DE3200073A1 - Process for the preparation of electroconductive polymers, and the use thereof in electrical engineering and for antistatic finishing of plastics - Google Patents

Process for the preparation of electroconductive polymers, and the use thereof in electrical engineering and for antistatic finishing of plastics

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DE3200073A1
DE3200073A1 DE19823200073 DE3200073A DE3200073A1 DE 3200073 A1 DE3200073 A1 DE 3200073A1 DE 19823200073 DE19823200073 DE 19823200073 DE 3200073 A DE3200073 A DE 3200073A DE 3200073 A1 DE3200073 A1 DE 3200073A1
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acetylene
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Volker Dipl.Chem.Dr. 6700 Ludwigshafen Muench
Herbert Dipl.Chem.Dr. 6719 Wattenheim Naarmann
Dieter Dipl.Chem.Dr. 6520 Worms Naegele
Klaus Dipl.Chem.Dr. 6710 Frankenthal Penzien
Johannes Dipl.Phys.Dr. 6700 Ludwigshafen Schlag
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BASF SE
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L49/00—Compositions of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Compositions of derivatives of such polymers
    • 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
    • H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/143—Polyacetylene; Derivatives thereof
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a process for the preparation of electroconductive polymers by polymerisation of acetylene and derivatives of acetylene, and of polycyclic aromatic compounds at temperatures of from -200 to +50 DEG C in the presence of an oxidising Lewis acid in amounts of from 1 to 50 % by weight. The oxidising Lewis acid may be a mixture of a cationic catalyst and a gaseous oxidant or a compound from groups VI-VIII and the subgroups of the Periodic Table of the Elements and/or a combination of Lewis acids from groups III to VI and from the subgroups of the Periodic Table of the Elements with auxiliary oxidants from groups V-VIII and from the subgroups of the Periodic Table of the Elements, and preferably acts on thin films of the monomers to be polymerised. The electroconductive polymers prepared can be used in electrical engineering for the production of solar cells, for the conversion and fixation of radiation, for the production of electrical and magnetic switches and for the antistatic finishing of plastics.

Description

Verfahren zur Herstellung von elektrisch leitfähigen Poly-Process for the production of electrically conductive poly

meren und deren Verwendung in der Elektrotechnik und zur antistatischen Ausrüstung von Kunststoffen Die Erfindung betrifft ein Verfahren zur Herstellung von elektrisch leitfähigen Polymeren durch Polymerisation von Acetylen oder Derivaten des Acetylens, sowie von mehrkernigen Aromaten bei Temperaturen von -200 bis +50°C in Gegenwart eines kationisch wirkenden Katalysators.mers and their use in electrical engineering and for antistatic Finishing of plastics The invention relates to a method for production of electrically conductive polymers through the polymerization of acetylene or derivatives of acetylene and polynuclear aromatics at temperatures from -200 to + 50 ° C in the presence of a cationic catalyst.

Bei derartigen Polymerisationsverfahren sind kationische Katalysatoren erforderlich, um eine Polymerisation in Gang zu bringen.Cationic catalysts are used in such polymerization processes required to initiate polymerization.

Es ist bereits bekannt, Vinylverbindungen mit Hilfe kationisch wirkender Katalysatoren zu polymerisieren (vgl.It is already known to use cationic vinyl compounds To polymerize catalysts (cf.

W.R.Soerenson u. T.W.Campbell, "Preparative Methods of Polymer Chemistry", Interscience Publ., New vork 1968, Seite 265).W.R.Soerenson and T.W. Campbell, "Preparative Methods of Polymer Chemistry", Interscience Publ., New vork 1968, p. 265).

Es ist auch bereits bekannt, elektrisch leitfähige Polymere durch oxidative Kupplung von aromatischen Verbindungen mit Hilfe von Lewis-Säuren herzustellen (vgl. "Naturwissenschaften, 56, [1969], Seite 308). Dieses Verfahren wurde jedoch nur bei aromatischen und cycloaliphatischen Systemen durchgeführt. Die erhaltenen Polymeren waren relativ niedermolekular mit Polymerisaticnsgraden bis zu ca. 50 und dementsprechend spröde und schwer zu verarbeiten. Acetylen ist nach S. Ikeda (vgl. Makromolekulare Chemie 179 [1978], Seite 1565) oder Journal Chemistry Society Chemical Communication 1980, Seite 931 polymerisierbar.It is also already known to use electrically conductive polymers to produce oxidative coupling of aromatic compounds with the help of Lewis acids (see "Naturwissenschaften, 56, [1969], page 308). This method, however only carried out for aromatic and cycloaliphatic systems. The received Polymers were relatively low molecular weight with degrees of polymerisation up to approx. 50 and accordingly brittle and difficult to process. Acetylene is according to S. Ikeda (cf. Makromolekulare Chemie 179 [1978], page 1565) or Journal Chemistry Society Chemical Communication 1980, page 931 polymerizable.

