DE3226780A1 - Process for the preparation of electrically conductive polyaromatics and their use in electrical engineering and for the antistatic finishing of plastics - Google Patents

Process for the preparation of electrically conductive polyaromatics and their use in electrical engineering and for the antistatic finishing of plastics

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Publication number
DE3226780A1
DE3226780A1 DE19823226780 DE3226780A DE3226780A1 DE 3226780 A1 DE3226780 A1 DE 3226780A1 DE 19823226780 DE19823226780 DE 19823226780 DE 3226780 A DE3226780 A DE 3226780A DE 3226780 A1 DE3226780 A1 DE 3226780A1
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Prior art keywords
polyaromatics
electrically conductive
electrical
plastics
preparation
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DE19823226780
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German (de)
Inventor
Volker Dipl.-Chem.Dr. 6700 Ludwigshafen Muench
Herbert Dipl.-Chem.Dr. 6719 Wattenheim Naarmann
Peter Dipl.-Chem.Dr. 6908 Wiesloch Neumann
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BASF SE
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BASF SE
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Priority to DE19823226780 priority Critical patent/DE3226780A1/en
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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
    • H01B1/06—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
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hybrid Cells (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a process for the preparation of electrically conductive polyaromatics; in which the polyaromatics are treated with 0.5 to 5% by weight of a strong Lewis acid having pks values from -10 to +4, with the exclusion of aqueous moisture and of oxygen, and in which the polyaromatics used are compounds having conjugated pi -systems in which at least two polyene chains of the formula (I) and (II): <IMAGE> in which n = 1 to 100 and m = 0 to 50 run in parallel. Suitable polyaromatics are quarterylene, quinquerylene, sesquicylene or dianthracene. The electrically conductive polyaromatics can be used in electrical engineering for the production of solar cells, for the conversion and fixation of radiation, for the preparation of electrical and magnetic switches and electrical memories and for the antistatic finishing of plastics.

Description

verfahren zur Herstellung elektrisch leitfähiger Poly-process for the production of electrically conductive poly-

aromaten und deren Verwendung in der Elektrotechnik und zur antistatischen Ausrüstung von Kunststoffen Die Erfindung betrifft ein Verfahren zur Herstellung von elektrisch leitfähigen Polyaromaten mit elektrischen Leitfähigkeitswerten größer als 10-1 S/cm, wobei den Polyaromaten unter Ausschluß von Wasserfeuchtigkeit und von Sauerstoff 0,5 bis 5 Gew.-%, bezogen auf den eingesetzten Polyaromaten, einer starken Lewis-Säure mst pks-Werten von -10 bis +4 zugesetzt wird.aromatics and their use in electrical engineering and for antistatic Finishing of plastics The invention relates to a method for production of electrically conductive polyaromatics with electrical conductivity values greater than 10-1 S / cm, the polyaromatics to the exclusion of water moisture and of oxygen 0.5 to 5 wt .-%, based on the polyaromatic used, one strong Lewis acid with pks values of -10 to +4 is added.

3ei derartigen Verfahren sind Zusätze erforderlich, um die elektrische Leitfähigkeit von Polyaromaten zu erhöhen.Such processes require additives to improve the electrical properties To increase the conductivity of polyaromatics.

Es ist bereits aus der DE-OS 30 05 299 bekannt, Polyaromaten, die nicht linear augebaut sind, sondern sog. polycyclische aromatische Kohlenwasserstoffe sind und anellierte 3enzolRerne enthalten, wie Tetraphenylen, Dianthren, Peropyren, Anthracen, Pluoranthen und ähnlichen Verbindungen durch Zusatz einer starken Lewis-Säure mit ?ks-wvrten von -10 bis +4 unter Ausschluß von Wasserfeuchtigkeit und Sauerstoff eine erhöhte elektrische Leitfähigkeit zu verleihen.It is already known from DE-OS 30 05 299, polyaromatics, the are not linear, but so-called polycyclic aromatic hydrocarbons and contain fused 3enzene rings, such as tetraphenylene, dianthrene, peropyrene, Anthracene, fluoranthene and similar compounds by adding a strong Lewis acid with? ks-words from -10 to +4 with exclusion of water moisture and oxygen to give an increased electrical conductivity.

