[go: up one dir, main page]

DE3933901A1 - New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc. - Google Patents

New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc.

Info

Publication number
DE3933901A1
DE3933901A1 DE3933901A DE3933901A DE3933901A1 DE 3933901 A1 DE3933901 A1 DE 3933901A1 DE 3933901 A DE3933901 A DE 3933901A DE 3933901 A DE3933901 A DE 3933901A DE 3933901 A1 DE3933901 A1 DE 3933901A1
Authority
DE
Germany
Prior art keywords
benzoquinone
electrically conductive
acid
fluoride
addn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE3933901A
Other languages
German (de)
Inventor
Herbert Dr Naarmann
Klaus Prof Dr Muellen
Werner Wohlfahrt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE3933901A priority Critical patent/DE3933901A1/en
Publication of DE3933901A1 publication Critical patent/DE3933901A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Polymeric materials contg. structural units of formula (I) are new. In formula, n = 1-1000. (I) are prepd. by Diels-Alder condensn. of tetramethylene cyclooctane (II) with benzoquinone (III) to form a condensate which is then treated with FeCl3 to convert it back into a benzoquinone form, and opt. repeating the process with addn. of (II) or (III). USE/ADVANTAGE - The (I) are converted into electrically conductive materials by addn. with exclusion of moisture of an effective amt. of a cpd. chosen from AsF5, SbF5, an aromatic sulphonic acid- or nitro-cpd., an anhydrous fluorocarboxylic acid or an anhydrous mineral acid and/or iodine. The electrically conductive polycondensates are useful antistatic additives for polymers, for prodn. of solar cells, for conversion and fixing of radiation, for prodn. of electric and magnetic switches, and for prodn. of electrodes. Addn. of a strong Lewis acid to the polycondensate gives p-conductors.

Description

Die Erfindung betrifft polymere Stoffe, die elektrisch leitfähige Polykondensate mit einer elektrischen Leitfähigkeit von mehr als 10-2 S/cm herzustellen erlauben und deren Verwendung in der Elektroindustrie sowie zur antistatischen Ausrüstung von Kunststoffen.The invention relates to polymeric substances which allow the production of electrically conductive polycondensates with an electrical conductivity of more than 10 -2 S / cm and their use in the electrical industry and for the antistatic finishing of plastics.

Es ist bereits bekannt, Polykondensate durch oxidative Kupplung nach Macromolecular Syntheses Collective Vol. 1, Seiten 109 bis 110, (1979), Verlag John Wiley & Sons und Naturwissenschaften 56, Seiten 308 bis 313, (1969) herzustellen. Außerdem ist die Herstellung von Polykondensaten durch stufenweise Polykondensation nach R. Gehm und W. Kern aus Makromolekulare Chemie 7 (1951) Seiten 46 bis 61 bekannt, wobei besonders einheitliche, p-verkettete methylsubstituierte Benzolderivate erhalten werden, die nicht zusätzlich durch ortho- oder meta-verknüpfte Polymere verunreinigt sind. Ebenfalls bekannt sind Polykondensate, die z. B. durch Tetrachlorbenzochinon mit Na₂S erhalten werden und in dem DE-PS 1 19 719 beschrieben sind.It is already known to post polycondensates by oxidative coupling Macromolecular Syntheses Collective Vol. 1, pages 109 to 110, (1979), John Wiley & Sons Verlag und Naturwissenschaften 56, pages 308 to 313, (1969). In addition, the production of polycondensates through gradual polycondensation according to R. Gehm and W. Kern from Macromolecular Chemistry 7 (1951) pages 46 to 61, where particularly uniform, p-linked methyl-substituted benzene derivatives are obtained that are not additionally linked by ortho- or meta-linked Polymers are contaminated. Also known are polycondensates e.g. B. obtained by tetrachlorobenzoquinone with Na₂S and in which DE-PS 1 19 719 are described.

Der Erfindung lag die Aufgabe zugrunde, Polykondensate zu schaffen, die durch an sich bekannte Zusätze in elektrisch leitfähige Polymere mit elektrischen Leitfähigkeiten größer als 10-2 S/cm umzuwandeln sind.The invention had for its object to provide polycondensates which can be converted into electrically conductive polymers with electrical conductivities greater than 10 -2 S / cm by additives known per se.