Der Erfindung liegt die Aufgabe zugrunde, hochmolekulare, nicht spröde Polymere mit guter Verarbeitbarkeit und hoher elektrischer Leitfähigkeit zu schaffen.The invention is based on the object of high molecular weight, not brittle To create polymers with good processability and high electrical conductivity.

Diese Aufgabe wurde dadurch gelöst, daß als Katalysator für die Polymerisaton von Acetylen oder seinen Derivaten, sowie von mehrkernigen Aromaten eine oxidierend wirkende Lewis-Säure in Mengen von 1 bis 50, bevorzugt 10 bis 40 Gew.-%, bezogen auf das Gewicht des jeweils eingesetzten Monomeren, verwendet wird. This object was achieved in that as a catalyst for the Polymerisaton of acetylene or its derivatives, as well as of polynuclear aromatics one oxidizing acting Lewis acid in amounts of 1 to 50, preferably 10 to 40 wt .-%, based based on the weight of the particular monomer used.

Unter Derivaten des Acetylens und mehrkernigen Aromaten werden verstanden Phenylacetylen, Methylpropin, Propargylalkohol etc. bzw. Terphenyl, Quaterphenyl, Anthracen, Coronen. Derivatives of acetylene and polynuclear aromatics are understood to mean Phenylacetylene, methylpropine, propargyl alcohol etc. or terphenyl, quaterphenyl, Anthracene, coronene.