Die nach bekannten Verfahren erhaltenen elektrisch leitfähigen Systeme weise Jedoch den Nachteil auf, daß ihre elektrische Leitfähigkeit noch zu wünschen übrig läßt.The electrically conductive systems obtained by known processes However, they have the disadvantage that their electrical conductivity is still to be desired leaves.

Aufgabe der vorliegenden Erfindung war es daher, das bekannte Verfahren auf Polyaromaten zu übertragen, die Systeme mit einer erhöhten elektrischen Leitfähigkeit ergeben.The object of the present invention was therefore to develop the known method to transfer to polyaromatics, the systems with an increased electrical conductivity result.

Diese Aufgabe wurde dadurch gelöst, daß als Polyaromaten Verbindungen mit durchkonjugierten #-Systemen, In denen parallel mindestens zwei Polyenketten entsprechend den Formein (I) und (II): worin n = 1 bis 100, bevorzugt 2 bis 30 und m = O bis 50, vorzugsweise 0 bis 20, verwendet werden.This object was achieved in that, as polyaromatics, compounds with fully conjugated # systems, in which at least two polyene chains in parallel according to the forms (I) and (II): where n = 1 to 100, preferably 2 to 30 and m = 0 to 50, preferably 0 to 20, are used.

Bevorzugte Polyaromaten sind Quarterylen, Quinquerylen, Sesquicylen oder Dianthracen.Preferred polyaromatics are quarterylene, quinquerylene, sesquicylene or dianthracene.

Die elektrische Leitfähigkeit der erfindungsgemäßen Polyaromaten ist größer als 10-1S/cm. Die Leitfähigkeitswerte werden in S/cm bei 300C gemessen, die Messung selbst erfolgt nach der Methode von F. Beck, "Berichte Bunsengesellschaft, Physikalische Chemie" 63 (1964) Seiten 558 bis 567.The electrical conductivity of the polyaromatics according to the invention is greater than 10-1S / cm. The conductivity values are measured in S / cm at 300C, the Measurement itself takes place according to the method of F. Beck, "Reports Bunsengesellschaft, Physikalische Chemie "63 (1964) pages 558 to 567.

Die Zugabe der Lewis-Säure erfolgt entsprechend der DE-OS 30 05 299 unter Ausschluß von Wasserfeuchtigkeit ur.d Sauerstoff, wobei unter Lewis-Säuren die dort aufgeführten Verbindungen verstanden werden. Geeignete Lewls-Säuren sind die Verbindungen AsF5, HClO4,NO+SbF6-, NO2+SbF6 NO+, AsF6-, NO+PF6-, NO2+PF6-, NO+BF4-, NO2+BF4-, NO+ClO4-, xCF3)2S04, 2,4,6-Trinitrophenol, 2,4,6-Trinitrophenylsulfonsäure oder 2,4,6-Trinitrobenzoesäure.The Lewis acid is added in accordance with DE-OS 30 05 299 with exclusion of water moisture and oxygen, with Lewis acids the compounds listed there are understood. Suitable Lewls acids are the compounds AsF5, HClO4, NO + SbF6-, NO2 + SbF6 NO +, AsF6-, NO + PF6-, NO2 + PF6-, NO + BF4-, NO2 + BF4-, NO + ClO4-, xCF3) 2S04, 2,4,6-trinitrophenol, 2,4,6-trinitrophenylsulfonic acid or 2,4,6-trinitrobenzoic acid.

Die erfindungsgemäß zu verwendenden polyaromatischen Verbindungen entsprechend den Formeln (I) und (II) sind an sich bekannt Evgl. E. Klar, "Aromatische Kohlenwasserstoffe", Springer Verlag, Heidelberg, 2. Auflage (1952) Seiten VI bis XX]. Die Verbindungen enthalten mehr als drei Naphthalin- oder zwei Anthraceneinheiten im polycyclischen System und weisen Molgewichte zwischen 300 und 3000, vorzugsweise zwischen 400 und 1500 auf.The polyaromatic compounds to be used according to the invention according to the formulas (I) and (II) are known per se Evgl. E. Sure, "Aromatic Hydrocarbons ", Springer Verlag, Heidelberg, 2nd edition (1952) pages VI to XX]. The compounds contain more than three naphthalene or two anthracene units in the polycyclic system and have molecular weights between 300 and 3000, preferably between 400 and 1500.

