go.But also can additionally or substitute those and not play the activity anticorrosion anion ground of oxidation, add at least a activity anticorrosion anion that plays simultaneously the oxidant effect, such as molybdate and/or tungstates.

In the methods of the invention, at least a etch-proof movable anion is preferably at least a based on benzoate, carboxylate such as lactate, dithiol, fumarate, complex fluorides, lanthanite, metaborate, molybdate is such as the nitro compound based on nitro-salicylic acid salt, caprylate, phosphorous negative oxygen ion such as phosphate closes/or phosphonate, phthalic acid, salicylate, silicate, sulfoxylate such as formaldehyde sulfoxylate salt, mercaptan, titanate, those of vanadate and/or zirconates, particularly preferably be at least aly to close/or the anion of zirconium complex fluorides based on the titanium complex fluorides, all can be expressed as MeF ₄And/or MeF ₆, and other stoichiometric proportion also can appear.

In the methods of the invention, as at least a corrosion-inhibiting or bonding promotion property anion, preferably can use a kind of particularly preferably based at least a above-mentioned etch-proof movable anion and phosphonate, silane, siloxanes, polysiloxanes and/or surfactant, particularly with the mixture of at least a fluoro complex, titanate, zirconates, molybdate and/or tungstates.

Oxidisability, be inserted into that anion in the storage substance can be selected from especially based on alkanoic acid, aromatic acid, boronic acid containing, fluoric-containing acid, heteropoly acid, isopolyacid, contains acid iodide, silicic acid, lewis acid, mineral acid, contains molybdic acid, peracid, phosphoric acid, contains vanadic acid, contains wolframic acid, their salt and composition thereof those.

The preferred anticorrosion anion that adds with respect at least a activity of polymer unit content 1 to 33mol%, more preferably 5 to 33mol%.These additions are corresponding to the doping level of conducting polymer.On the other hand, these anion also can excessively add.

Can be according to select at least a anion to get off, namely these anion want can be in water, movable in another kind of at least polar solvent and/or a kind of mixture that also comprises at least a non-polar solven.

But can exist except the anticorrosion anion of at least a activity does not at least aly have corrosion-resisting function and/or does not have can be inserted in the structure and/or the migration anion of ability out from structure yet.But, to compare with so-called activity anticorrosion anion, the amount of these anion usually should preferably can not be excessive.Utilization usually need to change into the oxidant of conducting polymer with feed oxygen and partly also insert another kind of anion, for example utilizes the oxidant peroxydisulfate.If but with for example H ₂O ₂And Fe ^2+/3+Salt is then worked as Fe as oxidant ^2+/3+Salt is with mainly less than 10 ^-4When the catalytic amount of Mol/L adds, just can not insert extra anion.The anion that belongs to activity anticorrosion anion, its amount should be selected high as far as possible in many embodiments, thereby could obtain very high corrosion-resisting function.

In the methods of the invention, particularly preferably to select the anticorrosion anion of comings and goings, so that these anion can be not excessive, thereby can not produce detrimental effect in conducting polymer and the mobility of closing in the material to these anion.Preferably select for example anion less than poly styrene sulfonate of molybdate, because poly styrene sulfonate is normally excessive and can only be with the anion that fixes and insert for activity.

The diameter that the anticorrosion anion of preferred at least a activity has can not be greater than the average pore size of conducting polymer pore system, even and described diameter preferably than the average pore size of pore system less than at least 8% at least 15%.Wherein, anion can be moved in the conducting polymer by very a large amount of holes such as duct and thus rapidly migration or mainly be at first to move out in possible situation especially.When having an electrical potential difference owing to the difference gradient between the corrosion potential of the redox potential of conducting polymer and corroding metal, can be more possibly not interrupted or seldom hinder the ground migration and pass through pore system much smaller than the anion of the average pore size of pore system yet.

If make in the methods of the invention the coating that is rich in binding agent, then movable anticorrosion anion just should have very little size, so that they enter that motion in all the other components of coating also can not be subjected to or be substantially not interrupted.When corrosion was encroached on, these anion can be moved in the affected area that almost always has the electromotive force less than complete interface.

The anticorrosion anion of preferred at least a activity is selected from based on carboxylic acid, contains the hydroxyl carboxylic acid, the hydroxycarboxylic acid dicarboxylic acids, tricarboxylic acids, two and/or trisubstituted aralkyl carboxylic acid, the neighbour, between and/or the aralkyl carboxylic acid that replaces of contraposition, contain amino, nitro, the aralkyl carboxylic acid of sulfonic group and/or OH group, sulfonic acid, inorganic oxacid, boronic acid containing contains mangaic acid, contains molybdic acid, phosphoric acid, phosphonic acids, fluoro silicic acid, silicic acid, contain the acid of at least a rare earth element and/or yttrium as containing the acid of cerium, sulfur acid contains metatitanic acid, contain vanadic acid, contain wolframic acid, contain stannic acid, contain zirconic acid, their salt, the anion of their ester and their mixtures.

Preferred at least a anion is selected from based on alkyl phosphonic acid, aryl phosphoric acids, benzoic acid, butanedioic acid, tetrafluoro silicic acid, the hexafluoro metatitanic acid, hexafluoro zirconate, gallic acid, hydroxacetic acid, silicic acid, lactic acid, molybdic acid, niobic acid, nitro-salicylic acid, oxalic acid, phosphinylidyne molybdic acid, phosphoric acid, phosphorus silicic acid, phthalic acid, salicylic acid, tantalic acid, vanadic acid, tartaric acid, wolframic acid, the anion of their salt, ester and their mixture.

The electric conductivity of formed coating usually can be owing to have added and can present different valence state and obtain raising at the corrosion anion of the easily at least a activity of conversion between different valence state.

Also can insert those and exchange (ligand conversion) such as the anion of the ligand conversion between hexafluoro titanate and/or fluorozirconate in the meeting particle diameter valence state conversion of damaged location place and/or dentate.Preferably also can bring thus deliquescent change, this will cause the anion of original dissolving to be deposited in the affected area or form erosion shield.The valence state conversion can occur with the form of oxidation or reduction.Preferred these layers are layers of oxide layer and/or difficulty soluble salt.If use hexafluoro titanate and/or fluorozirconate, then should in mixture, add hydrofluoric acid valuably.

Now record in test anticorrosion anion such as the TiF of at least a activity ₆ ^2-, ZrF ₆ ^2-, CeO ₄ ^4-, MnO ₄ ^-, MnO ₄ ^2-, MoO ₄ ^2-, VO ₄ ^2-, WO ₄ ^2-, WO ₄ ^4-Can go through ligand conversion, valence state conversion and/or changes in solubility effect, and form the oxidation protection layer at the defect area place and/or at the delamination area place.This anionoid is useful especially equally as most complex salt.

At N ₂Can confirm now in layering under the atmosphere experiment, molybdate ion be in fact under electromotive force drives, from the conducting polymer based on polypyrrole, discharge and move to fault location, can detect molybdate with XPS there.

At least a bonding in the methods of the invention promotes preferably a kind of based on phosphorous negative oxygen ion of property anion, such as phosphonate, silane, siloxanes, polysiloxanes and/or surfactant.

In the methods of the invention, promote the property anion preferably to use the mixture of at least two kinds of anion as at least a corrosion-inhibiting and/or bonding, particularly preferably a kind of based on the movable anion of at least a above-mentioned anticorrosive property and at least a above-mentioned bonding promotion property anion, be selected from especially based on carboxylate, complex fluorides, molybdate, nitro compound, based on phosphorous negative oxygen ion such as phosphonate, polysiloxanes, silane, those of siloxanes and/or surfactant, extremely preferred a kind of based on the movable anion of at least a above-mentioned anticorrosive property and at least a above-mentioned bonding promotion property anion.The anion mixture that particularly preferably uses by being selected from the one hand based on carboxylate, complex fluorides, molybdate and nitro compound on the other hand the anionic species based on phosphorous oxygen anion, polysiloxanes, silane, siloxanes and/or surfactant to consist of.

Particularly preferably select can similar chromate to form can anode also can---at least part of---anion of protecting the protective material of affected area in negative electrode ground.Wherein preferred those can be gone through anion and/or fissionable complex anion of valence state conversion.

Particularly preferably also to add the anion, particularly negative oxygen ion of the subgroup element with high oxidation valence state more such as 4+ or 6+.When setting contained the organic coating of conductive coating particle on the metal surface, their can give play to high corrosion-resisting function in metal surface to be protected.

For the anticorrosion anion, preferably make they and the cation that is present in the affected area, the cation that comes such as the stripping that disappears from the metal surface in when corrosion together, consist of a fine and close as far as possible and passivation layer of sealing as far as possible in the metal surface, wherein this at least a formed passivation layer material be can not conducting ion and in used at the interface pH value scope, be stable.These materials can for example be oxide, hydroxide and phosphate or their mixture.

Usually, improve the electric conductivity of the coating that will form by the content that improves the anticorrosion anion of at least a activity in the conducting polymer.The content that preferably is inserted at least a anion that goes in the conducting polymer is 1Mol% at least, more preferably at least 5Mol%, particularly preferably at least 10Mol%, extremely preferably at least 15Mol%, particularly 20Mol% at least to the ratio (=doping level) of material content.Can reach 50Mol% in theory, but obviously can not obtain in the production practices.

Hydrogenant agent:

The task of oxidant in raw mix is for example to start the chain tectonism of carrying out according to radical cation mechanism and keep this effect when consuming.Therefore generally in raw mix, excessively add the preferred oxidant that surpasses 33mol% content.For making at least a raw material reaction become at least a product, need to be suitable for the electroneutral anion of conducting polymer and the optional oxidant that is suitable for polymerisation.Particularly ought there be at least a anion in the chemical polymerization process, to play simultaneously doing the time spent and/or so long as not electrochemistry and/or photochemical polymerization, then preferably adding at least a oxidant of oxidant yet.

Oxidant can be based on H ₂O ₂Such as barium peroxide, peracetic acid, benzylhydroperoxide, cross mangaic acid, cross sulfate mono, cross pyrosulfuric acid, lewis acid, molybdic acid, niobic acid, tantalic acid, metatitanic acid, wolframic acid, zirconic acid, contain yttrium acid, contain lanthanum acid, contain Fe ³⁺Acid, contain Cu ²⁺Acid, their salt, ester and/or mixture at least a.

Can use for example at least a based on acid, the salt that can multivalence attitude form exists such as the compound of molysite, based on the compound of peroxide and/or peracid such as peroxydisulfate as oxidant.

For having a plurality of valence states and the oxidant of conversion easily more or less, usually to select suitable and substantially be lower or in the middle of the pH value.In many cases, the pH value is in 2 to 6, particularly 2 to 4 or 3 to 5 scope.The very important point is that the oxidation potential that is noted that oxidant will be higher than the oxidation potential of the raw material for the treatment of oxidation or equates with it at least in addition.

Preferably contain conducting polymer and add the particle that goes in the present composition to and do not contain or substantially oxygen-freeization agent.

As nuclear for the preparation of the particle of nucleocapsid particles:

Composition, content and structure of organic and/or inorganic particle can change in wide range.

When preparation is suitable in SEM, and separately estimate and the individual particle of counting aggegation piece and evaluation and counting aggregation as under the larger individual particle condition, count and on average go through in the scope of mean value more than or equal to 0.1 μ m; Particle size range is that 5nm extremely then should utilize the Zeta-Sizer type laser Doppler anemometer of Malvern Instruments company to determine less than the mean value of 0.1 μ m; Then preferably measure with electronic diffraction for less average grain diameter.Here, can realize approx for the particle that SEM obtains, the divided aggregation that contains separable individual particle is estimated and counted as a plurality of individual particles in the various situations, the effect that this just haply can corresponding faint grinding.

Usually when applying, organic and size inorganic particle should can not change in fact.

Choosing wantonly can be to the particle precoating, chemical modification and/or physical modification.For example for SiO ₂Particle can have the differentiation between bronsted lowry acids and bases bronsted lowry, the hydrophilic and hydrophobic granule.

Particle described here can exist with at least a form, it is selected from: bunch shape basically, respectively large, fibrous, needle-like, strip, plate-like and/or the spherical particle such as to be approximately, through applying and/or particle, hollow bead and/or spongy particle through filling.Particularly preferred be respectively basically planar shaped or linear interlayer particle or the pigment through applying such as the phyllosilicate through applying.

Especially for inorganic bunch body, nano particle or granule and contain those of conducting polymer, preferably by suitable measure as adding pyrophosphate and suppress the cohesion tendency in the aqueous dispersion and disperseing well.