Oxidierende Lewis-Säuren nach der erfindungsgemäßen Verfahren sind solche der Gruppe VIII KrF2, XeF4, XeOF4, XeF6, XeO2F2, HXe04 sowie der Gruppe VII ClF, ClF3, ClF5, BrF3, IF5, IF7, BrCL, BrI, I2, Br2, Cl2O, Cl2O3, ClO2, ClOClO3, Cl2O6, Cl2O6, Cl2O7, Br2O, BrO2, Br2O5, BrO3, I4O9, I2O5, HOCl, HClO2, HClO3, HClO4, HOBr, HBr02, HBr03, HBr04, HIO3, HI04 FClO3, CLf3O, ClF3O2, FClO2, FClO, BrO2F, BrO3F, IO2F, IOF3, IO2F3, IOF5 wie auch der Gruppe VI SO3, H2SO4, H2SeO4, FSO3H, (FSO3F), R(SO2F) mit R = NH, HC(SO2F)3, FXe(SO3F), FXe(OSeF5), FXe(OTeF5), Xe(OSeF5)4, Xe(OTeF4), FXe(OSeF5), F6-xCl(OSeF5)x mit x = 1 bis 5 FW (OSeF5)@ mit x = 1 bis 6, sowie den Nebengruppen AuF5, PtF6, IrF60sF6, PtF5, IrF5, OsF5, CrF5, MoF6, WF6, WF5, MoF5, VF5, NbF5, TaF5, UF6, PuF6, ReF7, ReOF5, CrO2F2, CrO2Cl2, CrO3, AuCl3, PtCl4, AuCl3 vorzugsweise werden verwendet XeF4, ClO2, Cl2O4, IF5, HBrO3, FS03H sowie CrO2C12, OsF5 und auch MoF6 od. OsF6 Nach dem erfindungsgemäßen Verfahren sind jedoch auch Kombinationen von Lewis-Säuren mit Hilfsoxidationsmitteln geeignet. Als Lewis-Säuren sind geeignet solche der VI. Gruppe CF3SO3H, CF3(CF2)nSO3H, ClSO3H, Cl2CHSO3H, sowie der V. Gruppe H3PO4, H3AsO4, HPO2F2, P2O3F4, PF5, BiX3 mit X = F, Cl, Br, i der IV. Gruppe SiF4, H2SiF6, GeX4, SnX4, PbX4 mit X = F, C1, Br der III. GrupDe BX3, AlX3, GaX3, InX3, TLX3 mit X = F, CL Br I sowie der Nebengruppen ReF6, ReCl5, ReCl4, ReOF4, VOF3, NbOF3, TaOF3, VCl3, VF3, NbCl5, TaCl5, NbOCL3, TuOCl3, UCl5, CuX2, AgX, AuX (X = Cl, Br) ZnX2, CdX2, HgX2 (X = Cl, Br, I) NiX, PdX2, PtX2 (X = Cl, Br, I) COX2, PhX2, IrX2(X = Cl, Br, I) FeX2, FeX3, RuX2, OsX2 (X = Cl, Br, I) MnX2, (X = C1, Br, I) TiX4, ZrX4, HfF4 (X = F, Cl, Br, I) SeX3, Y3X, LaX3 Lanthamide X3 (X = F, Cl, Br, I) Actinide X3, X5 (X = F, Cl, Br) Als Hilfsoxidationsmittel kommen solche der VIII. Gruppe XeF2, KrF#, XeF#, Xe2#, Xe2F#, XeOF3#, XeOF5#, XeO2F# RaF2 der VII. Gruppe F2, Cl2, Br2, I2, O2F2, ClF, Cl2F#, ClF2#, ClF4#, BrF2# BrF4#, IF4#, IF#, ClF2O2#, ClO2#, BrO2#, IO2#, IOF2#, IO2F2, Brn 1 I@ mit n = 1 bis 5 sowie der VI. Gruppe O3, O2#, CF3OF, CF2(OF)2, SF5OF, CF3OCl, CF3OBr, CF3OOSF5, CF3OOOCF3, CFOOOC(O)F, SF5OOOSF5, SO4F#, HOF, H2O2, H3O#2 der V. Gruppe NO, NO2, N2O3, N2O4, NO#, NO2#, NOF, NOCl, NO2F, NO3F, N2F2, N2F4, NHF2, NF3, NF3O, N2F#, N2F3#, NF2O#, NF4#, NH3F#, NF4, NH3F#, NH2F2#, NCl2F, NF2Cl, NBr2F, NBrF2, NCl3, RNCl2, R2NCl mit R = H oder organischem Rest NBr3, RNBr2, R2NBr mit R = " " NI3, RNI2, R2NI mit R = " " " " RNF2, R2NI mit R = H " " " R2C = NF, mit 4 = " " " R-NClO3 und aus den mit R = " " " " Nebengruppen CoF3, FeO4²#, OsO4, MnO2, MnO3#, MnO4#, Mn2O7, CrO3, CrO5, CrO42#, Cr2O72#, CrO2Cl2, CrO2F2 in Frage.Oxidizing