EP0236367B1 - Verfahren zur herstellung eines elektrisch leitfähigen polymers in der form eines formbaren pulvers - Google Patents

Verfahren zur herstellung eines elektrisch leitfähigen polymers in der form eines formbaren pulvers Download PDF

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Publication number
EP0236367B1
EP0236367B1 EP19860905179 EP86905179A EP0236367B1 EP 0236367 B1 EP0236367 B1 EP 0236367B1 EP 19860905179 EP19860905179 EP 19860905179 EP 86905179 A EP86905179 A EP 86905179A EP 0236367 B1 EP0236367 B1 EP 0236367B1
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EP
European Patent Office
Prior art keywords
particles
filler
polymer
electroconductive
electroconductive polymer
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Expired - Lifetime
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EP19860905179
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English (en)
French (fr)
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EP0236367A1 (de
Inventor
Günter Bellmann
Van-Tao Nguyen
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Battelle Memorial Institute Inc
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Battelle Memorial Institute Inc
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Priority claimed from CH385885A external-priority patent/CH666364A5/fr
Priority claimed from CH385985A external-priority patent/CH666976A5/fr
Application filed by Battelle Memorial Institute Inc filed Critical Battelle Memorial Institute Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes

Definitions

  • the subject of the present invention is a process for the preparation of an electrically conductive organic polymer in the form of a powder which may contain mineral or organic fillers, this powder being compactable under pressure and moldable in the form of electrically conductive articles.
  • This polymer is obtained by chemical oxidation of one or more pentacyclic hetero-compounds such as thiophene, selenophene, furan, pyrrole, thiazole, oxazole or pyrazole in the presence of a doping agent.
  • the powders thus obtained have a conductivity of between 10 -2 and 50 S / cm that is to say, a resistivity 100-2x10 -2 Ohm. cm.
  • Document GB-A-2,133,022 describes the production of electroconductive polymers with a negative temperature coefficient by treatment of dimethylpyrroles with oxidizing salts such as perchlorate or ferric chloride in an aqueous medium or with chlorine gas in an acetonitrile medium.
  • oxidizing salts such as perchlorate or ferric chloride in an aqueous medium or with chlorine gas in an acetonitrile medium.
  • the polymers thus obtained have a low conductivity (resistivity greater than 10 Ohm. Cm).
  • electroconductive polymers in the form of films or in the form of products for impregnating porous materials has also been disclosed.
  • the document DE-A-33 21 281 mentions the impregnation of insulating materials such as cellulose fibers, papers, porcelain or epoxy resins with an aqueous solution of a salt of a metal of varying degree of oxidation, this metal being at a high oxidation level, in particular FeCl 3 , La (S0 4 ) 2 , K 3 Fe (CN) 6 , Cr0 3 , preferably in the presence of an acid, then the addition in gaseous or liquid form of a pyrrolic compound in an alkolic solution or in a nitrile.
  • the resistivity of the products obtained is however not less than 65 Ohm. cm (see example 1).
  • electroconductive polymers can be obtained by homogeneous polymerization of aromatic heterocycles, for example in an anhydrous organic solvent , and using, both as an oxidant and as a dopant, Lewis acids with oxidizing capacity.
  • the halides and other salts and complexes of mineral and organic acids of metals having the character of Lewis acids in an oxidation state of a higher level and capable of passing, by reaction with an aromatic heterocycle, at a lower oxidation level by polymerizing oxidation of said heterocycle, and, simultaneously, to form doping anions of the polymer thus obtained.
  • Lewis acids the following bodies may be mentioned: FeCl 3 , FeBr 3 , CuCl 2 , BiCl s , AsCl s , SbCl 5 , SbF S , MnCI 3 and others.
  • salts having only a weak character of a Lewis acid such as, for example, Fe2 (SO 4 ) 3 and Fe (NO 3 ) 3 may also be suitable.
  • the principle of the reaction according to the invention can be illustrated by the following diagram relating to the reaction of pyrrole (PYR) with FeCl 3 , it being understood that similar criteria are applicable to the other cases encompassed by the invention: with x being between 2 and 12.
  • the polymer obtained has a charge + for x pyrrole groups; the value of x being between 2 and 12 and preferably 3 and 10.
  • the important factor, underlined by this diagram, is however the fact that the salt or the Lewis acid used functions both as an oxidative polymerization agent pyrrole and as a doping agent which makes it possible to achieve relatively high conductivities without the addition of additional dopant.
  • solvents having an ether function such as ethyl, propyl or butyl ethers, "glymes", in particular monoglyme (ethylene glycol dimethyl ether), dioxane, THF, esters such as ethyl acetate and propionate, nitromethane, nitrobenzene, chlorinated solvents such as CCI 4 , chlorobenzene, ethyl chloride, methyl chloride , ethylene or methylene chloride. From a practical point of view, the implementation of the method of the invention is very simple.
  • a solution of Lewis acid in the chosen organic solvent is prepared and, on the other hand, a solution of pyrrole or another heterocycle in this solvent or another solvent and the procedure is carried out. mixing of the two solutions at ordinary temperature or with cooling to moderate the reaction when it is lively. It is also possible to add the heterocyclic compound when it is liquid undiluted by a solvent.
  • relative amounts of reagents are preferably used in accordance with the stoichiometry of the reaction; for example, in the reaction schematized above, yields close to the theory will be obtained by using 3 moles of FeCl 3 per mole of pyrrole; however, there is no need to strictly observe these conditions and a similar polymer will be obtained (albeit with a lower yield) using, for example, 1 mole of FeCl 3 per mole of pyrrole.