Especially, when needed can be at mixing material or add to and generate the mixture of conducting polymer for reaction or add to before composition for coating metal surfaces goes, to a great extent or completely under the drying regime or in dispersion liquid, grind, dry, calcination and/or disperse again inorganic particle.

The bed thickness of conducting polymer can change in very wide scope on the particle.The part of preferred bed thickness and/or granule interior is 1 to 200nm, and particularly preferably in 2 to 100nm, first-selection is the scope 1 to 40 or 3 to 80nm.In the possible situation, more thinner than the organic granular for these layers that inorganic particle makes.Although can consider thicker layer in principle, the particles no longer after applying has also just reached its upper limit in the time of disperseing.The bed thickness of these shells depends on reaction time, material concentration and the interface between particle and raw mix liquid parts that has especially.

But, from through the particle that applies different be, usually want preferably with the inorganic particle of coating is disperseed again before the matrix that contains binding agent mixes, particularly when having coagula and/or agglomerate.The inorganic particle that is provided as on the other hand nuclear and is wrapped up by conducting polymer is because they can mix in organic composite by mixing and/or simply grinding comparatively easily, such as japanning.

In mixture of the present invention or at the composition that is used for coating metal surfaces and particle, all can there be at least a particle that contains the conducting polymer of following kind:

1.) typical nucleocapsid particles (particle through applying), it with conductive polymer coated, and is commonly referred to as inorganic coated particle here by partially or completely,

2.) be at least partially contained within inside or also have the particle of conducting polymer inside, and be commonly referred to as the organic granular that makes with conducting polymer here,

3.) conducting polymer, it can be shaped arbitrarily or make, and special shape exists and does not optionally form round granular core separately and/or exceptionally, does not also namely constitute the coating on the particle; Optional conducting polymer also can come across in the particle that will apply, special or when they still in growth, mutually when symbiosis and/or healing,

4.) so-called " adhesive particle " that is consisted of by conducting polymer, this described polymer has at least a chemical group that can give bonding at molecule, such as phosphonate groups,

5.) a) particle shell of conducting polymer and/or b) contain conducting polymer particle fragment and/or

6.) individually, do not having particle that form and that contain conducting polymer in the situation of granular core, it is made of conducting polymer in fact or fully.

All these particles can be chosen wantonly and also be inserted in the coating of the present invention.All these may be summarized to be term " particle through applying " or " particle that contains conducting polymer " in category of the present invention.These all types of granule contents can be less or larger.The statement of relevant painting method also can correspondingly be used in other schemes of all " particles through applying ".

Organic granular:

For the material of organic granular, so-called " polymer " can be regarded as is at least a polymer that is selected from homopolymers, copolymer, block copolymer and/or graft copolymer.These particles can be as the core of nucleocapsid particles.For the preparation of organic granular, conducting polymer partly, largely or fully can be placed to this granule interior, and in the application's category, also this class particle can be regarded as " particle of coating " and nucleocapsid particles at this especially.

Especially, organic polymer is comprised of following polymer in fact:

The organic granular that contains conducting polymer preferably mainly or fully is to be selected from by styrene-based, acrylate, methacrylate, Merlon, cellulose, polyepoxide, polyimides, polyethers, polyurethane.In one group of the polymer composition of siloxanes, polysiloxanes, polysilane and polysilazane those.

1. the polymer of styrene-based, acrylate and/or methacrylate, two schemes in back are at (methyl) acrylate of following being called.They can be made of (methyl) acrylate in fact especially, and (methyl) acrylate is selected from (methyl) acrylate, (methyl) butyl acrylate, (methyl) hydroxyalkyl acrylate, (methyl) glycidyl acrylate and (methyl) acrylic acid glycol ester, and/or they are in fact by styrene and/or be made of the substituted phenylethylene that has independently mutually substituting group such as hydroxide, alkyl, alkoxyl and/or sulphonic acid ester in fact.

2. based on the polymer of Merlon: they can be particularly preferably in fact by consisting of based on two minutes A, B, C, F and/or Z and the optional organic carbonate that replaces for for example alkyl, alkoxyl and/or aryl.

3. based on cellulosic polymer: they can particularly preferably be made of the cellulose that is selected from alkylcellulose and hydroxy alkyl cellulose in fact, and optional also be substituting group replacement such as hydroxylate, alkyl, alkoxyl, carboxylate and/or sulfonate.

4. based on the polymer of polyepoxide: they can particularly preferably consist of by being selected from the substituent epoxides that does not replace and/or have such as hydroxylate, alkyl, alkoxyl and/or sulfonate in fact.

5. based on polyolefinic polymer: they particularly preferably essence consist of by the polyolefin that is selected from ethene, propylene, isobutene, butylene and 4-methylpentene and/or by at least a replacement polyolefin with substituting group such as alkyl, amino and/or hydroxyl.

6. based on the polymer of polyimides: its particularly preferably essence consist of by being selected from substituent poly-(acid imide) that do not replace and/or have such as hydroxylate, alkyl, alkoxyl and/or sulfonate.

7. based on the polymer of polyethers: they particularly preferably essence by being selected from oxirane and expoxy propane and/or having substituting group such as the epoxides of alkyl, aryl, amino and/or muriatic substituted epoxide consists of.

8. based on the polymer of polyurethane: based on the polymer of polyurethane: they particularly preferably essence consist of by being selected from the substituent polyurethane that does not replace and/or have such as hydroxylate, alkyl, alkoxyl and/or sulfonate.They can be especially make via vulcabond and glycol or via the diamines of vulcabond and primary/second month in a season, and are hydroxy-end capped glycol, polyester, polyethers, Merlon and/or oligomeric (methyl) acrylate and as the alkyl diamine that has especially n=5 to 12 of diamines as glycol.

9. based on the polymer of siloxanes and/or polysiloxanes and silicone: they particularly preferably essence formed by the siloxanes and/or the polysiloxanes that do not replace and/or have substituting group such as hydroxylate, alkyl, alkoxyl, amino, sulfydryl and/or sulfonate.

10. based on the polymer of polysilane and/or polysilazane: they can essence be made of polysilane and/or the polysilazane with substituting group such as hydroxylate, alkyl, alkoxyl and/or sulfonate that do not replace and/or replace.For example, they can be in fact by poly-(cyclohexyl methyl) silane, poly-(dihexyl) silane and/or poly-(phenyl methyl) silane or in fact by poly-(1, the 2-dimethyl) silazane and/or poly-(1,1-dimethyl) silazane consist of.

But for applying organic granular or being prepared with the preparation conducting polymer; thereby so that the common section within it of the organic granular that forms thus has the more conducting polymer of high-load, the specially suitable nuclear that can be dispersed with organic polymer such as polyacrylate, polystyrene, polyurethane and/or polysiloxanes that is based on.In with the method for conductive polymer coated organic polymer, also can process polymer, wherein, at first the preparation organic granular also then applies these organic granulars according to the present invention---particularly at same solution or dispersion liquid and/or in identical colloidal sol or gel---, perhaps basic simultaneously or prepare simultaneously organic granular and conducting polymer, thereby so that the particle that forms thus within it section usually be inserted with conducting polymer and part also has conducting polymer in its surface.Preferably changing method is a kind of single still method and/or a kind of continuous in fact method.The preparation of organic granular is preferably based on emulsion polymerisation, does not particularly contain surfactant.The method of emulsion polymerisation, approach and product are known basically.The organic granular of these emulsion polymerisations is present in the stable dispersions usually owing to prepare in advance.

In many embodiments, particularly preferably organic granular and conducting polymer are made together.Can make in this process and have that specific narrow particle diameter distributes, the particle of unimodal or bimodal particle size distribution, and/or make organic polymer wherein and conducting polymer closely mixes or fork is given birth to particle.Can for example form scope in this process at the unimodal or bimodal distribution of 30 to 400nm sizes.But also can at first make organic granular, then or be right after in later phases with conductive polymer coated or sneak into nearly surface.

To guarantee during organic granular in preparation, can not damage significantly the formation of micella, this especially can because inappropriate oxidant, owing to ion and/or the overgenerous stirring of too high amount causes.Because in many embodiments, organic granular is all formed by micella.Here also it is also noted that the chemical compatibility of institute's adding ingredient.Polymerization process also can be that chemistry, electrochemistry and/or photochemistry mode are carried out.

Can come with the various organic granulars of conductive polymer coated according at least a painting method in principle optional can not the dispersion or dispersed very poor particle by sealing.Can be dispersed in the context and refer to, can in solution or dispersion liquid and/or colloidal sol or gel, form stable inorganic particle dispersion liquid, thereby cohesion substantially can not occur.

Inorganic particle:

Preferred inorganic particle is made of at least a inorganic material in fact, particularly be selected from fact respectively at least a boride, carbide, carbonate, cuprate, ferrate, fluoride, fluorinated silicate, niobates, nitride, oxide, phosphate, phosphide, phosphosilicate, selenides, silicate, contain aluminosilicate, sulfate, sulfide, tellurides, titanate, zirconates, be selected from least a carbon, be selected from least a stone powder, be selected from least a glass, clinker, glassy material, the powder of non-crystalline material and/or composite is selected from least a alloy and/or at least a metal---as long as alloy and/or metal can just not corrode and form local cell when conducting polymer prepares---and/or their mixed crystal, their fork is given birth to body and/or their mixture.

Inorganic particle can be made of at least a material in fact, and particularly be selected from fact at least a alkaline earth metal carbonate, titanates of alkali-earth metals, alkaline earth metal zirconate, SiO ₂, silicate is as containing aluminosilicate, mica, clay mineral, zeolite, indissoluble sulfate such as barium sulfate or calcium sulfate hydrate, be selected from for example based on SiO ₂And/or the thin slice of silicate, be selected from the oxide that contains aluminium, iron, calcium, copper, manganese, titanium, zinc, tin and/or zirconium.

The extra fine particle can be for example makes via colloidal sol and/or gel such as Ludox.Although collosol coating is a little that dense composition still has very high activity.This particle has 10 to 120nm average grain diameter usually.Because the tiny granularity of formed particle will form equally distributed especially conducting polymer especially in the process in the thin layer of shell.

Optional also can in the preparation process of this inorganic particle, make conducting polymer partly, largely or be inserted completely into the inside of this particle, and also these particles can be seen as in category of the present invention be " particle through applying " and nucleocapsid particles.

Particularly preferably particle diameter distributes narrower than what occur in the inorganic particle in some embodiments.This can by for example mix different distribution system, by screening or filter or obtain by grinding.

Particularly preferably be the inorganic particle that substantially is configured as sheet, basic linear and/or basic needle-like.Therefore, they also can play the effect that is better than the interlayer particle.

Inorganic particle can partly also be present in the stable dispersions, and to depend on granularity especially, concentration, density, electrolyte content etc.

Monomer/oligomer for the preparation of conducting polymer:

Need in raw mix, add monomer and/or the oligomer that is fit to reaction generation conducting polymer for forming conducting polymer.Monomer and/or oligomer are called " raw material ".Monomer and/or oligomer are preferably from monomer and/or the oligomer of inorganic and/or organic nature, be selected from aromatics and/or undersaturated hydrocarbon compound such as alkynes, heterocycle, carbocyclic ring, their derivative and/or their composition, it is suitable for forming thus the oligomer/polymer/block copolymer of conduction/graft copolymer, the particularly preferably replacement of X=N and/or S and/or undersaturated heterocycle.

Particularly preferably add the unsaturated or saturated compound based on imidazoles, naphthalene, phenanthrene, pyrroles, thiophene and/or benzenethiol.

Usually, can pass through especially hydrogen (H), hydroxyl (OH), halogen (Br/Cl/F), alkoxyl (O-alkyl), alkyl (C _xH _y), carboxyl (COH), carboxylate (COOH), amine (NH ₂), amino (NH ₃), acid amides (CONH ₂), uncle ammonium (NRH ₃ ⁺), imines (NH), acid imide (COHNH), phosphate (PO ₃H ₂), diphosphate, sulfydryl (SH), sulfone (SO ₂H), sulfonate (SO ₃H), aryl ((C ₆H ₅) _n) and/or the alkyl chain that has or do not have other substituent non-grafting or a grafting oligomer, polymer, copolymer, block copolymer and/or the graft copolymer that come substituted monomer and/or form thus, and wherein said substituting group preferably can not be excessive.

Preferably add the raw material for the preparation of conducting polymer in the mixture, and wherein at least a raw material have looser molecular structure and/or wherein at least a formed conducting polymer have looser molecular structure, so make it possible to especially bring larger average pore size (the normally form of molecular channel) to the hole of conducting polymer.

