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 plasticsInfo
- 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
- Authority
- DE
- Germany
- Prior art keywords
- polyaromatics
- electrically conductive
- electrical
- plastics
- preparation
- 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- Withdrawn
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
- 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
Landscapes
- 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
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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19823226780 DE3226780A1 (en) | 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 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3128890 | 1981-07-22 | ||
DE19823226780 DE3226780A1 (en) | 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 |
Publications (1)
Publication Number | Publication Date |
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DE3226780A1 true DE3226780A1 (en) | 1983-02-10 |
Family
ID=25794745
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DE19823226780 Withdrawn DE3226780A1 (en) | 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 |
Country Status (1)
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DE (1) | DE3226780A1 (en) |
Cited By (1)
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 |
-
1982
- 1982-07-17 DE DE19823226780 patent/DE3226780A1/en not_active Withdrawn
Cited By (2)
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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