  • the precipitation of the desired product is rapidly observed, in the form of a pulverulent mass which may be fibrous.
  • This mass can be collected by filtration and spinning and dried by the usual means.
  • the mass is then compacted in an appropriate form and molded according to the shape of the desired object.
  • the present electroconductive polymer can be used to obtain, in the presence of an inorganic or organic pulverulent filler, a pulverulent substance making it possible to manufacture, by the usual methods of compacting and pressure molding or by sintering, compact electroactive articles.
  • electroactive we refer to electroconductive materials capable of being subjected to reversible electro-oxidation-reduction processes involving a variation in the rate of electrical charge (doping) without the participation of metals or metal ions.
  • polyacetylene As an example of such a known material, mention may be made of polyacetylene. This polymer is normally a semiconductor but, by oxidizing or reducing doping, its conductivity can be varied by a factor of the order of 10 12 (see Chemical & Engineering News, January 26, 1981, pages 39 ⁇ 40). Such a polymer can be used in particular for the manufacture of accumulators and plastic batteries (see Research, No. 126, October 1981, vol.
  • electroconductive powder thus obtained from the electroconductive polymer of the invention and a charge lends itself to all the usual applications involving the use of metallic powders such as electroconductive paints, electroconductive articles in the electrical industry, electrodes in the chemical industry.
  • the pulverulent filler it is preferred to use carbon black or mineral particles.
  • the particle size of the filler is preferably from 0.01 nm to 1 ⁇ m, more preferably from 5 to 1000 nm.
  • carbon black particles it is possible to use the various types of carbon black available on the market and whose dimensions are of the order of 0.001 to 1 ⁇ m with a specific surface of 1 mg to 100 mg / m 2 . Such carbon blacks are described in document EP-A-98,338.
  • mineral particles all mineral materials in fine powder such as, for example, those containing silica, alumina or other metal oxides can be used.
  • submicron particles such as precipitated or pyrogenic silica are used, such dimensional requirements however not being critical and can be overridden if desired.
  • a description of such mineral materials can be found in the document.
  • Other silicate particles such as talc, bentonite, vollastonite, montmorillonite, may also be suitable.
  • the amount by weight of electroconductive polymer relative to the. particulate matter in the present powder is preferably between about 10 and 100% depending on the desired properties.
  • the thickness of the polymer layer which is deposited on the particles during the polymerization can be of the order of a few Angstroms to several micrometers.
  • the resistivity of the powder (as measured on an article made by compression) generally varies between 10000 and 10- 2 ohm. cm depending on the rate of fixation of the electroconductive polymer, and according to the method of preparation.
  • the present pulverulent substance it is possible to proceed in various ways including the simultaneous bringing into contact of the particulate filler, the polymerization reagent and the monomer to be polymerized, or the impregnation of the filler with said reagent and, subsequently, the in the presence of the charge thus treated with said monomer in liquid (solution) or vapor phase.
  • the procedure is, for example, in organic solution using one of the aforementioned reagents simultaneously playing the role of polymerization catalyst and dopant, in particular FeCl 3 .
  • the present powder is subjected, in a mold, to a pressure sufficient to promote the adhesion between them of the electroconductive particles, this operation being able to take place, according to cases, in the presence or absence of a usual binder.
  • this filler can be dispersed in a solution of a polymer or in a liquid monomer and then proceed to the polymerization of this monomer. It will be noted that one of the significant advantages of the present powder is its excellent compatibility (good wettability) with most organic polymers, which clearly distinguishes it from the electroconductive powders of the prior art.
  • the volume electrical conductivity measured on a pellet obtained by compacting under a pressure of 15 t / cm 2 is 28 Ohm -1 cm -1 , that is to say 3.5 ⁇ 10 -2 Ohm. cm.
  • Example 3 Comparative example in an aqueous medium
  • the volume electrical conductivity, measured on a pellet obtained by compacting under a pressure of 15 t / cm 2 is 2.10 hm -1 cm -1 , ie a factor of 10 less than the sample obtained in an anhydrous medium (example 1) .
  • Example 2 The procedure is as in Example 1 but using 22.43 g (0.075 mole) of SbCl 5 in 150 ml of CCI 4 . The precipitate is washed with CCI 4 and dried under vacuum. 10.8 g of powder are obtained, the volume conductivity of which after compacting is 3.6 ⁇ 10 ⁇ 3 Ohm ⁇ 1 cm ⁇ 1 .
  • Example 2 The procedure is as in Example 1 but using 16.25 g (0.075 mole) of SbF 5 in 150 ml of CCI 4 . The precipitate is washed with CCI 4 and dried under vacuum. 12.6 g of powder are obtained, the volume conductivity of which after compacting is 0.28 Ohm -1 cm -1.
  • the carbon black dispersion thus obtained was treated with 16.22 g of anhydrous FeC) 3 , then with 3.35 g of pyrrole. After a few hours of stirring, the dispersion was filtered off, washed and dried; yield 5.12 g.
  • the volume conductivity of the black powder thus obtained was 13.27 Siemens / cm.
  • Example 11 The procedure was as in Example 11 but using 10 g of silicas of various types and making vary, on the one hand, the amount of FeCl 3 adsorbed on the silica and, on the other hand, the contact time in vapor phase with the pyrrole.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Claims (13)