The so-called raw material that replaces particularly preferably is that at least a compound and its are selected from benzimidazole, 2-alkylbenzene thiophenol, 2-alkoxy benzene thiophenol, 2,5-dialkyl benzene thiophenol, 2,5-dialkoxy benzenethiol, the 1-alkyl pyrroles who has especially 1 to 16 C atom, the 1-alkoxyl pyrroles who has especially 1 to 16 C atom, the 3-alkyl pyrroles who has especially 1 to 16 C atom, the 3-alkoxyl pyrroles who has especially 1 to 16 C atom, has especially 3 of 1 to 16 C atom, 4-dialkyl group pyrroles, has especially 1 of 1 to 16 C atom, 3,4-trialkyl pyrroles, has especially 1 of 1 to 16 C atom, 3,4-tri-alkoxy pyrroles, the 1-aryl-pyrrolidine that has especially 1 to 16 C atom, the 3-aryl-pyrrolidine, 1-aryl-3-alkyl pyrroles, the 1-aryl-3 that has especially 1 to 16 C atom, 4-dialkyl group pyrroles, the 1-aryl-3 that has especially 1 to 16 C atom, 4-one alkoxyl pyrroles, the 3-alkylthrophene that has especially 1 to 16 C atom, the 3-alkoxy thiophene that has especially 1 to 16 C atom, has especially 3 of 1 to 16 C atom, 4-dialkyl group thiophene, has especially 3 of 1 to 16 C atom, the 4-dialkoxythiophene, 3,4-ethylenedioxy thiophene and their derivative.Here; can select at least a based on following compound; namely based on the pyrroles who has especially 1 to 16 C atom-1-base alkyl phosphonic acid; has especially the pyrroles of 1 to 16 C atom-1-base alkyl-phosphoric acid; has especially the pyrroles of 1 to 16 C atom-3-base alkyl phosphonic acid; has especially the pyrroles of 1 to 16 C atom-3-base alkyl phosphoric acid; the 5-alkyl-3 that has especially 1 to 12 C atom; 4-ethylenedioxy thiophene; 5-(ω-phosphono) alkyl-3; 4-ethylenedioxy thiophene and their derivative; particularly have 1 to 12 C atom, they can make as alkali for the preparation of storage medium or add in the composition and go.The C atom number can be 1,2,3,4 independently of each other all, 5,6,7,8,9,10,11,12,13,14,15 and/or 16.

The so-called raw material that replaces; the extremely preferred at least a following compound that is selected from; namely be selected from the 2-methylbenzene phenyl-sulfhydrate; the 2-methoxybenzenethiol; 2; the 5-thiophenol dimethyl benzene; 2; 5-dimethoxy benzenethiol; the 1-methylpyrrole; the 1-N-ethyl pyrrole N-; has especially the pyrroles of 10 and/or 12 C atoms-1-base alkyl phosphonic acid; has especially the pyrroles of 12 C atoms-1-base alkyl phosphate; 1-methoxyl group pyrroles; 1-ethyoxyl pyrroles; have especially 6; the pyrroles of 8 and/or 11 C atoms-3-base alkyl phosphonic acid; 3-methoxyl group pyrroles; 3-ethyoxyl pyrroles; 3; the 4-dimethyl pyrrole; 3; 4-dimethoxy pyrroles; 1; 3; 4-trimethyl pyrroles; 1; 3; 4-trimethoxy pyrroles; the 1-phenylpyrrole; the 3-phenylpyrrole; 1-phenyl-3-methylpyrrole; 1-phenyl-3-methoxyl group pyrroles; 1-phenyl-3; the 4-dimethyl pyrrole; 1-phenyl-3; 4-dimethoxy pyrroles; 3 methyl thiophene; the 3-ethylthiophene; the 3-hexyl thiophene; 3-octyl group thiophene; the 3-methoxythiophene; 3-ethyoxyl thiophene; the own oxygen base of 3-thiophene; 3-octyloxy thiophene; 3; the 4-thioxene; 3; the 4-dimethoxy-thiophene; 5-((ω-phosphono) methyl-3; 4-dioxy thiophene and derivative thereof, they can make; as the preparation storage substance alkali or add in the composition and go.

Particularly preferably at least a compound is selected from ethylthiophene, ethylenedioxy thiophene, methylthiophene, 3-N-ethyl pyrrole N-, 3-methylpyrrole, N-N-ethyl pyrrole N-, N-methylpyrrole, 3-phenylpyrrole and derivative thereof, and they can make, be used as the alkali of preparation storage substance or add in the composition and go.Particularly preferred or heterocyclic pentylene (HCP), dioxy-3,4-heterocyclic pentylene (ADO-HCP), two to eight yuan of heterocyclic pentylenes (OHCP) and benzheterocycle pentadiene (BHCP).

When the pH value for them and inappropriate the time, the conducting polymer of coated particle of the present invention or contain the particle of conducting polymer can be owing to nucleophillic attack is subject to chemical erosion.Therefore, the preferred use has at least a substituting group such as the particularly again alkoxyl on 3-and/or the 4-position and/or the raw material of alkyl, they can form and can not be subject to conducting polymer nucleophillic attack or deactivation effect adverse effect, and these detrimental effects can cause electric conductivity impaired.It can be based on especially has at least one alkyl chain nuclear/or has the raw material of the heterocycle of at least one member ring systems.In addition, this class raw material also is preferred, because crosslinkable can be restricted therefrom preferably, also because the conducting polymer that forms thus mainly has the pore system that contains king-sized hole path.Particularly preferred compound, monomer whose and/or oligomer can be at least in part soluble in water and/or polymerization in wherein.Particularly preferably be at least part of or off and on can be in water or in the moisture solvent mixture those of polymerization.

Equally also preferably to for the preparation of add in the mixture of conducting polymer at least a water-soluble and preferably after its oxidation (=polymerization) no longer or only have very little water miscible raw material.

Therefore, especially to use monomer, because they can more cheaply maybe can have higher solubility and the diffusion coefficient of Geng Gao.Then, can not polymerization and when only having oligomer can polymerization the time when corresponding monomer, then particularly preferably use oligomer.Can have more activity than monomer under the more susceptible condition of oligomer.

The raw material of copolymer and/or block copolymer form can be chosen wantonly except monomer/oligomer Already in the raw mix, graft copolymer usually then at first is by for example carrying out other chemical reaction with other organic principles of carboxyl and/or ester group with another kind of at least, and is created on especially on the polymeric matrix of coating.

Preferred interpolation is at least a to keep stable raw material in a wider pH value scope after polymerization generates conducting polymer.Preferably on selected pH value, used oxidant also is stable.Preferred this pH value scope comprises at least 1 or at least 2 units, also namely for example the pH value in 3 to 4.5 scope.

The conducting polymer that forms:

By adding a certain amount of monomer and/or oligomer (raw material e) that is suitable for forming conducting polymer, just can be formed to the polymer (=product, storage medium) of small part conduction by oxidation.If the interpolation oxidant, then can be obtained subsequently by raw material can polymerization and can add the raw material of the oxidation of other groups thereon.Less oligomer, for example n is about those of 8, can or not show hardly the effect of conducting polymer at this.Conducting polymer is electroneutral under reducing condition.Can form the cation that can correspondingly absorb anion during conducting polymer oxidation (=polymerization).Can adopt at least a oxidant in chemical mode ground, obtain to electrochemistry and/or photochemistry mode oxidation state.Preferably do not carry out electropolymerization, but only carry out to a great extent chemistry and/or photochemical polymerization, especially just chemistry and/or photochemistry mode.Particularly preferably just or just adopt to a great extent chemical mode.

Storage medium in principle can chemistry, electrochemistry and/or the polymerization of photochemistry mode.Preferably with at least a storage medium or contain its composition chemistry and/or mechanically be coated on especially on particle or the metal surface.During electrochemical coating, at first the more inexpensive metal surface of passivation is molten to suppress strongly disappearing of metal material.Therefore, must be always when electrochemical coating to by adding the corrosion-inhibiting anion in the solution of at least a raw material of its polymerizable, thereby at first always form passivation layer.The conducting polymer that forms by this way thereby contain automatic etch-proof anion, but those documents of having put down in writing the corrosion-inhibiting anion obviously not enlightenment these anion can discharge because electromotive force descends.

When electrochemical polymerization, particle must have negative ζ-electromotive force usually.The coating that makes at particle by electrochemical polymerization is verified to have relatively poor quality.When photochemical polymerization, usually need semiconductive particle, this particle for example can discharge defect electron (Defektelektronen) when the UV radiation.Here, the coating that makes at particle by photochemical polymerization is verified also to have relatively poor quality.In addition, polymer shell can sustain damage under the UV radiation.Best coating can make by chemical polymerization now comparatively speaking.

Conducting polymer has salt like structure, thereby so that the conducting polymer of load anion can be referred to as salt.

Below at least a polymer, copolymer, block copolymer and/or graft copolymer be called for short make " polymer " or " conducting polymer ".In the methods of the invention, at least a storage medium is at least a conducting polymer preferably, at least a conducting polymer based on imidazoles, naphthalene, phenanthrene, pyrroles, thiophene and/or benzenethiol particularly, and first-selection is based on pyrroles and/or thiophene.Be preferably formed the conducting polymer based on polyhenylene, poly-furans, polyimidazole, poly-phenanthrene, polypyrrole, polythiophene and/or polyphenyl thiophenol, perhaps at least part of or those of polymerization in water off and on.Belonging to particularly preferred conducting polymer, can be for example based on polypyrrole (PPy), polythiophene (PTH), poly-(to phenylene) (PPP) and/or poly-(to the phenylene vinyl) (PPV) those.Storage medium can separate or make in mixture in advance, then adds to go in the composition and/or add to as raw material in situation seldom and remove and/or be reacted into storage medium in the composition in composition and/or in coating.

In the method for the present invention, preferred at least a storage substance and at least a anion selected, it can realize largely or fully anion being discharged from storage medium, can obviously reduce especially cation thus from electrolyte and/or from the B that fault location moves out, also can reduce thus at metal/coating interface place and form prejudicial free radical.

Preferably make according to the present invention or used conducting polymer is thermodynamically stable under oxidation state (=mix), thereby so that its---will go through the long period---discharge itself and its anion can not be subjected to still that the original place discharges alone.Thus with these chemical systems and other wherein storage medium can not in advance anion be discharged, be not that the storage system of conducting polymer makes a distinction.

Particularly preferably prepare at least a polymer and/or it is added in the mixture and go, this polymer is selected from based on following compound, namely based on poly-(the 1-alkyl pyrroles) that have especially 1 to 16 C atom (P1APy), have especially poly-(the 1-alkoxyl-pyrroles) of 1 to 16 C atom (P1AOPy), have especially poly-(the 3-alkyl pyrroles) of 1 to 16 C atom (P3APy), have especially poly-(the 3-alkoxyl pyrroles) of 1 to 16 C atom (P3AOPy), gather (1-aryl-pyrrolidine) (P1ArPy), gather (3-aryl-pyrrolidine) (P3ArPy), have especially poly-(the 3-alkylthrophene) of 1 to 16 C atom (P3ATH), have especially poly-(the 3-alkoxy thiophene) of 1 to 16 C atom (P3ATH), gather (3-aryl thiophene) (P3ArTH), poly-(3-alkyl two thiophene) that have especially 1 to 16 C atom, poly-(3,3 '-dialkyl group, two thiophene), poly-(3,3 '-dialkoxy, two thiophene), poly-(alkyl three thiophene), poly-(alkoxyl three thiophene), poly-(3,4-ethylene dioxythiophene) (PEDOT) and poly-(benzo [b] thiophene) (PBTH).

Particularly preferably prepare at least a polymer described later and/or it is added in the composition and go, described polymer is selected from poly-(1-methylpyrrole) (P1MPy), gather (1-methoxyl group pyrroles) (P1MOPy), gather (3-methylpyrrole) (P3MPy), gather (3-methoxyl group pyrroles) (P3MOPy), gather (1-phenylpyrrole) (P1PhPy), gather (3-phenylpyrrole) (P3PhPy), poly-(3 methyl thiophene), poly-(3-hexyl thiophene), poly-(3-methoxythiophene), poly-(the own oxygen base of 3-thiophene), poly-(3-phenyl thiophene), poly-(3-methyl two thiophene), poly-(3-hexyl two thiophene), poly-(3,3 '-dimethyl, two thiophene), poly-(3,3 '-dihexyl thiophene), poly-(3,3 '-dimethoxy, two thiophene), poly-(3,3 '-two own oxygen base two thiophene), poly-(3-methyl three thiophene), poly-(3-methoxyl group three thiophene), poly-(the 5-alkyl-3 that has especially 1 to 12 C atom, 4-ethylene two oxy thiophene), gather (isothianaphthene) (PITN), poly-heterocyclic pentylene (PHCP), dioxy-3,4-heterocyclic pentylene (ADO-HCP), two to ten yuan of heterocyclic pentylenes (OHCP), gather (3-hexyl thiophene) (P3HT), replace and/or trapezoidal poly-(to phenylene) (PPP or LPPP) and replacement and/or trapezoidal poly-(to the phenylene vinyl) (PPV or LPPV).

