DE3721534A1 - Polymers containing thiadiazole groups, and the use thereof in the electrical industry - Google Patents

Polymers containing thiadiazole groups, and the use thereof in the electrical industry

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Publication number
DE3721534A1
DE3721534A1 DE19873721534 DE3721534A DE3721534A1 DE 3721534 A1 DE3721534 A1 DE 3721534A1 DE 19873721534 DE19873721534 DE 19873721534 DE 3721534 A DE3721534 A DE 3721534A DE 3721534 A1 DE3721534 A1 DE 3721534A1
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Germany
Prior art keywords
parts
polymers containing
polymers
electrical industry
polymers according
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Withdrawn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
DE19873721534
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German (de)
Inventor
Herbert Dr Naarmann
Helmut Dr Hagen
Juergen Dr Pfister
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
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE19873721534 priority Critical patent/DE3721534A1/en
Publication of DE3721534A1 publication Critical patent/DE3721534A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/32—Polythiazoles; Polythiadiazoles
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • 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

Abstract

The invention relates to polymers containing recurring structural units of the formula I or II: <IMAGE> in which X is NH, S, O, P, As or Sb, and the use thereof for electroconductive systems and electrodes.

Description

Die Erfindung betrifft neue Thiazolgruppen enthaltene Polymere.The invention relates to new polymers containing thiazole groups.

Es bestand die Aufgabe Polymere aufzufinden, die thermostabil sind und bei 300°C einen Gewichtsverlust von weniger als 1 Gewichtsprozent auf­ weisen, thermoplastisch verarbeitbar, löslich und elektrisch leitfähig sind.The task was to find polymers that are thermostable and at 300 ° C a weight loss of less than 1 percent by weight exhibit, thermoplastically processable, soluble and electrically conductive are.

Diese Aufgabe wurde durch Polymere nach Patentansprüchen 1 bis 3 gelöst.This object was achieved by polymers according to patent claims 1 to 3.

Die Synthese der Polymere ist auf zwei verschiedenen Wegen möglich. Sie erfolgt analog Literatur "Liebigs Annalen der Chemie", 1980, 12 bis 1231.The synthesis of the polymers is possible in two different ways. they takes place analogously to literature "Liebigs Annalen der Chemie", 1980, 12 to 1231.

1) Kondensation von Thiophen- bzw. Pyrrolmonoaldehyd zum entsprechenden Thiodiazol, dann oxidative Kupplung, chemisch oder elektrochemisch, eventuell mit zusätzlichem Pyrrol oder Thiopen:
Synthese, 1. Route:1) Condensation of thiophene or pyrrole monoaldehyde to the corresponding thiodiazole, then oxidative coupling, chemically or electrochemically, possibly with additional pyrrole or thiophene:
Synthesis, 1st route:

Synthese, 2. Route: Synthesis, 2nd route:

wobei statt NH auch S, O, P, As oder Sn verwendet werden kann.S, O, P, As or Sn can also be used instead of NH.

Die Synthese wird in Dimethylformamid, Toluol, N-Methylpyrrolidin etc. oder Gemischen dieser organischen Lösungsmittel durch Erhitzen der ent­ sprechenden Komponenten durchgeführt. Die erhaltenen Polymeren haben Grenzviskositätswerte [η] von mindestens 0,5 dl/g gemessen bei 25°C in N,N-Dimethylformamid, entsprechend einem Molekulargewicht von mehr als 20 000.The synthesis is carried out in dimethylformamide, toluene, N-methylpyrrolidine etc. or mixtures of these organic solvents by heating the corresponding components. The polymers obtained have intrinsic viscosity values [ η ] of at least 0.5 dl / g measured at 25 ° C. in N, N-dimethylformamide, corresponding to a molecular weight of more than 20,000.

Die erhaltenen Polymeren sind thermoplastisch und auch in Lösung ver­ arbeitbar. Die elektrische Leitfähigkeit liegt bei 50 S/cm.The polymers obtained are thermoplastic and also ver in solution workable. The electrical conductivity is 50 S / cm.

Die Polymeren sind verwendbar zur Herstellung von Formkörpern, Dichtungs­ material, elektrisch leitfähige Systeme, antistatischem Ver­ packungsmaterial oder Sensoren.The polymers can be used for the production of moldings, seals material, electrically conductive systems, antistatic Ver packing material or sensors.

Beispiele 1 bis 4Examples 1 to 4 (Die angegebenen Teile sind jeweils Gewichtsteile)(The specified parts are parts by weight)