Lewis acids according to the process according to the invention are those of group VIII KrF2, XeF4, XeOF4, XeF6, XeO2F2, HXe04 and group VII ClF, ClF3, ClF5, BrF3, IF5, IF7, BrCL, BrI, I2, Br2, Cl2O, Cl2O3, ClO2, ClOClO3, Cl2O6, Cl2O6, Cl2O7, Br2O, BrO2, Br2O5, BrO3, I4O9, I2O5, HOCl, HClO2, HClO3, HClO4, HOBr, HBr02, HBr03, FClO3, HIFO4 FCIO , FClO, BrO2F, BrO3F, IO2F, IOF3, IO2F3, IOF5 as well as group VI SO3, H2SO4, H2SeO4, FSO3H, (FSO3F), R (SO2F) with R = NH, HC (SO2F) 3, FXe (SO3F) , FXe (OSeF5), FXe (OTeF5), Xe (OSeF5) 4, Xe (OTeF4), FXe (OSeF5), F6-xCl (OSeF5) x with x = 1 to 5 FW (OSeF5) @ with x = 1 to 6, as well as the subgroups AuF5, PtF6, IrF60sF6, PtF5, IrF5, OsF5, CrF5, MoF6, WF6, WF5, MoF5, VF5, NbF5, TaF5, UF6, PuF6, ReF7, ReOF5, CrO2Cl3, CrO2Cl2, CrO2Cl2., CrO2Cl2 , AuCl3 preferably used XeF4, ClO2, Cl2O4, IF5, HBrO3, FS03H and CrO2C12, OsF5 and also MoF6 or OsF6 However, combinations are also possible according to the method according to the invention of Lewis acids with auxiliary oxidizing agents. Suitable Lewis acids are those of VI. Group CF3SO3H, CF3 (CF2) nSO3H, ClSO3H, Cl2CHSO3H, as well as the V group H3PO4, H3AsO4, HPO2F2, P2O3F4, PF5, BiX3 with X = F, Cl, Br, i of the IV group SiF4, H2SiF6, GeX4, SnX4 , PbX4 with X = F, C1, Br of III. GrupDe BX3, AlX3, GaX3, InX3, TLX3 with X = F, CL Br I and the subgroups ReF6, ReCl5, ReCl4, ReOF4, VOF3, NbOF3, TaOF3, VCl3, VF3, NbCl5, TaCl5, NbOCL3, TuCl5, CuX2, UCl2 , AgX, AuX (X = Cl, Br) ZnX2, CdX2, HgX2 (X = Cl, Br, I) NiX, PdX2, PtX2 (X = Cl, Br, I) COX2, PhX2, IrX2 (X = Cl, Br , I) FeX2, FeX3, RuX2, OsX2 (X = Cl, Br, I) MnX2, (X = C1, Br, I) TiX4, ZrX4, HfF4 (X = F, Cl, Br, I) SeX3, Y3X, LaX3 Lanthamide X3 (X = F, Cl, Br, I) Actinide X3, X5 (X = F, Cl, Br) The auxiliary oxidizing agents are those of Group VIII XeF2, KrF #, XeF #, Xe2 #, Xe2F #, XeOF3 #, XeOF5 #, XeO2F # RaF2 of Group VII F2, Cl2, Br2, I2, O2F2, ClF, Cl2F #, ClF2 #, ClF4 #, BrF2 # BrF4 #, IF4 #, IF #, ClF2O2 #, ClO2 #, BrO2 #, IO2 #, IOF2 #, IO2F2, Brn 1 I @ with n = 1 to 5 as well as the VI. Group O3, O2 #, CF3OF, CF2 (OF) 2, SF5OF, CF3OCl, CF3OBr, CF3OOSF5, CF3OOOCF3, CFOOOC (O) F, SF5OOOSF5, SO4F #, HOF, H2O2, H3O # 2 of the V group NO, NO2, N2O3, N2O4, NO #, NO2 #, NOF, NOCl, NO2F, NO3F, N2F2, N2F4, NHF2, NF3, NF3O, N2F #, N2F3 #, NF2O #, NF4 #, NH3F #, NF4, NH3F #, NH2F2 # , NCl2F, NF2Cl, NBr2F, NBrF2, NCl3, RNCl2, R2NCl with R = H or organic residue NBr3, RNBr2, R2NBr with R = "" NI3, RNI2, R2NI with R = """" RNF2, R2NI with R = H """R2C = NF, with 4 = """R-NClO3 and from the with R =""""subgroups CoF3, FeO4² #, OsO4, MnO2, MnO3 #, MnO4 #, Mn2O7, CrO3, CrO5, CrO42 #, Cr2O72 #, CrO2Cl2, CrO2F2 in question.