The especially polypyrrole (PPy) that belongs to particularly preferred conducting polymer, gather (N-methylpyrrole) (PMPy), gather (3-alkyl pyrroles) (P3AlPy), gather (3-aryl-pyrrolidine) (P3ArPy), gather (isothianaphthene) (PITN), gather (3-alkylthrophene) (P3AlTH), poly-(alkyl two thiophene), poly-(alkyl three thiophene), gather (ethylenedioxy thiophene) (PEDOT), gather (3-aryl thiophene) (P3ArT), replace and/or trapezoidal poly-(to the phenylene vinyl) (PPV), gather (3-hexyl thiophene) (P3HT), gather (3-hexyl thiophene) (P3HT), polyhenylene (PP), gather (to the phenylene vinyl) (PPV), poly-heterocyclic pentylene (PHCP), poly-dioxy base-3,4-heterocyclic pentylene (PADO), polyphenyl and heterocyclic pentylene (PBHCP), polythiophene (PT), wherein R=alkyl such as methyl, poly-(the 3-alkylthrophene) of butyl etc. (P3AT), polypyrrole (PPy), gather (isothianaphthene) (PITN), poly-(3, the 4-ethylenedioxy thiophene) (PEDOT), what alkyl replaced gathers (to the phenylene vinyl) (MEH-PPV), poly-(2,5-dialkoxy-to the phenylene vinyl) (MEH-PPV), trapezoidal gathers (to phenylene) (LPPP), poly-(p-diphenyl sulfide) (PPS) and poly-(3-hexyl thiophene) (P3HT).

Also can select to gather (1 for polymer, 3-dialkyl group pyrroles), poly-(3,4-dialkyl group pyrroles), poly-(3,4-dialkyl group thiophene), poly-(1,3,4-trialkyl pyrroles), poly-(3, the 4-dialkoxythiophene), poly-(1,3,4-tri-alkoxy pyrroles), poly-(2-aryl thiophene), has especially independently mutually 1 to 16 C atom, perhaps corresponding raw material.For aryl compound can select especially the 1-phenyl-, the 3-phenyl-, the 1-diphenyl-, the 3-diphenyl-, 1-(4-azobenzene)-and/or 3-(4-azobenzene)-compound.

Here it is 1,2,3,4 that preferred preparation or use has the C atom independently of each other, 5,6,7,8,9,10,11,12, and the compound of 13,14,15 and/or 16 alkyl chain.

For raw material and/or polymer, as can be the independently of each other preferred H of substituting group, OH, O, COOH, CH ₂OH, OCH ₃, the C of n=2 to 12 particularly _nH _2n-1, the OC of n=2 to 12 particularly _nH _2n-1, alkyl, alkoxyl, aryl, amine, amino, acid amides, uncle's ammonium, imino group, acid imide, halogen, carboxyl, carboxylate, sulfydryl, phosphonate, S, sulfone and/or sulfonate.

Although it is normally substantially known to be suitable for this conducting polymer, great majority are not also put down in writing as at least a etch-proof scheme; But wherein put down in writing in the document of corrosion-resisting function of this polymer at those, for the non-precious metal surface if not having existed passivation layer then not have corrosion-resisting function.In each embodiment, at least a storage medium consists of at least part of matrix in the composition, particularly at close metal/coating interface place.The polymer of minimum electric conductivity is commercially available to be got.

Preferred use by substituting group and/or the conducting polymer by another substrate molecule (monomer/oligomer) modification and/or contain the conductive copolymer of at least two kinds of different substrate molecules with roughly different redox potentials (monomer/oligomer), with the oxidation-reduction quality of obvious change storage medium from a kind of compound to another compound.Alternative or other, also can mutually mix corresponding different storage substance.Filter out thus at least a compound, it has redox potential standard suitable for the chemical system that comprises the metal surface.Specially suitable storage substance redox potential is corrosion potential at least 75mV, at least 100mV or the 150mV at least that is higher than the metal surface, preferably at least 200mV or at least 250mV, extremely preferred at least 300mV or the potential value of 350mV at least.

Preferably by forming coating and/or mixture and be adjusted to when dry the average pore size of oligomer, polymer, copolymer, block copolymer and/or graft copolymer that higher temperature increases the conduction that will form, especially will be under inert atmosphere with adjustment to 60 to 200 ℃ scope, in air, then want special in 30 to 80 ℃ scope.

The solvent of raw material or product mixture:

In some embodiments, water can be as unique solvent with the preparation conducting polymer.Preferably water is used as a kind of solvent in the solvent mixture, and the water content of solvent mixture is at least 5 % by weight.Just can carry out thus comparatively simple and the processing of environmental friendliness ground, and the anion of main quantity can both enter solution.The water of high level preferably being arranged in solvent mixture or only have water fully as solvent, particularly so that many anion are soluble in water, but is not to be dissolved in the organic solvent or to be insoluble in some organic solvent usually.

Preferably as solvent just or substantially just add water, perhaps for the situation of solvent mixture as another kind of at least solvent add at least a-30 to 200 ℃, particularly preferably in-10 to 160 ℃ or extremely preferably be liquid material in 1 to 95 ℃ of scope.Here, solvent can be chosen wantonly and play in fact selectively acting and mainly maybe can only dissolve raw material or main or can only dissolved anion and oxidant.Even in addition also preferred solvent can only not half not with the oxidant chemical reaction, even under higher temperature.Usually, solvent can or can only not half on oligomer, polymer, copolymer and/or the graft copolymer of the formed conducting polymer of dissolving.

Preferably for the situation of solvent mixture as the another kind of at least solvent except water particularly, interpolation is selected from following at least a, namely is selected from the aprotic liquid that how much has polarity, dipolar nature and the protic liquid of dipolar nature.Polarity and the dielectric constant that brings thus can change in very wide scope.The aprotic liquid of the liquid of faint polarity such as chloroform and/or carrene or dipolar nature such as acetonitrile and/or propylene carbonate can be used in particular for wherein can not making in the raw material of water, especially in the compound based on thiophene for example.The protic liquid of polarity such as water and/or alcohol then in most cases are used for oxidant and anion.The solvent of very little polarity such as alcohol are preferred for dissolving raw material, and those with high polarity then are preferred for dissolved oxidant and salt and are used for dilute acid such as water.

For solvent mixture, preferably add at least a solvent that is selected from acetonitrile, chloroform, carrene, ethanol, isopropyl alcohol, methyl alcohol, propyl alcohol, propylene carbonate and water as another kind of at least solvent.Usually use the solvent mixture that is consisted of by water and at least a alcohol, and the optional liquid that also can contain the non-solvent of another kind of at least solvent and/or another kind of at least as oil of this mixture.

Also particularly preferably use the solvent mixture that is formed by water and at least a organic solvent, because, for example molybdate can only water dissolving and also because there are some azole derivatives usually can only be under desired concn enough to dissolve with at least a organic solvent that can mix with water of addition at least seldom, wherein, the content of at least a organic solvent is in particular at least 2 % by weight in the solvent mixture, preferred at least 6 % by weight, at least 12 % by weight particularly preferably, extremely preferably at least 18 % by weight, particularly at least 24 % by weight.

The order of magnitude 85 to 99% is read usually in the reaction that raw material generates conducting polymer, and great majority are in 88 to 96% scope.

The mixed meeting of product thing:

The product mixture that wherein forms and/or be formed with conducting polymer contains identical with raw mix or essentially identical constituent content, if do not consider chemical reaction.Therefore, identical content is also just arranged accordingly.

Also can add or add at least a stabilizing agent in the product mixture, its optional can being used in the emulsion polymerization process that at first adopts.At least a stabilizing agent preferably also is at least a ion or non-ionic stabilizing agent, particularly at least a polymerisable and/or polymerization, surfactant with optional emulsifier performance.Particularly preferably stabilizing agent is selected from the water-soluble polymer based on polyvinyl alcohol, polyethylene alkyl ether, PSS, PEO, poly-alkyl sulfonic ester, poly-aromatic yl sulphonate, anion and/or cationic surfactant, quaternary ammonium salt and tertiary amine.Extremely preferably from anion and/or cationic, as to be preferably sodium alkyl sulfate and the surfactant of alkylsulfonate, also has especially the C atom and is 10 to 18 alkyl chain length.These water miscible polymer or surfactant are preferred, better discrete particles.

Product mixture can be chosen at least a stabilizing agent that is suitable for particle in anion, cation, space and/or indifferent equilibrium raw mix and the formation product mixture wherein that is substantially devoid of or preferably contains 0.01 to 5 % by weight wantonly, and particularly preferably be 0.5 to 4 % by weight or 0.05 to 3 % by weight, extremely preferred 0.1 to 2 % by weight.

The processing of the coated particle of conduction:

Preferably pass through the method for decantation, filtration and/or freeze-drying, particularly when filtering by Rotary drying or centrifugal drying, and/or particularly in inert atmosphere, be no more than 200 ℃ temperature or preferably be no more than 150 ℃ or be no more than under 120 ℃ the condition and come the dry products mixture by the method for gas circulation and/or heating.Usually in the inorganic particle through applying, need way like this.Thus at utmost or fully will to contain the mixture of liquid dry.If for example can remove largely liquid by decantation, filtration and/or drying through the inorganic particle that applies, then the content of solvent is usually about 1,2,3,4,5 % by weight or usually just in the content that is no more than 10 % by weight.Be called " conductive powder " below dry " mixture ".Under this form, coating of the present invention on the particle is very stable, be long-term conduction and also be can keep chemical for a long time and physics stable, only otherwise nucleophilic occurs to be corroded, for example when being used for inappropriate japanning system, when heat load is too high, for example be higher than 300 ℃ or owing to for example have photolytic activity particle such as TiO ₂(anatase) and when having photochemistry to decompose and/or in strong weather conditions lower times.The coating of this formation normally bond special firmly and/or be largely or complete closed.

Preferably when drying, do not remove the liquid of all amounts, but preferably in pile of grounds, for example keep in the content liquid of 0.1 to 12 % by weight of inorganic uncoated particle particularly.This point is useful, because hole can (again) not become less owing to expanding again.

If needed, can grind fast and/or grind inorganic particle through applying with faint effect, thereby smash so-called cake piece, aggegation piece and/or optionally also have agglomerate and/or so that have the ability of toppling over.Choose wantonly and also will sieve conductive powder.

Preferably at first the inorganic particle that applies is carried out decantation, filtration and/or drying.Then extract leachable component from conductive coating, mode is so that there is no the anion of insertion and there is no that the conducting polymer that is required to be carries out stable oxidant and is dissolved.Can basically not change thus conduction rock-steady structure and the conduction state of conducting polymer.For example can in extraction process, remove with the unnecessary oxidant of japanning reaction, the anion, unreacted monomer and the oligomer that do not insert and all the other impurity and other unwanted components.Extracting operation can particularly preferably adopt acidic aqueous solution such as sulfuric acid, hydrochloric acid and/or carry out with at least a organic solvent such as acetonitrile, chloroform and/or methyl alcohol.This step can obviously be improved the quality of coating.

Now show, after making nucleocapsid particles, sometimes preferably can add stabilizing agent, but usually also do not need so.Yet in certain embodiments, stabilizing agent is added to go in the stable product mixture be disadvantageous.On the other hand, for example select when too high when the concentration of conducting polymer particularly, unsettled product mixture then can be stablized by adding stabilizing agent.

Particle coated with conducting polymer:

In addition, the solution of task of the present invention also depends on inorganic and/or organic particle coated with conducting polymer, and wherein said conducting polymer essence exists with oxidation, conduction state, and also be inserted with anticorrosion anion and optional a certain amount of bonding promotion property anion of a certain amount of activity in this conducting polymer, the preferred the method according to this invention of particle applies simultaneously.

Constituent content in the conductive coating can change in wide range.The thickness of coating is depended in this variation especially: can be coated with and be covered with ultra-thin, thin, thick or very thick coating, and layer thickness is 0.1 to 10hm,＞10 to 100nm,＞100nm to 1 μ m or＞scope of 1 μ m to 20 μ m in.Can also select the component of less or higher density.In addition, the specific area of inorganic particle also can be subject to very strong effect, for example for the SiO that makes by the calcining hydrolysis ₂Particle.