1. Verfahren zur Herstellung eines elektrisch leitfähigen Polymeren in Form eines unter Druck verdichtbaren und verformbaren Pulvers, das durch chemische Oxidation von aromatischen heterocyclischen Verbindungen in Gegenwart einer Lewissäure erhalten ist, dadurch gekennzeichnet, daß man in einem wasserfreien Reaktionsmedium arbeitet, daß man als Lewissäure ein Salz oder einen Komplex eines mehrwertigen Metalls bei einem höheren Oxidationsgrad verwendet, der während der Reaktion in einen niedrigeren Oxidationsgrad übergeht, und daß man ohne Eintrag eines zusätzlichen Dotierstoffes oder Oxidationsmittels arbeitet.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Reaktionsmedium ein oder mehrere Lösungsmittel verwendet, die aus der Gruppe Ether, Dioxan, Monoglyme (Ethylenglykoldimethylether), THF, Ethylacetat, Nitromethan, Nitrobenzol, CCI4, Ethylchlorid und Methylchlorid ausgewählt sind.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Lewissäure mindestens eine der folgenden Verbindungen verwendet: FeCl3, FeBr3, AsCls, SbCls, CuCl2, BiCl5, SbFs.
4. Verfahren zum Unwandeln des gemäß Patentanspruch 1 erhaltenen elektrisch leitfähigen Polymeren in eine elektrisch leitende pulverförmige Substanz, die sich durch Verdichten und Verformen zur Herstellung von elektroaktiven Erzeugnissen eignet, dadurch gekennzeichnet, daß man dem Polymeren Mineralteilchen oder Ruß zusetzt.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das elektrisch leitfähige Polymere aus der Gruppe der Polypyrrole, der Polythiophene und der Polyfurane ausgewählt ist.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Gewichtsverhältnis des elektrisch leitfähigen Polymeren zu den Teilchen 0,1 bis 10 beträgt.
7. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Leitfähigkeit der Substanz nach der Verdichtung 10-4 bis 100 S/cm (p=10 +4 bis 10-2 Ohm. cm) beträgt.
8. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Teilchen der Substanz zwischen 5 nm und 1000 nm schwanken.
9. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man einen Eintrag der Ruß- oder Mineralstoffe einerseits der Gegenwart der Reaktionsteilnehmer der Polymerisation und der Dotierung der monomeren heterocyclischen Verbindungen aussetzt und andererseits eines oder mehrerer dieser Monomeren, welch letztere dann unter Bildung des elektrisch leitfähigen Polymeren polymerisieren, auf die Oberfläche der Teilchen des genannten Eintrags gibt.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man zunächst den FeCl3-Mineraleintrag tränkt, wobei dieser Reaktionsteilnehmer die Rolle des Polymerisationsmittels und des Dotierstoffes spielt, wonach man den so getränkten Mineralstoffeintrag der Gegenwart des Monomeren aussetzt.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man in einer wasserfreien Reaktionsflüssigkeit oder in der Gasphase arbeitet.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß man den getränkten FeCl3-Eintrag der Gegenwart von Pyrroldampf bei unteratmosphärischem Druck aussetzt.
13. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß man bei Umgebungstemperatur arbeitet.
EP19860905179 1985-09-06 1986-09-01 Verfahren zur herstellung eines elektrisch leitfähigen polymers in der form eines formbaren pulvers Expired - Lifetime EP0236367B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH3859/85 1985-09-06
CH385885A CH666364A5 (fr) 1985-09-06 1985-09-06 Substance electroconductrice en poudre pour la fabrication par compactage d'articles electroactifs.
CH385985A CH666976A5 (fr) 1985-09-06 1985-09-06 Procede de preparation d'un polymere electroconducteur en poudre compactable et moulable.
CH3858/85 1985-09-06