Die Reaktion kann mit den gasförmigen Reaktanten oder mit Hilfssäuren wie HF, HOSeF5, HOTeF5, CH3SO3H, CF3COOH, CF3PO3H, (CF3)2 POOH, HPF6, H2SiF6, H2PO2F2, oder gegebenenfalls in inerten Lösungsmitteln wie SO2, SO2Cl2, SO2F2, SO2CIF, Frigene z.B. CHCl3 (Frigen 11), HF, CX3CN, CH3N02, C2H5NO2 durchgeführt werden.The reaction can be carried out with the gaseous reactants or with auxiliary acids such as HF, HOSeF5, HOTeF5, CH3SO3H, CF3COOH, CF3PO3H, (CF3) 2 POOH, HPF6, H2SiF6, H2PO2F2, or optionally in inert solvents such as SO2, SO2Cl2, SO2F2, SO2CIF, Frigene e.g. CHCl3 (Frigen 11), HF, CX3CN, CH3N02, C2H5NO2 can be carried out.

Als Polymerisationstemperatur wird der Bereich von -200 bis +50°C, vorzugsweise von -80 bis OOC eingestellt. Das erfindungsgemäße Polymerisationsverfahren kann in üblichen Lösungsmitteln oder Hilfsflüssigkeiten, jedoch auch direkt in Substanz durchgeführt werden.The polymerisation temperature is from -200 to + 50 ° C, preferably set from -80 to OOC. The polymerization process according to the invention can in common solvents or auxiliary liquids, but also directly in substance be performed.

Die besonders bevorzugte Verfahrensvariante ist die oxidierende kationische Polymerisation, bei der dünne Filme der oben genannten Monomeren auf Glas oder polymeren Trä- gern, vorzugsweise Kunststoffolie - ein- oder beidseitig - mit gasförmigen Initiatoren wie N2F4, N2F2, XeF4, ClF3, FC103 polymerisiert werden.The particularly preferred process variant is the oxidizing cationic one Polymerization, in which thin films of the above monomers on glass or polymers Weary gladly, preferably plastic film - one or both sides - be polymerized with gaseous initiators such as N2F4, N2F2, XeF4, ClF3, FC103.

Die nach dem erfindungsgemäßen Verfahren hergestellten Polymeren sind löslich und haben Intrinsic Viskositäten [7] 0,5, d.h. Molgewichte größer als 25000 (entsprechend der Umrechnungsformel in der Literatur "Macromolecular Synthesis, Vol.I, [1974], Seite 83). Die so hergestellten Polymeren haben elektrische Leitfähigkeitswerte von ca. The polymers produced by the process according to the invention are soluble and have intrinsic viscosities [7] 0.5, i.e. molecular weights greater than 25000 (according to the conversion formula in the literature "Macromolecular Synthesis, Vol.I, [1974], page 83). The polymers produced in this way have electrical conductivity values from approx.

10-10 bis 10-³S/cm, in Abhängigkeit von der Menge des im Polymeren verbliebenen Katalysators. 10-10 to 10 -³S / cm depending on the amount of the in the polymer remaining catalyst.

Durch Erhöhung der Menge des erfindungsgemäßen Katalysators während oder nach der Polymerisation bis zu 50 Gew.% gelingt es, elektrische Leitfähigkeit bis zu 10+²S/cm zu erreichen. Die Messung der elektrischen Leitfähigkeit erfolgt nach F. Beck, Ber. der Bunsenges. 68, (1964), Seite 559. By increasing the amount of the catalyst of the invention during or after the polymerization up to 50% by weight it is possible to achieve electrical conductivity up to 10 + ²S / cm can be achieved. The electrical conductivity is measured after F. Beck, Ber. the Bunsenges. 68, (1964), p. 559.

Die erfindungsgemäß hergestellten elektrisch leitfähigen Polymeren mit elektrischen Leitfähigkeiten größer als 10-² S/cm sind zur antistatischen Ausrüstung von Kunststoffen, zum Herstellen von Sonnenzellen, zur Umwandlung und Fixierung von Strahlung sowie zur Herstellung elektrischer und magnetischer Schalter geeignet. Durch die Zusätze der starken Lewis-Säuren zu den Monomeren, bzw. Polymeren, entstehen sog. p-Leiter (vgl. J.Chem. The electrically conductive polymers produced according to the invention with electrical conductivities greater than 10-² S / cm are for antistatic treatment of plastics, for making solar cells, for transforming and fixing from radiation as well as for the production of electrical and magnetic switches. The addition of strong Lewis acids to the monomers or polymers are created so-called p-conductor (see J. Chem.

Education, Vol. 46, [1969] (2), Seite 82). Education, Vol. 46, [1969] (2), p.82).

Die in den folgenden Beispielen genannten Teile sind Gewichtsteile, bzw. Molprozente. The parts mentioned in the following examples are parts by weight, or mole percent.

Beispiel 1 Eine Lösung von 10 Teilen Terphenyl wird in 100 Teilen Toluol bei -70°C gelöst und bei dieser Temperatur mit 1 Teil X2F4 versetzt. Nach der Zugabe wid die Lösung im Verlauf von 5 Stunden auf 25°C erwärmt und das Lösungsmittel abgezogen. Das Polymerisat ist löslich in Benzol und hat ein Molgewicht von ca. 1200. Die elektrische Leitfähigkeit dieses Produktes beträgt 5,5 . 1o-².Example 1 A solution of 10 parts of terphenyl is made in 100 parts Toluene dissolved at -70 ° C and treated with 1 part of X2F4 at this temperature. To the addition, the solution is warmed to 25 ° C. over the course of 5 hours and the solvent is added deducted. The polymer is soluble in benzene and has a molecular weight of approx. 1200. The electrical conductivity of this product is 5.5. 1o-².