Conducting polymer content in the preferred conductive coating is in coating about 50,52,54,56,58,60,62,64,66,68,70,72,74,76,78,80,82,84,86,88,90,92,94,96,98 or 100 % by weight.Particularly preferably the conducting polymer content in the conductive coating is in the scope of 48 to 100 % by weight, and 61 to 97 % by weight particularly are extremely preferably in 69 to 95 % by weight.

The content of anion is in the conducting polymer of coating about 10,12,14,16,18,20,22,24,26,28,30 or 32 % by weight.Preferably in coating, the amount of oxidant is 0 and is not higher than as far as possible this value.Particularly preferably in the conductive coating amount of anion in 8 to 35mol% scope, particularly preferably in 15 to 33mol%, usually 19 to 32mol%.

In the granule content that comprises its coating and intercalation, take conducting polymer as the basis, the content of particle is about 6,8,10,12,14,16,18,20,22,24,26,28,30,32,34,36,38,40,42,44,46,48,50,52,54,56,58,60,62,64,66,68,70,72,74,76,78,80,82,84,86,88,90,92,94,96 or 98 % by weight.Especially, with conducting polymer in the conductive coating that is rich in binding agent for extruding, comprise the content of particle of its coating and intercalation in 5 to 100 % by weight, particularly preferably in the scope of 55 to 99 % by weight, extremely preferred 75 to 98 % by weight, first-selected 85 to 97 % by weight.

Preferably improve the method for the swellability of the conducting polymer that will form by the organic liquid that can be easy to volatilize by interpolation, increase the average pore size of the conducting polymer that will form, as adding chloroform for polythiophene or for example adding alcohol for polypyrrole and some Polypyrrole derivatives.

Coating of the present invention is normally obviously coloured although thickness is very little.Its majority is to have dyed light green color to bottle green, light blue to navy blue, light gray to Dark grey, light red to peony, purple, brown or black.Conducting polymer is normally hydrophobic, but also it can be configured to comparatively hydrophilic or more hydrophobic according to anion-content, oxidant state, pH value and the substituent kind of side group and content.

Be the coating on the particle of the coating parcel that contains conducting polymer, its electric conductivity can be according to the kind of oxidizability, charge carrier and/or charge carrier activity and 10 ^-8To 10 ⁰In the scope of S/cm, preferably 10 ^-6To 10 ^-1S/cm is particularly preferably in 10 ^-5To 10 ^-2S/cm.

Doping level available element analytic approach or XPS (x-ray spectrometry) record.Usually should be worth in 5 to 33% scope, and in production practices, can only partly realize being higher than 28% doping level.Usually, doping level is in 20% to 33% scope.

Preferably, by the conducting polymer that contains movable anticorrosion anion is regulated the quality that the doping level that obtains maximum possible improves conductive coating, this can bring very high storage effect and also usually can bring enough electric conductivity to the coating that will form.This sufficient electric conductivity is just enough in many application scenarios, because too high electric conductivity may cause potential gradient to destroy rapidly and the driving force that is suitable for anion transport also may be cancelled rapidly or stop (short-circuiting effect), so that anion can not be brought into play its corrosion-resisting function.

The coating that contains conducting polymer on the particle should preferably not contain or contain hardly oxidant, because they are unfavorable for containing the corrosion-resisting function of the organic coating of coated particle.Therefore suggestion is for example removed excessive oxidant by dialysis, extraction and/or filtration from product mixture.

The layer thickness of conducting polymer can change in wide range on the particle.Preferred layer thickness in 1 to 200nm, particularly preferably 2 to 100nm scope, first-selected 3 to 80nm.In the possible situation.Be thinner than organic granular for inorganic particle these layers.Although thicker layer also can be considered in principle, also exists a limiting value, this moment, coating granule no longer can disperse.

The what is called " adhesive accelerant-particle " that preparation and interpolation conducting polymer consist of

Also can add the what is called " adhesive accelerant " of at least a conducting polymer based on making by emulsion polymerisation especially in the mixture that is rich in binding agent.It is at least aly to have respectively per molecule at least one can improve close-burning substituent storage medium for the metal surface.Especially, can improve thus the caking property on the interface of metal and binder substrate and improve anticorrosive property.Because " adhesive accelerant " also always contains the anticorrosion anion of at least a activity, so this anionoid can very rapidly be moved to affected area when producing potential gradient when the coating damage, because " adhesive accelerant " the metal surface applied be rich in coating binding agent and that also contain water after, on purpose preferred diffusion to metal on the interface between the binder substrate and therefore and especially near being absorbed at the interface (nearly storage at the interface).Thus, " adhesive accelerant " can be enriched in closely at the interface more consumingly, and the coated particle of conduction can more or less be realized even distribution at least on the layer thickness of layer simultaneously.

The monomer/copolymer unit that is made of same monomer/oligomer in monomer/copolymer and bound groups replacement is carried out in the specific polymerization process, can make at least a " adhesive accelerant ".Monomer/oligomer can be selected from based on those of benzene, furans, imidazoles, naphthalene, phenanthrene, phenol, pyrroles, thiophene and/or benzenethiol.Substituting group can be selected from alkanoic acid such as carboxylic acid, and at least one C atomicity that has of phosphonic acids, phosphoric acid, sulfonic acid and they is 6 to 20 non-grafting alkyl chain independently of each other, and wherein also optionally can form at least one two strands.Particularly preferredly be based at least one substituted monomer that has independently of each other the substituent benzene, two pyrroles, furans, imidazoles, naphthalene, phenanthrene, phenol, pyrroles, thiophene and/or the benzenethiol that replace at least one phosphonic acids and/or replace oligomer

" adhesive accelerant " can be different from the preparation described in the application and painting method and make in optional agranular mixture by emulsion polymerisation individually, and this mixture comprises at least a water-alcohol mixture, at least a oxidant---preferably contain and at least aly possess the oxidant effect and can be at least part of substitute those of activity corrosion anion of independent oxidant, the anticorrosion anion of at least a activity, at least a monomer/oligomer and at least a material with monomer/oligomer of bound groups replacement, and this material is made of identical monomer/oligomer.Emulsion polymerisation preferred at room temperature or carry out under the slightly higher temperature or pH value in preferred 2 to 4 scopes under carry out.Just can form thus at least size adjustable with particle substantially spherical, and described particle is comprised of the conducting polymer that mixes to a great extent or fully.But these particles are fine dispersion normally.The dispersion liquid that makes thus is normally stable, thereby so that its must be immobile and particle also be able to not disperse again.

Generation or except the inorganic and/or organic granular that applies, this class " adhesive accelerant-particle " also can be inserted in the matrix that contains binding agent.The addition of " adhesive accelerant-particle " can change in very wide scope, for example preferably adds the composition that is rich in binding agent of 0.01 to 20 % by weight in solid content, and particularly preferably its amount is 0.1 to 10 % by weight, extremely is preferably 1 to 5 % by weight.

The use of the coated particle of conduction:

The particle that applies according to the inventive method or can be used for the surface of coated metal, wire rod, section bar or part to reach etch-proof purpose coated with the inorganic and/or organic granular of conducting polymer; be used for coating surface to avoid static electrification and/or pollution is arranged; can be used as the electrode material in sensor, the battery; as the electrode material with catalytic performance; as the dielectric additive that is suitable for conductive coating and material; in art for electrical insulation, be used as packing material, as pigment or be used for the smooth layer of conductor.

The particular advantages of system of the present invention and particle and surprising effect:

Method for the preparation of conductive coating of the present invention is particularly suitable for commercial Application, and the more expensive raw material of amount can apply a large amount of particles in process neutralization very easy with respect to many other painting methods with very little equipment cost because only utilize seldom.But bring in the art methods of similar coatings in meeting, then be different from the inventive method and will preferably add adhesive accelerant such as silane, in raw material, insert the interval base such as alkyl chain, before oxidation, add in the mixture based on the stabilizing agent of water-soluble polymer such as CMC and/or add surfactant, thereby could improve the caking property of metal surface.The introducing of adhesive accelerant is normally very debatable in the prior art in the mixture, because all must adopt special adhesive accelerant for the particle of each type.Then usually need to before oxidation, for example surfactant not added in the mixture in the method for the invention.

When the powder that conducting polymer is formed be inserted into that organic composite is for example painted or similar japanning, mainly or fully be in the organic coating time, the color of powder that does not contain light color nuclear is obviously more stronger and can be used as the additive of organic coat composition and tone or spot or the shoft effect of coating not expect that give to form thus.Therefore the electric conductivity of the coating that this mode makes can be inhomogeneous and a kind of incomplete, i.e. different good or bad corrosion-resisting function in part is provided:---will there be conductive path in the diafiltration initial value---from this value too high at this.

Surprisingly, anion is moved to the corrosion-resisting function of the coating of the present invention of release that corrosion area goes and transport phenomena and carboxylic expectation from conducting polymer, not only in the test of very special test such as employing grating-Kelvin probe (SKP), can authenticate to, and the anticorrosion anion that discharges in corrosion area enrichment and have the remarkable rising of corrosion-resisting function on the metallic substrates of the organic coating that contains conducting polymer, also can be in macroscopic scope authenticate to the sample relevant with production practices and test example such as salt spray test.

The method of coating inorganic or organic granular is unexpectedly simple, can industry reproduces and is eco-friendly.In this process, as long as several cubic centimetres raw mix just can apply the particle of more grams.

Now be surprised to find, the coating of nano particle can be carried out fruitfully, can have very high coating degree and to a great extent not cohesion.On the other hand, also can apply thicker particle with the inventive method well in unusual ground, although because very large size and the very poor coating that still can form uniformly and normally seal of dispersibility are arranged on these particles.

Astoundingly, utilize the particle contain conducting polymer can be especially simply, stable and conducting polymer is dispersed in the composition that is rich in binding agent, particularly when film forming.

Surprisingly, the selection of insertable anion is almost without limits in the chemical polymerization process of conducting polymer.

Astoundingly, all be stable and also more stable than desired therein in very wide pH value scope when the particle of conducting polymer is in depositing in liquid medium, thereby do not observe the passivation of conducting polymer.

Astoundingly, the particle that contains conducting polymer is special mechanically stable, and its housing is attached on the particle well, thereby so that also is not aware of when ultrasonic wave is processed and damages or or even when conducting polymer is deposited on the particle in the mixture under ul-trasonic irradiation for a long time.

In addition surprisingly, can be when initial when depositing stable dispersion liquid and adhere to or gel can again disperse again and be inserted into with follow zero defect in the particle through applying on the container bottom in the basic organically dispersion liquid of composition of similar japanning, then can be inserted in the substantially organic coating.

Embodiment and comparative example:

Embodiment described below is used for more elaborating illustratively content of the present invention.

1. the preparation process of conducting polymer and changing coating inorganic in the situation of compositions of mixtures Particle:

In single still method and in constant preparation conducting polymer and the coating inorganic particle simultaneously of remaining under 50 to the 60 stable temperature in whole reaction.

At first under stirring condition, be added in the distilled water of 100ml isopropyl alcohol and respectively 10 to 15g be selected from Al ₂O ₃, BaSO ₄, CaCO ₃, CuO, SiO ₂, SnO ₂, anatase or rutile form TiO ₂, the biotite of ZnO, coarse-grain, treated montmorillonite, rich quartzous extra large sand, potter's clay or the pretreated cellulose powder that is suitable for column chromatography in addition powder.Then add 0.1 to 0.5ml concentrated vitriol, the pH value is adjusted in 4 to 6 the scope, the effect of the dissolve medium of molybdic acid and monomer/oligomer has also been played in wherein said acid simultaneously.Then, the monomer/oligomer in the isopropyl alcohol that is dissolved in 20 to 50ml room temperatures of interpolation 0.3ml.Can use respectively as raw material and to be selected from a kind of in pyrroles, N-methylpyrrole and the ethylenedioxy thiophene.Added 1.5 to 3g/L after the mixing time at 15 to 20 minutes and be preheating to the molybdic acid aqueous solution (H mixture temperature and that contain 20% isopropyl alcohol of having an appointment ₂MoO ₄).Within the whole reaction time, stir the mixture.After 30 to 150 minutes further mixing time, by filtering unnecessary solvent mixture and oxidant with the inorganic particle that applies and the particle separation that is formed at the conducting polymer in the dispersion liquid.Then under 60 to 80 ℃ in drying cupboard dried particles 20 to 30 minutes, form thus dry filter cake.Smashing the filter cake cake in mortar to pieces farthest ground it evenly in 10 to 15 minutes.Partly use alternately in addition ball milling.The inorganic particle that abrasive material contains fully and part applies, coating shell separate remnants, the particle of conducting polymer and uncoated inorganic particle (granulate mixture).Can assess with light microscope, about visible particle of 85 to 95% is the coated particle with conductive capability respectively.In principle, can adopt the inorganic particle of average grain diameter in 5nm to 5mm scope here.When grinding, can not or can only grind littlely according to its person's character inorganic particle not half.For greater than about particle of 100 to 200nm, the distribution of particles of inorganic particle can be in very wide particle size distribution range, be lower than to approach single the dispersion.The particle that only is less than about 100nm is only in fact spherical.Grain coating has 2 to 10nm bed thickness, and this can observe in projection electron microscope.The content of conducting polymer is determined by the heating power meter and is 3 to 10 % by weight of dried particles mixture.In each test, can both obtain electric conductivity and so higher doping.Electroconductive polymer coating on the particle (nucleocapsid particles) be the bonding good, thereby so that coating can not tear soon or grind down, even in ultrasonic bath, can not yet.Carried out a large amount of tests, wherein had in sub-fraction row and the table 1.