Die Aufgabe wird gelöst durch polymere Stoffe aus Einheiten der allgemeinen Formel IThe task is solved by polymeric substances from units of general formula I.

wobei n eine ganze Zahl zwischen 1 und etwa 1000 bedeutet. Solche Stoffe werden erhalten, wenn man Tetramethylencyclooctan (II) mit Benzchinon nach Diels-Adler kondensiert (III), das Kondensat mittels vorzugsweise FeCl₃ zu einer wiederum eine Benzochinonstruktur aufweisenden Verbindung (IV) kondensiert und ggf. diese Verfahrensschritte unter Zugabe von Tetramethylencyclooctan und/oder Benzochinon wiederholt.where n is an integer between 1 and about 1000. Such substances are obtained if one condenses tetramethylene cyclooctane (II) with benzoquinone according to Diels-Adler (III), the condensate is preferably condensed by means of FeCl₃ to a compound (IV) again having a benzoquinone structure and, if appropriate, these process steps with the addition of tetramethylene cyclooctane and / or Repeated benzoquinone.

Aus diesen Stoffen erhält man elektrisch leitfähige Polymere, wenn man zu den Polymeren der Struktur I eine Verbindung zusetzt, ausgewählt aus Arsen(V)fluorid, Antimon(V)fluorid, einer aromatischen Sulfonsäure oder Nitroverbindung, einer wasserfreien Fluorcarbonsäure oder einer wasserfreien Mineralsäure und/oder Jod.Electrically conductive polymers can be obtained from these substances if one goes to adding a compound to the polymers of structure I selected from  Arsenic (V) fluoride, antimony (V) fluoride, an aromatic sulfonic acid or Nitro compound, an anhydrous fluorocarboxylic acid or anhydrous mineral acid and / or iodine.

Die elektrischen Leitfähigkeitswerte werden in S/cm bei 30°C gemessen, die Messung selbst erfolgt nach der Methode von F. Beck, Berichte Bunsengesellschaft, Physikalische Chemie 68, Seiten 558 bis 567 (1964). Die elektrischen Leitfähigkeitswerte der erfindungsgemäßen leitfähigen Polykondensate sind größer als 10-2 S/cm.The electrical conductivity values are measured in S / cm at 30 ° C, the measurement itself is carried out according to the method of F. Beck, reports Bunsengesellschaft, Physikalische Chemie 68, pages 558 to 567 (1964). The electrical conductivity values of the conductive polycondensates according to the invention are greater than 10 -2 S / cm.

Erfindungsgemäß wird einem Polykondensat I unter Anschluß von Wasserfeuchtigkeit 0,5 bis 15 Gew.-%, bezogen auf das Polykondensat, einer oxidierenden Lewis-Säure, wie Antimon- oder Arsenpentafluorid, deren NO⁺- oder NO₂⁺-Salzen, ferner Nitroaromaten wie Trinitrophenol, Trinitrosulfonsäure, und/oder Fluorderivate wie CF₃-COOH oder auch Säuren wie Schwefelsäure, Salpetersäure oder Überchlorsäure zugesetzt und weiterhin, aus wirtschaftlichen oder mechanischen Gründen ein anderes Polymeres, wenn erforderlich.According to the invention, a polycondensate I with the connection of Water moisture 0.5 to 15 wt .-%, based on the polycondensate, one oxidizing Lewis acid, such as antimony or arsenic pentafluoride, the NO⁺- or NO₂⁺ salts, also nitroaromatics such as trinitrophenol, Trinitrosulfonic acid, and / or fluorine derivatives such as CF₃-COOH or acids such as sulfuric acid, nitric acid or overchloric acid and further, another for economic or mechanical reasons Polymer if required.