Publications (2)

Publication Number Publication Date
EP0236367A1 EP0236367A1 (de) 1987-09-16
EP0236367B1 true EP0236367B1 (de) 1990-08-01

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EP19860905179 Expired - Lifetime EP0236367B1 (de) 1985-09-06 1986-09-01 Verfahren zur herstellung eines elektrisch leitfähigen polymers in der form eines formbaren pulvers

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EP (1) EP0236367B1 (de)
DE (1) DE3673155D1 (de)
WO (1) WO1987001504A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3729566A1 (de) * 1987-09-04 1989-03-16 Zipperling Kessler & Co Intrinsisch leitfaehiges polymer in form eines dispergierbaren feststoffes, dessen herstellung und dessen verwendung
US5106690A (en) * 1989-10-16 1992-04-21 Kerr-Mcgee Chemical Corporation Method for producing electrically conductive pigmentary composites
WO1998039952A1 (en) * 1997-03-04 1998-09-11 C-Technologies Llc Apparatus and method for monitoring, controlling, displaying and dissipating an electrostatic charge

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Publication number Priority date Publication date Assignee Title
JPS584401B2 (ja) * 1977-02-16 1983-01-26 京セラミタ株式会社 固体導電剤
DE3321281A1 (de) * 1982-06-22 1983-12-22 ASEA AB, 72183 Västerås Verfahren zur erhoehung der elektrischen leitfaehigkeit impraegnierbarer materialien
DE3307954A1 (de) * 1983-03-07 1984-09-13 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von elektrisch leitfaehigen feinteiligen pyrrolpoylmerisaten

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EP0236367A1 (de) 1987-09-16
WO1987001504A1 (fr) 1987-03-12

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