In addition; in complementary testing; insert granulate mixture in the complete anhydrous ethanolic solution or in the ethyl acetate solution cake in ultrasonic bath, disperse; in order to then two sheet metals are suspended in this suspension; and also for via the cataphoresis method as in cathode electrode dip-coating process under the current strength of 10 to 100V voltage and 2 to 20mA, in 1 to 5 minute, the conductive particle of coating is deposited on the cathode sheet.Different from anaphoresis method or electric polarization method, for the metallic object that will apply, so owing to be that cataphoresis cataphoresis method does not have corrosion danger.But also just can realize thus with granulate mixture very equably, the thin and adhesion also complete coated metal lamina in two sides sometimes by force.Then the sheet drying after will applying.Layer thickness is estimated as 2 to 15 μ m.Coating on the thin slice will be significantly better than situation about for example applying with suspension when granulate mixture.The form of the coated particle that the structure of coating will be passed through to insert in fact on the thin slice is determined.And surprised is, in all research that sometimes will strongly process, the performance of conducting polymer---particularly its electric conductivity, its chemistry and heat endurance with and corrosion resistance---can be not deteriorated.

Table 1: have the composition of mixture of inorganic particle and the character of coating

Content, μ L, ml or g	B1	B2	B3	B4	B5	B6	B7	B8	B9	B10	B11
												The pyrroles, μ L	300	300	300	300	300	300	300	300
Ethylidene dioxy base thiophene, μ L									300	300	300
												Benzoate, g	6
Nitro-salicylic acid salt, g		6						3
												The hexafluoro titanate, g			6
Salicylate, g				6		6
												Tartrate, g					6		6
Molybdate ^*，g				3	3			2	3	3	3
												Tungstates ^*，g						3	3
Ce ⁴⁺-sulfate, g	3
												Fe ³⁺-nitrate, g		3
Fe ³⁺-sulfate, g			3
												Al ₂O ₃C，Degussa，12nm，g	15	15	15	15	15	15	15	15	15	15	15
Isopropyl alcohol, ml	100	100	100	100	100	100	100	100	100		100
												Distilled water, ml	150	150	150	150	150	150	150	150	150	250	200
The pH-value	4-6	4-6	4-6	4-6	4-6	4-6	4-6	4-6	4-6	4-6	4-6
												Temperature ℃	40-60	40-60	40-60	40-60	40-60	40-60	40-60	40-60	40-60	40-60	40-60
Electrical conductivity, S/cm	n.b.	10 ^-2	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.
												Color	Blue	Blue	Ash	Ash	Ash is blue	Ash	Ash is blue	Ash is blue	Ash is blue	Ash is blue	Ash is blue

Anion with oxidant effect

2. preparation and the coating of the organic granular under compositions of mixtures changes:

At first at room temperature prepare to contain and comprise organic granular and optionally do not have oxidation susceptibility but its anion has the water-containing material mixture of all components of the salt of Corrosion Protection, optional also add the ethanol of 1 to 10 % by weight, prepare conducting polymer with this---except the oxidant.Various compositions are described in the table 2.The anion of salt has Corrosion Protection if salt has oxidation characteristic, then can only be added into salt after homogenizing with just replacing.Then will before adding molybdate or tungstates raw mix be heated to 50 ℃ when using molybdate or tungstates as oxidant, condition is if the pH value is higher than 3.Regulate the pH value with phosphoric acid.Under this temperature, stir the raw mix strong mixing with the realization component in 20 minutes, be separated because may occur.Must there be the good uniformity in solution (raw mix) when adding oxidant.

As organic granular is to have specific composition and glass transition temperature T _gPolystyrene, Polyphenylethylene-butyl acrylate or butyl polyacrylate, they add with the form of aqueous dispersions.Organic granular has almost, and monodispersed particle diameter distributes and is spherical to a great extent.Average particle size distribution can be adjusted between 150 to 500nm, and distributes glass transition temperature T for each this class _gCan change with chemical composition.

Table 2: have the composition of mixture of organic granular and the character of coating

Content, ml or g	B21	B22	B23	B24	B25	B26	B27	B28	B29	B30	B31	B32	B33	B34
															Distilled water, ml	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Ethanol, ml	1	3	5	10					5	5	5	5	5	5
															Isopropyl alcohol, ml					1	3	5	10
The pyrroles, g	0.1	0.5	1.5	5	0.1	0.5	1.5	5
															The N-methylpyrrole, g									1.5
3-methoxyl group pyrroles, g										1.5
															The 3-methylpyrrole, g											1.5
The 3-N-ethyl pyrrole N-, g												1.5
															The 3-phenylpyrrole, g													1.5
Ethylidene dioxy base thiophene, g														1.5
															Benzoate, g	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0
NH ₄S ₂O ₈，g	0.1	0.5	1.5	5	0.1	0.5	1.5	5	1.5	1.5	1.5	1.5	1.5	1.5
															Polystyrene, g	10	10	10	10	10	10	10	10	10	10	10	10	10	10
Particle mean size, nm	300	300	300	300	300	300	300	300	300	300	300	300	300	300
															The glass transition temperature T of particle _g，℃	100	100	100	100	100	100	100	100	100	100	100	100	100	100
The pH-value	3	3	3	3	3	3	3	3	3	3	3	3	3	3
															Temperature, ℃	25	25	25	25	25	25	25	25	25	25	25	25	25	25
The size of organic coat particle, nm	305	310	315	320	305	310	315	320	315	315	315	315	315	315
															Electrical conductivity, S/cm	10 ^-6	10 ^-5	10 ^-4	10 ^-3	10 ^-6	10 ^-5	10 ^-4	10 ^-3	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.
Doping level, about %	30	30	30	30	30	30	30	30	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.

Content, ml or g	B35	B36	B37	B38	B39	B40	B41	B42	B43	B44	B45	B46	B47	B48	B49
																Distilled water, ml	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Ethanol, ml	5	5	5	5	5	5	5	5	5	5	5	5	5	5	5
																Isopropyl alcohol, ml
The pyrroles, g	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5				1.5
																The N-methylpyrrole, g												1.9	1.9	1.9
Molybdate ^*，g		1.65	3.30	10.2	13.6	20.3	10.2	10.2	10.2	10.2	10.2	10.2	13.6	20.3	10.2
																Tungstates ^*，g	3.3
Polystyrene, g	10	10	10	10	10	10
																Polyphenylethylene-butyl acrylate, g							10	10	10	10	10	10	10	10
Butyl polyacrylate, g															10
																Styrene: butyl acrylate ratio							9∶1	5∶1	2∶5	3∶5	4∶5	3∶5	3∶5	3∶5
Particle mean size, nm	300	300	300	300	300	300	300	300	300	300	300	300	300	300	300
																The glass transition temperature T of particle _g，℃	100	100	100	100	100	100	80	60	40	20	-10	20	20	20	-40
The pH-value	2	2	2	2	2	2	2	2	2	2	2	2	2	2	2
																Temperature, ℃	25	25	25	25	25	25	25	25	25	25	25	25	25	25	25
The size of organic coat particle, nm	315	315	315	315	315	315	315	315	315	315	315	315	315	315	315
																Electrical conductivity, S/cm	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.
Doping level, about %	17	15	19	23	27	30	23	23	23	23	23	18	21	24	23

Content, ml or g	B50	B51	B52	B53	B54	B55	B56	B57
									Distilled water, ml	100	100	100	100	100	100	100	100
Ethanol, ml	5	5	5	5	5	5	5	5
									The pyrroles, g	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Molybdate ^*，g	3.41	3.41	3.41	3.41
									Tungstates ^*，g					3.30	3.30	3.30	3.30
Polyphenylethylene-butyl acrylate, g	10	10	10	10	10	10	10	10
									Styrene: butyl acrylate ratio	3∶5	3∶5	3∶5	3∶5	3∶5	3∶5	3∶5	3∶5
Particle mean size, nm	300	300	300	300	300	300	300	300
									The glass transition temperature T of particle _g，℃	20	20	20	20	20	20	20	20
The pH-value	1	3	4	5	1	3	4	5
									Temperature, ℃	25	25	50	50	25	25	50	50
The size of organic coat particle, nm	315	315	315	315	315	315	315	315
									Electrical conductivity, S/cm	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.	n.b.
Doping level, about %	28	28	28	28	28	28	28	28

^*Anion with oxidant effect

The average grain diameter of the organic granular of uncoated and coating is determined under SEM.Conductive capability utilizes the two-point method on the briquetting of conductive doped powder and determines in interdigital structure (comb poles).All conductive coating organic granulars all are black.

For material solution, proving specially suitable is to contain those of pyrroles and N-methylpyrrole, and they preferably are coated on the organic granular based on Polyphenylethylene-butyl acrylate according to the ratio of 50 to 90 % by weight styrene umbers.Preferably as oxidant with particularly preferably be molybdate or tungstates as anion simultaneously.For molybdate and tungstates very important point be, can and preferred almost maximum conducting polymer doping about 28% for being no more than, in polymer unit.

To B28, along with pyrroles's content increases, the coating layer thickness liquid of conducting polymer can increase, approximately from 5nm to 10nm in Embodiment B 21.In Embodiment B 34, use thiophene to replace the pyrroles.Compare with B35 with B23, in Embodiment B 36 to B40, use molybdate.The concentration of movable anticorrosion anion is again higher and improve therefrom memory action.To B48, because the variation that organic granular forms, the film forming of particle also will change: film forming is best in B43 and B44 in Embodiment B 41, and if can not operate under the temperature of room temperature being lower than, at glass transition temperature T _gFilm forming then no longer can be controlled well during less than 20 ℃.PH value or oxidant can change in Embodiment B 50 to B57, and can reach best result for tungstates under for molybdate and the pH value 5 under 4 and 5 the pH value.Aspect the activity of the anticorrosion anion of activity, Embodiment B 52, B53 and B57 have shown best anion activity, because these anion are especially little and it is less to generate the tendency of larger polyanion under higher pH value.

3. change preparation and the coating procedure of organic granular under the oxidant condition

Basically all operate such as second preparation process in these embodiments.

In the distilled water of 50ml, at first add the altogether polystyrene that contains this class organic granular of 20 % by weight and its 350nm average grain diameter of having an appointment and/or the aqueous dispersions of butyl polyacrylate and the pyrroles of the fresh distillation of 1.4g, thus the raw materials solution in the first operating procedure of 50g.In other experiments, replace the pyrroles with the N-methylpyrrole.Agitating solution 20 minutes is at room temperature to make the mixture homogenising.

Then prefabricated oxidizing agent solution, method are the oxidant of dissolving 0.1 to 1Mol in the water of 50ml such as a) phosphomolybdate or b) contain≤10 ^-4Mole Fe ³⁺Muriatic H ₂O ₂And H ₂O ₂Excessive.After the material solution homogenizing, dropwise be added into this solution.Then formed mixture at room temperature stirred 4 to 6 hours.In this process, can in dispersion liquid, form the thick polypyrrole coating of about 10nm in organic granular.In addition, before adding oxidant, a) anion of oxidant is inserted into as the doping ion in polypyrrole or the corresponding derivative, and b) before oxidant adds, respectively the etch-proof movable anion (molybdate, hexafluoro titanate, fluorozirconate, tungstates) of Renyi is added in the raw mix in addition and goes.

Then the cellulose membrane at a 10.000MWCO made the reactant mixture dialysis 48 hours with two double distilled water, thereby unreacted raw material, oxidant and anion are removed.The coating of 5 to 20nm thickness is set at particle.The dispersion liquid that so obtains is stable and available surpassing in a year and a half.