Das Einarbeiten des Zusatzes erfolgt unter Ausschluß von Feuchtigkeit (Wasser), es wird vorzugsweise unter Argonatmosphäre gearbeitet. Vorzugsweise wird eine Hilfsflüssigkeit wie Tetrahydrofuran, Nitromethan, CCl₄ oder CHCl₃, jeweils im Molverhältnis 1 : 1 bis 1 : 50 eingesetzt, die nach dem Einarbeiten bei einer Temperatur unter 30°C im Vakuum abgezogen wird. Das Molverhältnis ist bevorzugt 1 : 2 bis 1 : 3.The addition is carried out with the exclusion of moisture (Water), it is preferably carried out under an argon atmosphere. An auxiliary liquid such as tetrahydrofuran, nitromethane, CCl₄ or CHCl₃, each in a molar ratio of 1: 1 to 1:50, which after incorporation at a temperature below 30 ° C in a vacuum becomes. The molar ratio is preferably 1: 2 to 1: 3.

Durch den genannten Zusatz kann die elektrische Leitfähigkeit um einige Größenordnungen gesteigert werden. Die Ausgangsleitfähigkeit des Polykondensates beträgt ca. 10-10 bis 10-8 S/cm. Das nach der stufenweisen Kondensation hergestellte Polykondensat hat eine Ausgangsleitfähigkeit von weniger als 10-6 S/cm, liefert aber nach der Zugabe des erfindungsgemäßen Zusatzes ebenfalls eine Leitfähigkeit von mindestens 10-2 S/cm.With the addition mentioned, the electrical conductivity can be increased by a few orders of magnitude. The output conductivity of the polycondensate is approx. 10 -10 to 10 -8 S / cm. The polycondensate produced after the stepwise condensation has an initial conductivity of less than 10 -6 S / cm, but also delivers a conductivity of at least 10 -2 S / cm after the addition of the additive according to the invention.

Die erfindungsgemäßen elektrisch leitfähigen Polykondensate I sind zur antistatischen Ausrüstung von Kunststoffen, zur Herstellung von Sonnenzellen, zur Umwandlung und Fixierung von Strahlung sowie zur Herstellung elektrischer und magnetischer Schalter sowie für Elektroden geeignet. Durch den Zusatz einer starken Lewis-Säure zum Polykondensat entstehen sogenannte p-Leiter.The electrically conductive polycondensates I according to the invention are for antistatic finishing of plastics, for the production of Solar cells, for converting and fixing radiation as well as for Manufacture of electrical and magnetic switches and for electrodes suitable. By adding a strong Lewis acid to the polycondensate so-called p-conductors arise.

Die in den folgenden Beispielen genannten Teile sind Gewichtsteile. Die Bestimmung der Gliederzahl n (Kettenlänge der Polykondensate) erfolgt durch Endgruppenanalyse, d. h. durch IR-Bestimmung des Verhältnisses der monofunktionellen Endgruppen zur difunktionellen Mittelgruppe.The parts mentioned in the following examples are parts by weight. The number of links n (chain length of the polycondensates) is determined by end group analysis, ie by IR determination of the ratio of the monofunctional end groups to the difunctional middle group.

Beispiel 1 (vgl. hierzu Schema)Example 1 (see diagram)

Tetramethylencyclooctan (1) 0,1 M entspr. 15 Gewichtsteile werden mit 0,1 M entspr. 11 Gewichtsteilen 1,45 Benzochinon versetzt und in 250 Gewichtsteilen Tetrachlorkohlenstoff 5 Stunden bei Raumtemperatur gerührt; man erhält in einer Ausbeute von über 90% das Rohprodukt (2) das zu 3 tautomerisiert. Dann wird Tetrachlorkohlenstoff bei einem Druck von 50 mbar bei Raumtemperatur abgezogen, das Rohprodukt (2) mit 5 Gewichtsteilen SiO₂ versetzt und dann in 500 Gewichtsteilen Hexan/Essigester Verhältnis 3 : 1 3 Stunden bei Raumtemperatur gerührt. Hierbei entsteht (3). Das Lösungsmittel wird wie oben abgezogen und das Rohprodukt in 200 Gewichtsteilen Ethanol mit 16 Gewichtsteilen FeCl₃ versetzt und 2 Stunden bei Raumtemperatur gerührt. Nach dem Umkristallisieren aus Aceton erhält man mit 80% Ausbeute das Chinondien (4).Tetramethylenecyclooctane (1) 0.1 M corresponds to 15 parts by weight 0.1 M corresponds to 11 parts by weight of 1.45 benzoquinone and in 250 parts by weight of carbon tetrachloride for 5 hours at room temperature touched; the crude product (2) is obtained in a yield of over 90% tautomerized to 3. Then carbon tetrachloride at a pressure of Subtracted 50 mbar at room temperature, the crude product (2) with 5 parts by weight SiO₂ added and then in 500 parts by weight of hexane / ethyl acetate Ratio 3: 1 stirred for 3 hours at room temperature. This creates (3). The solvent is removed as above and the crude product in 200 parts by weight of ethanol with 16 parts by weight of FeCl₃ and Stirred for 2 hours at room temperature. After recrystallization Acetone gives quinondiene (4) in 80% yield.