3esonders geeignete polycyclische Aromaten sind Quarterylen, Quinquenylen, Sesquicylen und Dianthracen.3Particularly suitable polycyclic aromatics are Quarterylen, Quinquenylen, Sesquicylene and dianthracene.

Das Einarbeiten der Zusätze erfolgt unter Ausschluß von t'euchtigkeit (Wasser) sowie Sauerstoff (Luft), es wird daher vorzugsweise unter Edelgas-Argonatmosphäre gearbeitet.The additives are incorporated with the exclusion of moisture (Water) as well as oxygen (air), it is therefore preferred under a noble gas-argon atmosphere worked.

Gegebenenfalls werden Hilfsflüssigkeiten wie Tetrahvdrofuran, Dimethoxyglykol, Nitromethan oder Methylenchlorid eingesetzt, die nach dem Einarbeiten bei Temperaturen unter 30°C in Vakuum abgezogen werden.If necessary, auxiliary liquids such as tetrahydrofuran, dimethoxyglycol, Nitromethane or methylene chloride used after incorporation at temperatures be removed under 30 ° C in vacuum.

Durch die genannten Zusätze können elektrische Leitfähigkeitsanstiege von einigen Größenordnungen erreicht erden.The additives mentioned can lead to increases in electrical conductivity reached by several orders of magnitude.

Die Ausgangsleitfähigkeiten der Polyaromaten betrugen ca.The initial conductivity of the polyaromatics was approx.

10-12, sie liefern aber nach der Zugabe der erfindungsgemäßen Zusätze Leitfähigkeiten größer als 10-1 S/cm.10-12, but they deliver after adding the additives according to the invention Conductivities greater than 10-1 S / cm.

Die erfindungsgem.ä hergestellten elektrisch leitfähigen Polyaromaten mit elektrischen Leitfähigkelten größer als 10-1 S/cm sind zur antistatischen Ausrüstung von Kunststoffen, zur Herstellung von Sonnenzellen, zur Umwandlung und Fixierung von Strahlung sowie zur Herstellung elektrischer und magnetischer Schalter und elektrischer Speicher ge- eignet. Durch die Zusätze der starken Lewis-Saure zum Polyaromaten entstehen sog. p-Leiter (vgl. J. Chem.The electrically conductive polyaromatics produced according to the invention with electrical conductivities greater than 10-1 S / cm are for antistatic equipment of plastics, for the production of solar cells, for conversion and fixation of radiation as well as for the production of electrical and magnetic switches and electrical Memory suitable. By adding the strong Lewis acid to the So-called p-conductors are formed from polyaromatics (cf. J. Chem.

Education, Vol. 46, Nr. 2, Seite 82 [1969]).Education, Vol. 46, No. 2, p.82 [1969]).

Die in den folgenden Beispielen genannten Teile sind Gewichtsteile bei den Ausgangskohlenwasserstoffen und Gew.-t bei den jeweiligen Zusatzstoffen.The parts mentioned in the following examples are parts by weight for the starting hydrocarbons and tonnes by weight of the respective additives.

Beispiele 1 bis 7 10 Teile eines Polyaromaten werden unter Argonatmosphäre und Ausschluß von Feuchtigkeit mit dem jeweiligen Zusatzstoff versetzt.Examples 1 to 7 10 parts of a polyaromatic are added under an argon atmosphere and exclusion of moisture mixed with the respective additive.