4. the preparation approach when conducting polymer matrix preparation " adhesive accelerant-particle ":

Under the room temperature, preparation contains the water-containing material mixture of 5% ethanol in the aqueous solution, and this mixture be based on monomer/oligomer that bound groups replaces with by same monomer/oligomer, i.e. the monomer/oligomer that consists of of pyrroles.As bound groups, can use the alkyl phosphonic acid with 10 or 12 C atoms of non-branching.The anticorrosion anion of interpolation activity in the solution for this reason, ammonium molybdate.This molybdate also plays the oxidant effect simultaneously.Within whole period, stir the mixture.In 2.5 to 4 pH value scope, operate, wherein regulate the pH value via the content of alkyl phosphonic acid.The pK of bonding promotion property group _sValue is being determined the pH value of raw mix and can form the micella of the monomer/oligomer of bound groups replacement in mixture.Under stirring condition, emulsion polymerisation 10 to 24 hours.By the dialysis dispersion liquid of purifying, with the pure aqueous dispersions that contains of " adhesive accelerant-particle " that obtain not containing to a great extent excessive anion and complete oxygen-freeization agent and unreacted monomer/oligomer.This dispersion liquid contains in fact spherical " adhesive accelerant-particle ", and its particle diameter distributes and approaches single disperse and its average grain diameter can be adjusted in arbitrarily in 50 to 400nm the scope.

Claims

1. method that applies organic and/or inorganic particle, wherein said particle is present in the mixture and/or when initial and is formed at wherein, and described mixture is dispersion, has material, colloidal sol and/or a gel that fluid ability maybe can be mediated, it is characterized in that, contain as the mixture of raw mix:

It is selected from-at least a monomer and/or at least a oligomer---below be called " raw material of conducting polymer " or just be called " raw material "---based on pyrroles's replacement and the not monomer of substituted compound and oligomer and based on the replacement of thiophene and not monomer and the oligomer of substituted compound, and they are suitable for forming the oligomer/polymer/copolymer of conduction/block copolymer/graft copolymer;

-at least a anion---optional at least a salt, ester and/or at least a acid are as the carrier of this anion---and at least a anion 1 in the conducting polymer) can be inserted into and/or be inserted in the structure of conducting polymer as the doping ion, 2) if conducting polymer has potential drop also can again discharge and 3 from this structure again) if exist the metal surface just can play corrosion-resisting function---below be called " the anticorrosion anion of activity ";

-at least a be selected from bunch, nano particle, nanotube, the particle of fibrous, pelletizing shape and/or loose structure, average grain diameter the particle of 10nm to 10mm and their aggregate and/or agglutination body and

-water and/or another kind of at least polar solvent and optional another kind of at least solvent;

And form the coating that thickness is at least an individual layer by this raw mix at least a portion particle surface, described coating randomly also contains a large amount of monomers and/or oligomer except the another kind of at least composition of raw mix, perhaps contain a large amount of conducting polymers

And, in dispersion, material, in colloidal sol or the gel or---optional at least after part removes liquid---under aerosol state, by adopting at least a oxidant and all having under the anticorrosion anion existence condition of at least a activity, during particle coating and/or afterwards, utilize the electrochemical method of voltage effect and/or the photochemical method under electromagnetic radiation to carry out oxidation reaction and at least a portion monomer and/or oligomer are being contained carry out at least in part chemical reaction in the mixture of water and/or another kind of at least polar solvent and generate at least a oligomer and/or optional part or fully generate respectively at least a polymer, copolymer, block copolymer and/or graft copolymer

2. method that applies organic and/or inorganic particle, wherein said particle is present in the mixture and/or when initial and is formed at wherein, and described mixture is dispersion, has material, colloidal sol and/or a gel that fluid ability maybe can be mediated, it is characterized in that, contain as the mixture of product mixture:

-at least a " conducting polymer " based on oligomer/polymer/copolymer/block copolymer/graft copolymer, its be selected from based on pyrroles's replacement and not substituted compound oligomer and based on the replacement of thiophene and the oligomer of substituted compound not;

-at least a anion---optional at least a salt, ester and/or at least a acid are as the carrier of this anion---and at least a anion 1 in the conducting polymer) can be inserted into and/or be inserted at least in part in the structure of conducting polymer as the doping ion, 2) if conducting polymer has potential drop also can again discharge and 3 from this structure again) if exist the metal surface just can play corrosion-resisting function---below be called " the anticorrosion anion of activity ";

-randomly, oxidant, water and/or another kind of at least solvent,

3. method as claimed in claim 1 or 2 is characterized in that, described mixture when the component blend until formed oxygen-freeization agent before at least one individual layers of one or more raw materials at least a portion surface of inorganic and/or organic granular.

4. method as claimed in claim 1 or 2, it is characterized in that, described mixture when the component blend until before at least a portion surface of particle has formed at least one individual layer that is made of the anticorrosion anion of at least a activity and optional oxidant, do not contain the raw material of conducting polymer.

5. method as claimed in claim 1 or 2 is characterized in that, at least a anion that does not play the oxidant effect adds in the mixture before individual layer forms or when forming and goes.

6. method as claimed in claim 1 or 2 is characterized in that, raw mix and/or product mixture contain:

-randomly, at least a monomer and/or at least a oligomer of material content in 0.001 to 20 % by weight scope,

-randomly, at least a oxidant, and oxygenate content is in the scope of 0.05 to 50 % by weight,

-at least a inorganic and/or organic particle and granule content in the scope of 1 to 95 % by weight,

-at least a the solvent that is suitable for raw material, anion and/or oxidant, and solvent is in the scope of 1 to 5000 % by weight, and it surpasses 100 % by weight,

7. method as claimed in claim 1 or 2 is characterized in that, raw mix has following composition:

-randomly, at least a monomer of 0.001 to 0.5mol/L raw mix and/or at least a oligomer, only otherwise can cause high concentration so that coated particle is assembled gets final product,

The anticorrosion anion of-0.01 to 1mol/L at least a activity, randomly at least a salt, ester and/or at least a acid is as the carrier of this anion, all in anion,

Inorganic and/or the organic granular of-1 to 96 % by weight,

-wherein, when---optional after---when having added monomer/oligomer or oxidant, all these content and optional other, at this additive of not mentioning---but not comprising solvent---satisfy summation 100 % by weight, and

-at least a the solvent that is suitable for raw material, anion and/or oxidant, and solvent is in the scope of 2 to 4000 % by weight, and it surpasses 100 % by weight.

8. method as claimed in claim 7 is characterized in that, described inorganic and/or organic granular is the inorganic and/or organic granular of at least a compound.

9. method as claimed in claim 1 or 2 is characterized in that, product mixture has following composition:

The anticorrosion anion of-0.01 to 1mol/L at least a activity, randomly at least a salt, ester or at least a acid is as the carrier of this anion, all in anion,

-randomly, with one times of at least a oxidant to the amount of five times of material quantities,

Inorganic and/or the organic granular of-1 to 96 % by weight,

10. method as claimed in claim 9 is characterized in that, described inorganic and/or organic granular is the inorganic and/or organic granular of at least a compound.

11. method as claimed in claim 1 or 2 is characterized in that, raw mix and/or product mixture have following composition:

-randomly, at least a monomer and/or at least a oligomer of material content in 1 to 25 % by weight scope,

-randomly, at least a oxidant, and oxygenate content is in the scope of 1 to 40 % by weight, and

-at least a inorganic and/or organic granular, its content are 35 to 95 % by weight.

12. method as claimed in claim 1 or 2 is characterized in that, raw mix and/or product mixture have following composition:

-randomly, at least a monomer and/or at least a oligomer of material content in 0.5 to 18 % by weight scope,

-randomly, at least a oxidant and its content in 0.2 to 30 % by weight scope, and

-at least a inorganic and/or organic granular, its content are 10 to 40 % by weight.

13. method as claimed in claim 1 or 2 is characterized in that, product mixture has following composition:

-product content is at least a conducting polymer of 1 to 25 % by weight, and

-granule content is at least a inorganic and/or organic granular of 35 to 95 % by weight.

14. method as claimed in claim 1 or 2; it is characterized in that; inorganic particle is made of at least a material basically; this material is selected from respectively at least a boride basically; carbide; carbonate; cuprate; ferrate; fluoride; fluorinated silicate; niobates; nitride; oxide; phosphate; phosphide; phosphosilicate; selenides; silicate; sulfate; sulfide; tellurides; titanate; zirconates; be selected from least a carbon; be selected from least a alloy, be selected from least a metal and/or their mixed crystal; mixture and/or fork are given birth to body.

15. method as claimed in claim 1 or 2 is characterized in that, inorganic particle is selected from least a material basically, and this material is selected from least a alkaline earth metal carbonate, titanates of alkali-earth metals, alkaline earth metal zirconate, SiO basically ₂, contain aluminosilicate, mica, clay mineral, zeolite, be selected from based on SiO ₂And/or the thin slice of silicate, be selected from the oxide that contains aluminium, iron, calcium, copper, manganese, titanium, zinc, tin and/or zirconium.

16. method as claimed in claim 1 or 2, it is characterized in that the organic granular that contains conducting polymer mainly or fully is to be selected from one group that polymer by styrene-based, acrylate, methacrylate, Merlon, cellulose, polyepoxide, polyimides, polyethers, polyurethane, siloxanes, polysiloxanes, polysilane and polysilazane forms those.

17. method as claimed in claim 1 or 2 is characterized in that, at mixing material or adding to go in the mixture before grinding, drying and/or calcination particle.

18. method as claimed in claim 1 or 2, it is characterized in that, monomer and/or oligomer are selected from monomer and/or the oligomer of the heterocyclic compound of X=N wherein and/or S, and it is suitable for forming thus the oligomer/polymer/copolymer of conduction/block polymer/graft polymers.

19. method as claimed in claim 1 or 2 is characterized in that, monomer and/or oligomer are selected from the compound that does not replace and/or replace based on pyrroles and/or thiophene.

20. method as claimed in claim 1 or 2 is characterized in that, the compound that does not replace or replace is selected from two thiophene, three thiophene, alkylthrophene, ethylenedioxy thiophene and/or alkyl pyrroles's monomer and/or oligomer.

21. method as claimed in claim 1 or 2, it is characterized in that, as monomer/oligomer, at least a compound is selected from 1-alkyl pyrroles, 1-alkoxyl pyrroles, 3-alkyl pyrroles, 3-alkoxyl pyrroles, 3,4-dialkyl group pyrroles, 3,4-dialkoxy pyrroles, 1,3,4-trialkyl pyrroles, 1,3,4-tri-alkoxy pyrroles, the 1-aryl-pyrrolidine, the 3-aryl-pyrrolidine, 1-aryl-3-alkyl pyrroles, 1-aryl-3-alkoxyl pyrroles, 1-aryl-3,4-dialkyl group pyrroles, 1-aryl-3,4-dialkoxy pyrroles, the 3-alkylthrophene, the 3-alkoxy thiophene, 3,4-dialkyl group thiophene, 3, the 4-dialkoxythiophene, 3,4-ethylenedioxy thiophene and their derivative.

22. method as claimed in claim 1 or 2, it is characterized in that, by hydrogen, hydroxyl, halogen, alkoxyl, alkyl, carboxyl, carboxylate, amine, amino, acid amides, uncle's ammonium, imines, acid imide, phosphate, diphosphate, sulfydryl, sulfone, sulfonate, aryl and/or have or do not have oligomer, polymer, copolymer, block copolymer and/or the graft copolymer that other substituent alkyl chains non-branch or branch come substituted monomer and/or oligomer or form thus.

23. method as claimed in claim 1 or 2, it is characterized in that, add in the mixture have the raw material of loose molecular structure and/or wherein at least a formed conducting polymer have comparatively loose molecular structure, this can cause the pore system average pore size of conducting polymer larger.

24. method as claimed in claim 1 or 2 is characterized in that, adds water miscible raw material in mixture.

25. method as claimed in claim 24 is characterized in that, described water miscible raw material is no longer water-soluble or only also be slightly soluble in water after its oxidation.

26. method as claimed in claim 1 or 2 is characterized in that, in mixture, form based on can with and/or with the polypyrrole of at least a anion and/or the product of polythiophene.

27. method as claimed in claim 1 or 2 is characterized in that, at least a anion is selected from based on carboxylic acid, contains the hydroxyl carboxylic acid, hydroxycarboxylic acid, dicarboxylic acids, tricarboxylic acids, two and/or trisubstituted aralkyl carboxylic acid, adjacent, and/or the aralkyl carboxylic acid that replaces of contraposition, contain amino, nitro, SO ₃The aralkyl carboxylic acid of H-and/or OH-group, sulfonic acid, inorganic oxacid, boronic acid containing, contain mangaic acid, contain molybdic acid, phosphoric acid, phosphonic acids, fluoro silicic acid, silicic acid, contain the acid of at least a rare earth element and/or yttrium, sulfur acid contains metatitanic acid, contain vanadic acid, contain wolframic acid, contain stannic acid, contain zirconic acid, their salt, those anion of the anion of their ester and their mixtures.