Beispiele 2 bis 5 Wird wie im Beispiel 1 beschrieben gearbeitet, jedoch Menge und. Art des Lösungsmittels und des Initiators variiert, so werden die folgenden Ergebnisse erhalten. Examples 2 to 5 If you work as described in Example 1, however amount and. Type of solvent and initiator will vary obtained the following results.

Nr. Lösungsmittel Temp. Initia- Leitfähig-0C tor keit Art Teile S/cm 30°C 2 Benzol 100 Tl. 10 ClO2 2 4,1.10-¹ 3 Toluol 100 Tl. -50 CSl3 3 2,5.10-¹ 4 Methylenchlorid 100 Tl. -50 CrO2Cl2 3 1,0.10-¹ 5 Diäthyläther 100 T1. 0 N022/BF35 2,7.10-² 6 Schwefeldioxid 100 TI. - 5 2H2SeO4 3,1.10 7 Frigen 11R CFCl3 1OOTl.- 5 5FS03H 4,2.10-² 8 Acetonitril 100 Tl 0 5HClO4 3,6.10-² Beispiel 6 Es wird wie im Beispiel 1 beschrieben gearbeitet, jedoch das Monomere variiert, so werden die folgenden Ergebnisse erzielt. No. Solvent Temp. Initia- Conductivity Type Parts S / cm 30 ° C 2 benzene 100 parts 10 ClO2 2 4.1.10-1 3 toluene 100 parts -50 CSl3 3 2.5.10-1 4 Methylene chloride 100 parts -50 CrO2Cl2 3 1.0.10-1 5 diethyl ether 100 parts. 0 N022 / BF35 2,7.10-26 sulfur dioxide 100 TI. - 5 2H2SeO4 3,1.10 7 Frigen 11R CFCl3 1OOTl.- 5 5FS03H 4,2.10-² 8 acetonitrile 100 Tl O 5HClO4 3,6.10-² Example 6 It is as worked described in Example 1, but the monomer varies, so the obtained the following results.

Nr. Monomeres Leitfähigkeit S/cm 30°C 9 Acetylen 0,9 10-¹ 10 Phenylacetylen 1,2 10-³ 11 Propanylalkohol 4,5 10-4 12 Methylpropin 1,5 10-³ Beispiele 10 bis 18 Nr. Polymerisat Lewis-Säure Leitfähigkeit S/cm nach Beispiel Art u. enge 300C 13 1 2BF3/3(SF5O)2 4,0.10-¹ 14 2 2TiCl4/3N2O4 7,5.10-² 15 3 2FeCl3/4HPF6 3,9.10-¹ 16 4 2VC13/2C102 4,5.10-¹ 17 5 2PtCl2/4CrO2Cl2 9,6.10-¹ 18 6 1Br3O8/2H3AsO4 7,8.10-¹No. Monomer conductivity S / cm 30 ° C 9 acetylene 0.9 10-1 10 phenylacetylene 1.2 10-3 11 propanyl alcohol 4.5 10-4 12 methylpropine 1.5 10-3 Examples 10-18 No. polymer Lewis acid conductivity S / cm according to example type and narrow 300C 13 1 2BF3 / 3 (SF5O) 2 4.0.10-1 14 2 2TiCl4 / 3N2O4 7.5.10-2 15 3 2FeCl3 / 4HPF6 3.9.10-1 16 4 2VC13 / 2C102 4,5.10-¹ 17 5 2PtCl2 / 4CrO2Cl2 9.6.10-¹ 18 6 1Br3O8 / 2H3AsO4 7.8.10-¹

Claims (6)