Werden 10 Gewichtsteile (4) in 100 Gewichtsteile ClCl₄ 100 Stunden bei Raumtemperatur gerührt, so fallen 1,2 Gewichtsteile eines unlöslichen Polymeren an, da aufgrund der C¹³ NMR Spektren dem erfindungsgemäßen Zielprodukt (I) entspricht. Analoge Produkte entstehen, wenn als 1,4-chinoide Systeme Systeme Tetracyanobenzochinon, Tetracyanmethylenbenzochinon bzw. Diaminobenzochinon verwendet werden.Are 10 parts by weight (4) in 100 parts by weight of ClCl₄ for 100 hours Stirred at room temperature, 1.2 parts by weight of an insoluble fall Polymers on because of the C¹³ NMR spectra of the invention Target product (I) corresponds. Analog products arise when as 1,4-quinoid systems, systems tetracyanobenzoquinone, tetracyanethylene benzoquinone or diaminobenzoquinone can be used.

Das Isolieren des nach Beispiel 1 hergestellten Polymeren wird in den folgenden Beispielen beschrieben.The isolation of the polymer prepared according to Example 1 is in the following examples.

Beispiel 2 bis 5 Examples 2 to 5

In einer 1%igen Lösung von Tetrabutylammoniumperchlorid in Acetonitril als Elektrolyt werden an Platinelektroden 100 mg (I) im Platin-Netz als Anode, mit einer Stromdichte von 2 mA/cm² 60 min beladen.In a 1% solution of tetrabutylammonium perchloride in acetonitrile 100 mg (I) in the platinum network are used as the electrolyte on platinum electrodes Anode, loaded with a current density of 2 mA / cm² for 60 min.

Schema zu Beispiel 1Scheme of example 1

Claims (2)

1. Polymerer Stoff, enthaltend Einheiten der allgemeinen Formel I wobei n eine ganze Zahl zwischen 1 und etwa 1000 bedeutet, wie es erhalten wird, wenn man Tetramethylencyclooctan (II) mit Benzochinon nach Diels-Alder kondensiert (III), das Kondensat mittels vorzugsweise FeCl₃ zu einer wiederum eine Benzochinonstruktur aufweisenden Verbindung (IV) kondensiert und ggf. diese Verfahrensschritte unter Zugabe von Tetramethylencyclooctan und/oder Benzochinon wiederholt.1. Polymeric material containing units of the general formula I where n is an integer between 1 and about 1000, as is obtained if one condenses tetramethylene cyclooctane (II) with benzoquinone according to Diels-Alder (III), the condensate by means of preferably FeCl₃ to a compound (IV) again having a benzoquinone structure and, if necessary, these process steps are repeated with the addition of tetramethylene cyclooctane and / or benzoquinone. 2. Elektrisch leitfähiger polymerer Stoff, enthaltend einen polymeren Stoff mit Einheiten der allgemeinen Formel (I) gemäß Anspruch 1, mindestens einen weiteren polymeren Stoff und - unter Wasserausschluß zugesetzt bzw. eingearbeitet - eine wirksame Menge einer Verbindung ausgewählt aus der Gruppe, die umfaßt: Arsen(V)fluorid, Antimon(V)fluorid, eine aromatische Sulfonsäure- oder Nitroverbindung, eine wasserfreie Fluorcarbonsäure oder eine wasserfreie Mineralsäure und/oder Jod.2. Electrically conductive polymeric material containing a polymeric Substance with units of the general formula (I) according to Claim 1, at least one other polymeric substance and - with exclusion of water added or incorporated - an effective amount of a compound selected from the group comprising: arsenic (V) fluoride, Antimony (V) fluoride, an aromatic sulfonic acid or nitro compound, an anhydrous fluorocarboxylic acid or an anhydrous mineral acid and / or iodine.
DE3933901A 1988-10-14 1989-10-11 New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc. Withdrawn DE3933901A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE3933901A DE3933901A1 (en) 1988-10-14 1989-10-11 New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3835029 1988-10-14
DE3933901A DE3933901A1 (en) 1988-10-14 1989-10-11 New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc.