28. method as claimed in claim 1 or 2 is characterized in that, at least a anion is selected from based on alkyl phosphonic acid, arylphosphonic acid, benzoic acid, butanedioic acid, tetrafluoro silicic acid, hexafluoro metatitanic acid, hexafluoro zirconate, gallic acid, hydroxacetic acid, silicic acid, lactic acid, molybdic acid, niobic acid, nitro-salicylic acid, oxalic acid, phosphinylidyne molybdic acid, phosphoric acid, phosphorus silicic acid, phthalic acid, salicylic acid, tantalic acid, vanadic acid, tartaric acid, wolframic acid, the anion of their salt, ester and their mixture.

29. method as claimed in claim 1 or 2 is characterized in that, the anticorrosion anion of at least a activity is gone through ligand exchange, variation of valence and/or changes in solubility, and forms the oxidation protection layer at the defect area place and/or in the layering interfaces location.

30. method as claimed in claim 29 is characterized in that, the anticorrosion anion of described at least a activity is TiF ₆ ^2-, ZrF ₆ ^2-, CeO ₄ ^4-, MnO ₄ ^-, MnO ₄ ^2-, MoO ₄ ^2-, VO ₄ ^2-, WO ₄ ^2-, WO ₄ ^4-

31. method as claimed in claim 1 or 2 is characterized in that, at least a anion is selected from based on complex fluorides, molybdate, nitro compound, those of phosphorous negative oxygen ion, polysiloxanes, silane, siloxanes and/or surfactant.

32. method as claimed in claim 31 is characterized in that, at least a anion is selected from based on those of carboxylate.

33. method as claimed in claim 1 or 2 is characterized in that, the diameter that at least a anion has is not more than the average pore size of conducting polymer pore system.

34. method as claimed in claim 1 or 2 is characterized in that, improves the electric conductivity of the coating that will form by the concentration that improves at least a anion in the conducting polymer.

35. method as claimed in claim 1 or 2 is characterized in that, improves the electric conductivity of the coating that forms by adding at least a anion that can have different valence state and can be transformed to simply other valence states.

36. method as claimed in claim 1 or 2 is characterized in that, for wanting shielded metal surface coated with the coating that contains the coating inorganic particle, optional, the anion that adds has corrosion-resisting function in addition on the metal surface.

37. method as claimed in claim 1 or 2 is characterized in that, for wanting shielded metal surface coated with the coating that contains the coating inorganic particle, optional, the anion that adds also has the effect that suppresses layering in addition on the metal surface.

38. method as claimed in claim 1 or 2 is characterized in that, by the concentration of raising oxidant, raw material and/or by adding the sizeable anion of at least a anion, improves the electric conductivity of the coating that will form.

39. method as claimed in claim 1 or 2 is characterized in that, adds at least a based on H ₂O ₂, lewis acid, molybdic acid, niobic acid, tantalic acid, metatitanic acid, wolframic acid, zirconic acid, contain yttrium acid, contain lanthanum acid, contain Fe ³⁺Acid, contain Cu ²⁺Acid, their oxidant of salt, ester and/or mixture.

40. method as claimed in claim 39 is characterized in that, and is wherein said based on H ₂O ₂Oxidant be barium peroxide, peracetic acid, benzylhydroperoxide, cross mangaic acid, cross sulfate mono or cross pyrosulfuric acid.

41. method as claimed in claim 1 or 2 is characterized in that, uses compound and/or at least a compound based on peroxide and/or peracid of the acid that at least a salt based on them can multivalence attitude form exists as oxidant.

42. method as claimed in claim 1 or 2 is characterized in that, the solvent that adds as at least a liquid is in a liquid state in the temperature range of 0 to 200 ℃, 2 to 160 ℃ or 5 to 95 ℃.

43. method as claimed in claim 1 or 2 is characterized in that, adds at least a in the protic liquid that is selected from dipolar nature aprotic liquids, dipolar nature and the nonpolar liquid as at least a liquid.

44. method as claimed in claim 1 or 2 is characterized in that, is selected from least a in acetonitrile, chloroform, ethanol, isopropyl alcohol, methyl alcohol, propyl alcohol, toluene, ethyl acetate and the water as at least a liquid selective.

45. method as claimed in claim 1 or 2, it is characterized in that, by by the swellability that adds the organic liquid that to be easy to volatilize and improve the conducting polymer that will form, increase the average pore size of conducting oligomers, polymer, copolymer and/or the graft copolymer that will form.

46. method as claimed in claim 1 or 2, it is characterized in that, prepare at least a oligomer as product, polymer, copolymer, block copolymer and/or graft copolymer and/or it is added in the composition go, they are selected from based on poly-(1-alkyl pyrroles), poly-(1-alkoxyl pyrroles), poly-(3-alkyl pyrroles), poly-(3-alkoxyl pyrroles), poly-(1-aryl-pyrrolidine), poly-(3-aryl-pyrrolidine), poly-(3-alkylthrophene), poly-(3-alkoxy thiophene), poly-(3-aryl thiophene), poly-(3-alkyl two thiophene), poly-(3,3 '-dialkyl group, two thiophene), poly-(3,3 '-dialkoxy, two thiophene), poly-(alkyl three thiophene), poly-(alkoxyl three thiophene), the compound of poly-(3,4-ethylene dioxythiophene) and poly-(benzo [b] thiophene).

47. method as claimed in claim 1 or 2 is characterized in that, by forming coating and/or mixture and be adjusted to when dry the average pore size of oligomer, polymer, copolymer and/or graft copolymer that higher temperature increases the conduction that will form.

48. method as claimed in claim 1 or 2 is characterized in that, adds auxiliary agent in mixture.

49. method as claimed in claim 48 is characterized in that, described auxiliary agent is that at least a surfactant, at least a protecting colloid, at least a sour agent for capturing and/or at least a complexing form agent.

50. method as claimed in claim 1 or 2, it is characterized in that, in mixture, add at least a stabilizing agent, and this stabilizing agent is selected from the water-soluble polymer based on polyvinyl alcohol, polyethylene alkyl ether, PSS, PEO, poly-alkyl sulfonic ester, poly-aromatic yl sulphonate, anion and/or cationic surfactant and tertiary amine.

51. method as claimed in claim 1 or 2 is characterized in that, by the method for decantation, filtration and/or freeze-drying, and/or by the next dry described mixture of the method for gas circulation and/or heating.

52. method as claimed in claim 51 is characterized in that, by heating comes dry described mixture under 200 ℃ the temperature being no more than.

53. method as claimed in claim 1 or 2 is characterized in that, does not remove the liquid of all amounts when drying, but keeps the content liquid in inorganic uncoated particle 0.1 to 12 % by weight.

54. method as claimed in claim 1 or 2, it is characterized in that, grind fast and/or grind inorganic particle through applying with faint effect, thereby smash so-called cake piece, aggregate and/or optional also have agglomerate and/or so that have the ability of toppling over, and/or sieve.

55. method as claimed in claim 1 or 2, it is characterized in that, at first inorganic particle is carried out decantation, filtration and/or drying, the then leachable component of extraction from conductive coating, mode are so that there is no the anion of insertion and there is no as conducting polymer carries out stable and required oxidant and be dissolved.

56. method as claimed in claim 1 or 2 is characterized in that, at the particle that is coated with conducting polymer other coatings is set.

57. method as claimed in claim 1 or 2 is characterized in that, will be inserted into coated with the particle of conducting polymer in inorganic and/or organic material or the dispersion.

58. contain just like the mixture described composition of one of claim 1 to 5 and that be used for coated particle.

59. mixture as claimed in claim 58 is characterized in that containing:

Monomer and/or the oligomer of-at least a material content in 0.1 to 30 % by weight scope,

The anion of-at least a anion-content in the scope of 0.1 to 40 % by weight,

-randomly, at least a content is at the oxidant of 0.1 to 30 % by weight,

-at least a inorganic and/or organic granular and granule content are 30 to 98 % by weight,

-all these content and randomly other, at this additive of not mentioning---but do not comprise solvent---satisfy summation 100 % by weight, and

-at least a the solvent that is suitable for raw material and/or anion or oxidant, and solvent is in the scope of 1 to 4000 % by weight, and it surpasses 100 % by weight.

60. such as claim 58 or 59 described mixtures, it is characterized in that containing:

At least a monomer and/or the oligomer of-material content in 0.5 to 18 % by weight scope,

-at least a anion and its content in 0.5 to 35 % by weight scope,

-at least a inorganic and/or organic granular and granule content are 10 to 40 % by weight.

61. such as claim 58 or 59 described mixtures, it is characterized in that, contain

At least a monomer and/or the oligomer of-material content in 1 to 25 % by weight scope,

The anion of-at least a anion-content in the scope of 1 to 35 % by weight,

-randomly, at least a oxidant, and oxygenate content is in the scope of 0.1 to 40 % by weight, and

-at least a inorganic particle and granule content are 35 to 95 % by weight.

62. contain the coating composition of conducting polymer, this conducting polymer be selected from based on pyrroles's replacement and not substituted compound oligomer and based on the replacement of thiophene and the oligomer of substituted compound not, it is characterized in that said composition contains:

The content of-at least a oligomer, polymer, copolymer, block copolymer and/or graft copolymer and conducting polymer in 0.1 to 30 % by weight scope,

The anion of-at least a anion-content in the scope of 0.1 to 40 % by weight, and it inserts in the conducting polymer at least in part,

-randomly, at least a oxidant,

-at least a particle, its content are 30 to 98 % by weight,

-all these content comprise randomly other, at this additive of not mentioning---but not comprising solvent---satisfy summation 100 % by weight, and

-randomly, at least a solvent that is suitable for product, anion and/or oxidant, and solvent is in the scope of 0.1 to 4000 % by weight, and it surpasses 100 % by weight.

63. coating composition as claimed in claim 62 is characterized in that containing the inorganic particle of 30 to 98 % by weight.

64. the inorganic and/or organic granular coated with conducting polymer, this conducting polymer be selected from based on pyrroles's replacement and not substituted compound oligomer and based on the replacement of thiophene and the oligomer of substituted compound not, it is characterized in that, conducting polymer is gone up substantially with oxidation, there be and insert anticorrosion anion and the bonding promotion property anion of certain content randomly of the activity of certain content in conductive state in conducting polymer, wherein at least a anion is selected from based on carboxylic acid, contain the hydroxyl carboxylic acid, hydroxycarboxylic acid, dicarboxylic acids, tricarboxylic acids, two and/or trisubstituted aralkyl carboxylic acid, the neighbour, between and/or the aralkyl carboxylic acid that replaces of contraposition, contain amino, nitro, SO ₃The aralkyl carboxylic acid of H-and/or OH-group, sulfonic acid, inorganic oxacid, boronic acid containing, contain mangaic acid, contain molybdic acid, phosphoric acid, phosphonic acids, fluoro silicic acid, silicic acid, contain the acid of at least a rare earth element and/or yttrium, sulfur acid contains metatitanic acid, contain vanadic acid, contain wolframic acid, contain stannic acid, contain zirconic acid, their salt, those anion of the anion of their ester and their mixtures.

65. coated with the inorganic and/or organic granular of conducting polymer, its according to claim 1 in 57 each described method make.

66. coated with the inorganic and/or organic granular of conducting polymer, it has the coating such as composition as described in the claim 62.

67. the inorganic and/or organic granular coated with conducting polymer, it has based on the coating of conducting polymer and contains the anion of titanium and/or zirconium, described conducting polymer be selected from based on pyrroles's replacement and not substituted compound oligomer and based on the replacement of thiophene and the oligomer of substituted compound not.

68. the purposes of the particle that each described method applies in 57 according to claim 1, be used for the surface of coated metal, wire rod, section bar or part to reach etch-proof purpose, be used for coating surface to avoid static electrification and/or pollution is arranged, as the electrode material in sensor, the battery, as the electrode material with catalytic performance, as being suitable for the dielectric additive of conductive coating and material, in art for electrical insulation, be used as packing material, as pigment or be used for the smooth layer of conductor.

69. the purposes such as each described particle through applying in the claim 64 to 67, be used for the surface of coated metal, wire rod, section bar or part to reach etch-proof purpose, be used for coating surface to avoid static electrification and/or pollution is arranged, as the electrode material in sensor, the battery, as the electrode material with catalytic performance, as being suitable for the dielectric additive of conductive coating and material, in art for electrical insulation, be used as packing material, as pigment or be used for the smooth layer of conductor.