P a t e n t a n s p r ü c h e 1. Verfahren zur Herstellung von elektrisch leitfähigen Polymeren durch Polymerisation von Acetylen und Derivaten des Acetylens, sowie von mehrkernigen Aromaten bei Temperaturen von -200 bis +500 C in C-egenwart eines kationisch wirkenden Katalysators, dadurch gekennzeichnet, daß als Katalysator eine oxidierend wirkende Lewis-Säure in Mengen von 1 bis 50 Gew.-%, bezogen auf das Gewicht des jeweils eingesetzten Monomeren, verwendet wird.P a t e n t a n s p r ü c h e 1. Process for the production of electrical conductive polymers through polymerization of acetylene and derivatives of acetylene, as well as polynuclear aromatics at temperatures from -200 to +500 C in C-present a cationically acting catalyst, characterized in that as a catalyst an oxidizing Lewis acid in amounts of 1 to 50 wt .-%, based on the weight of the particular monomer used is used. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die oxidierend wirkende Lewis-Säure ein Gemisch von einem kationisch wirkenden Katalysator und einem gasförmigen Oxidationsmittel ist.2. The method according to claim 1, characterized in that the oxidizing acting Lewis acid is a mixture of a cationically acting catalyst and is a gaseous oxidizing agent. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die oxidierende Lewis-Säure eine Verbindung der Gruppen VI-VIII sowie der Nebengruppen des Periodensystems der Elemente und/oder eine Kombination von Lewis-Säuren der Gruppen III bis VI sowie der Nebengruppen des Periodensystems der Elemente mit Hilfsoxidationsmitteln der Gruppen V-VIII sowie der Nebengruppen des Periodensystems der Elemente ist.3. The method according to claim 1, characterized in that the oxidizing Lewis acid a compound of groups VI-VIII and the subgroups of the periodic table of the elements and / or a combination of Lewis acids of groups III to VI as well as of the subgroups of the periodic table of the elements with auxiliary oxidants of Groups V-VIII and the subgroups of the Periodic Table of the Elements. 4. Verfahren nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der Katalysator auf dünne Filme der zu polymerisierenden Monomeren, aufgebracht auf Glas oder polymeren Trägern, einwirkt.4. Process according to Claims 1 and 2, characterized in that the catalyst is applied to thin films of the monomers to be polymerized acts on glass or polymeric substrates. '5. Verwendung der nach Anspruch 1 hergestellten elektrisch leitfähigen Polymeren in der Elektrotechnik zur Herstellung von Sonnenzellen, zur Umwandlung und Fixierung von Strahlung und zur Herstellung elektrischer und magnetischer Schalter.'5. Use of the electrically conductive produced according to claim 1 Polymers in electrical engineering for the production of solar cells, for conversion and fixation of radiation and for making electrical and magnetic switches. 6. Verwendung der nach Anspruch 1 hergestellten elektrisch leitfähigen Polymeren zur antistatischen Ausrüstung von Kunststoffen. 6. Use of the electrically conductive produced according to claim 1 Polymers for the antistatic treatment of plastics.
DE19823200073 1981-01-10 1982-01-05 Process for the preparation of electroconductive polymers, and the use thereof in electrical engineering and for antistatic finishing of plastics Withdrawn DE3200073A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195380A2 (en) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Process for manufacturing electrically conductive foam materials
EP0206133A1 (en) * 1985-06-12 1986-12-30 BASF Aktiengesellschaft Use of polypyrrole to deposit metallic copper onto non-electroconductive materials
EP0241728A1 (en) * 1986-03-19 1987-10-21 BASF Aktiengesellschaft Films of electrically conducting polymers, and electrodes coated with these films
DE19717952A1 (en) * 1997-04-29 1998-11-05 Eike Gerhard Huebner Permanently electrically conductive plastic

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195380A2 (en) * 1985-03-20 1986-09-24 BASF Aktiengesellschaft Process for manufacturing electrically conductive foam materials
EP0195380A3 (en) * 1985-03-20 1987-04-29 Basf Aktiengesellschaft Process for manufacturing electrically conductive foam materials
EP0206133A1 (en) * 1985-06-12 1986-12-30 BASF Aktiengesellschaft Use of polypyrrole to deposit metallic copper onto non-electroconductive materials
EP0241728A1 (en) * 1986-03-19 1987-10-21 BASF Aktiengesellschaft Films of electrically conducting polymers, and electrodes coated with these films
DE19717952A1 (en) * 1997-04-29 1998-11-05 Eike Gerhard Huebner Permanently electrically conductive plastic
DE19717952C2 (en) * 1997-04-29 1999-06-17 Eike Gerhard Huebner Permanently electrically conductive polymer

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