Nr. Polyaromat Zusatzstoff Leitfähigkeit S/cm 30°C Typ und Menge Art un Menge vor dem Zusatz, nach dem Zusatz (Gew.-%) 1a 1 Teil Quarterylen AsF5 10 10-13 6,5.10-1 1 1 Teil " AsF5 20 10-13 9,5.10-1 2 1 Teil Quinquerylen SbF5 10 10-13 3,5.10-1 3 1 Teil " HClO4 10 10-13 4,8.10-1 4 1 Teil Sesquincylen HClO4 15 5 1 Teil " 2,4,6-Trinitro- 10 10-13 3,9.10 phenylsulfosäure 6 1 Teil Dianthren " 10 10-13 4,8.10+1 7 1 Teil " NO+SbF6 15 10-13 7,5.10+1No. Polyaromatic additive conductivity S / cm 30 ° C Type and quantity Art un amount before addition, after addition (% by weight) 1a 1 part Quarterylen AsF5 10 10-13 6.5.10-1 1 1 part "AsF5 20 10-13 9.5.10-1 2 1 part Quinquerylen SbF5 10 10-13 3.5.10-1 3 1 part "HClO4 10 10-13 4.8.10-1 4 1 part Sesquincylene HClO4 15 5 1 part "2,4,6-trinitro- 10 10-13 3,9,10 phenylsulfonic acid 6 1 part dianthrene" 10 10-13 4.8.10 + 1 7 1 part "NO + SbF6 15 10-13 7.5.10 + 1

Claims (4)

Patentansprüche # 1. # Verfahren zur Herstellung von elektrisch leitfähigen Polyaromaten mit elektrischen Leitfähigkeitswerten großer als 10-1 S/cm, wobei den Polyaromaten unter Ausschluß von Wasserfeuchtigkeit und von Sauerstoff 0,5 bis 5 Gew.-%, bezogen auf den eingesetzten Polyaromaten, einer starken Lewis-Säure mit pks-lVerten von -10 bis +4 zugesetzt wird, dadurch gekennzeichnet, daß als Polyaromaten Verbindungen mit durchkonjugierten -Systemen, in denen parallel mindestens zwei Polyenketten verlaufen, entsprechend den Formeln (I) und (II): worin n = 1 bis 100 und m = 0 bis 50, verwendet werden.Claims # 1. # Process for the production of electrically conductive polyaromatics with electrical conductivity values greater than 10-1 S / cm, the polyaromatics, with the exclusion of water moisture and oxygen, 0.5 to 5% by weight, based on the polyaromatics used, a strong Lewis acid with pks-I values of -10 to +4 is added, characterized in that the polyaromatic compounds are compounds with conjugated systems in which at least two poly chains run in parallel, corresponding to formulas (I) and (II): where n = 1 to 100 and m = 0 to 50 are used. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Polyaromat Quarterylen, Quinquerylen, Sesquicylen oder Dianthracen verwendet wird.2. The method according to claim 1, characterized in that the polyaromatic Quarterylene, quinquerylene, sesquicylene or dianthracene is used. '3. Verwendung der nach Anspruch 1 hergestellten elektrisch leitfähigen Polyaromaten in der Elektrotechnik zur Herstellung von Sonnenzellen, zur Umwandlung und Fixierung von Strahlung, zur Herstellung elektrischer und magnetischer Schalter und elektrischer Speicher.'3. Use of the electrically conductive produced according to claim 1 Polyaromatics in electrical engineering for the production of solar cells, for conversion and fixation of radiation, for making electrical and magnetic switches and electrical storage. 4. Verwendung der nach Anspruch 1 hergestellten elektrisch leitfähigen Polyaromaten zur antistatischen Ausrüstung von Kunststoffen.4. Use of the electrically conductive produced according to claim 1 Polyaromatics for the antistatic treatment of plastics.
DE19823226780 1981-07-22 1982-07-17 Process for the preparation of electrically conductive polyaromatics and their use in electrical engineering and for the antistatic finishing of plastics Withdrawn DE3226780A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1302950A2 (en) * 2001-10-15 2003-04-16 Fujitsu Limited Electrically conducting organic compound and electronic device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1302950A2 (en) * 2001-10-15 2003-04-16 Fujitsu Limited Electrically conducting organic compound and electronic device
EP1302950A3 (en) * 2001-10-15 2009-03-25 FUJIFILM Corporation Electrically conducting organic compound and electronic device

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