Publications (1)

Publication Number Publication Date
DE3933901A1 true DE3933901A1 (en) 1990-04-19

Family

ID=25873243

Family Applications (1)

Application Number Title Priority Date Filing Date
DE3933901A Withdrawn DE3933901A1 (en) 1988-10-14 1989-10-11 New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc.

Country Status (1)

Country Link
DE (1) DE3933901A1 (en)

Similar Documents

Publication Publication Date Title
EP0031967B1 (en) Process for preparing electrically conductive poly-aromatic polymers, their use in electrical engineering and as antistatic additives for plastics
EP0035713B1 (en) Process for preparing electrically conductive heteropolyphenylenes and their use in electrotechnics and in the antistatic equipment of synthetics
EP0129698B1 (en) Process for the preparation of polypyrroles, and film-like products obtained by such a process
EP0035715B1 (en) Process for preparing electrically conductive heteropolyaromatic substances and their use in electrotechnics and in the antistatic equipment of synthetics
EP0098988B1 (en) Electrically conductive copolymers of pyrroles, and process for their preparation
EP0045366B1 (en) Process for preparing electrically conductive soluble heteropolyphenylenes, and their use
DE3104408A1 (en) PROCESSES FOR THE MANUFACTURE OF STABILIZED CONDUCTIVE POLYMER SYSTEMS AND THEIR USE IN ELECTRICAL ENGINEERING AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
DE3318856A1 (en) METHOD FOR PRODUCING POLY (HETEROAROMATS) AND FILM-SHAPED PRODUCTS OBTAINED BY THIS METHOD
DE3105948A1 (en) METHOD FOR THE PRODUCTION OF STABLE ELECTRICALLY CONDUCTIVE POLYMERIC SYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
DE3027529A1 (en) METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYMERIC SYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
EP0047903B1 (en) Process for the manufacture of electrically conductive polyaromates and their use in electrical engineering and in the antistatic finishing of plastics
EP0023596A1 (en) Process for preparing electrically conductive polyphenylenes and their use in electrical engineering and in rendering plastics antistatic
DE3933901A1 (en) New polymers from tetra;methylene cyclo-octane and benzoquinone - form electrically conductive material with arsenic penta:fluoride and/or iodine etc.
EP0037924B1 (en) Process for preparing electrically conducting polycondensates and their use in electrical engineering and as antistatic additives for plastics
EP0039829B1 (en) Process for preparing electroconductive soluble heteropolyphenylenes and their use in electrotechnics and for the antistatic equipment of synthetic materials
EP0045852B1 (en) Process for producing electrically conductive polymer systems, and their use in electrotechnics and in the antistatic treatment of synthetic products
EP0023595A1 (en) Process for preparing electrically conductive polyphenylenes and their use in electrical engineering and in rendering plastics antistatic
DE2948454A1 (en) METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYAROMATS AND THE USE THEREOF IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
EP0100509B1 (en) Process for the manufacture of electrically conductive polyarylene compounds with electron-accepting side groups and their use in the electrotechnique and for rendering synthetic materials antistatic
DE3210546A1 (en) METHOD FOR PRODUCING ELECTRICALLY CONDUCTIVE OLIGOPHENYLE, THE PRODUCTS PRODUCED BY THE METHOD AND THE USE THEREOF
DE3026328A1 (en) METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYMERIC SYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
DE3005299A1 (en) METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYAROMATS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS
DE3417942A1 (en) Process for preparing thiophene polymers
DE3005300A1 (en) METHOD FOR THE PRODUCTION OF ELECTRICALLY CONDUCTIVE POLYAROMATS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS

Legal Events

Date Code Title Description
8139 Disposal/non-payment of the annual fee