1. 19 Teile Pyrrolaldehyd werden in 100 Teilen Methylglykol bei Raum­ temperatur mit 5 Teilen Hydrazinhydrat versetzt und dann nach 5stündigem Erwärmen bei 50°C aufgearbeitet. Nach dem Absaugen des Aldazins, wird das Reaktionsprodukt mit 10 Teilen Schwefel versetzt und dann der Kondensation 3 h bei 120°C unterworfen. Es entstehen 20,5 Teile des Dipropylthiadiazol, das sich nach dem Umkristalli­ sieren im Chloroform bei Temp. 185°C zersetzt. 2,0 Teile des oben hergestellten Dipropylthiadiazol werden in einer Elektrozelle in einem Elektrolyten aus Acetonitril mit 10 Gew.-% Methylenchlorid mit 2 Gew.-%Phenylsulfonsäure versetzt und bei Raumtemperatur innerhalb von 2 Stunden bei einer Stromdichte von 2 mA/cm² an der Anode (Platinblech 6 cm²) abgeschieden. Der Abstand der Anode zur Gegen­ elektrode (ebenfalls Platinblech 6 cm²) betrug 2 cm. Der erhaltene, von der Anode ablösbare Polymerfilm ist schwarz, 70 µm dick und hat eine spez. elektrische Leitfähigkeit von 75 S/cm.1. 19 parts of pyrrolaldehyde in 100 parts of methyl glycol at room temperature mixed with 5 parts of hydrazine hydrate and then after Worked up for 5 hours at 50 ° C. After vacuuming the Aldazin, 10 parts of sulfur are added to the reaction product and then subjected to the condensation at 120 ° C for 3 h. Arise 20.5 parts of dipropylthiadiazole, which after recrystallization decompose in chloroform at temp. 185 ° C. 2.0 parts of the above Dipropylthiadiazole are manufactured in an electrocell an electrolyte from acetonitrile with 10 wt .-% methylene chloride 2% by weight of phenylsulfonic acid are added and inside at room temperature of 2 hours at a current density of 2 mA / cm² at the anode (Platinum sheet 6 cm²) deposited. The distance from the anode to the counter electrode (also platinum sheet 6 cm²) was 2 cm. The received Polymer film which can be removed from the anode is black, 70 µm thick and has a spec. electrical conductivity of 75 S / cm.

2. Wie 1, aber unter Verwendung des entsprechenden N-Methylpropyl­ aldehydes (22 Teile), werden bei der Kondensation 20,5 Teile des Thia­ diazolderivates erhalten, das bei der anodischen Polymerisation einen Film mit einer Leitfähigkeit von 45 S/cm ergibt.2. As 1, but using the corresponding N-methylpropyl aldehyde (22 parts), 20.5 parts of the thia Obtained diazole derivatives that in the anodic polymerization Film with a conductivity of 45 S / cm results.

3. Wie 1, aber die Durchführung der elektrochemischen anodischen Oxi­ dation erfolgt in Gegenwart von NOSbF₆, an Stelle der Phenylsulfo­ säure. Es wird ein Polymerfilm von 70 µm Dicke mit einer spez. elektr. Leitfähigkeit von 105 S/cm erhalten. 3. Like 1, but carrying out the electrochemical anodic oxi dation takes place in the presence of NOSbF₆, instead of phenylsulfo acid. It is a polymer film of 70 microns thick with a spec. electr. Obtained conductivity of 105 S / cm.  

4. 12,3 Teile Pyrroldialdehyd werden in 40 Teilen Methylglykol und 40 Teilen Ethanol gelöst und dann bei Raumtemperatur unter Rühren 16 Teile Hydrazinhydrat zugefügt. Nach 1stündigem Erwärmen auf 70°C werden 19,2 Teile Schwefel sowie 1 Teil Triethylamin zugefügt und die Reaktionsmischung 15 Stunden bei 90°C gehalten, dann wird abgekühlt und das erhaltene Polymer abfiltriert und durch Waschen mit CS₂ von anhaftendem Schwefel befreit.4. 12.3 parts of pyrrole dialdehyde in 40 parts of methylglycol and 40 parts of ethanol dissolved and then at room temperature with stirring 16 parts of hydrazine hydrate added. After heating to 70 ° C for 1 hour 19.2 parts of sulfur and 1 part of triethylamine are added and the Reaction mixture kept at 90 ° C for 15 hours, then it is cooled and the polymer obtained is filtered off and washed with CS₂ by adhering sulfur freed.

Das erhaltene Polymere, 11,8 Teile, ist löslich in Dimethylformamid, das Festprodukt zersetzt sich größer 250°C.The polymer obtained, 11.8 parts, is soluble in dimethylformamide, the solid product decomposes above 250 ° C.

Wird eine 1%ige Dimethylformamidlösung als Elektrolyt eingesetzt entsprechend der im Beispiel 1 beschriebenen elektrochemischen Oxi­ dation, so wird ein Polymerfilm auf der Anode erhalten, der eine elektrische Leitfähigkeit von 25 S/cm aufweist.If a 1% dimethylformamide solution is used as the electrolyte corresponding to the electrochemical oxi described in Example 1 dation, a polymer film is obtained on the anode, the one has electrical conductivity of 25 S / cm.

Claims (6)

1. Polymere mit einer Grenzviskosität [η] von mindestens 0,5 dl/g, gemessen bei 25°C in N,N-Dimethylformamid, die wiederkehrende Strukturelemente der Formel I und II: enthalten, worin X = NH, S, O, P, As oder Sb.1. Polymers with an intrinsic viscosity [ η ] of at least 0.5 dl / g, measured at 25 ° C. in N, N-dimethylformamide, the recurring structural elements of the formula I and II: contain, where X = NH, S, O, P, As or Sb. 2. Polymere nach Anspruch 1, die aus wiederkehrenden Strukturelementen der Formel (I) oder (II) bestehen.2. Polymers according to claim 1, which consist of recurring structural elements of the formula (I) or (II). 3. Polymere nach Anspruch 1, dadurch gekennzeichnet, daß X = NH, S oder O.3. Polymers according to claim 1, characterized in that X = NH, S or O. 4. Verwendung der Polymeren nach Anspruch 1 für elektrisch leitfähige Systeme und Elektroden.4. Use of the polymers according to claim 1 for electrically conductive Systems and electrodes. 5. Verwendung der Polymeren nach Anspruch 1 als Dichtungs- oder Verpackungsmaterial.5. Use of the polymers according to claim 1 as a sealing or Packing material. 6. Verwendung der Polymeren nach Anspruch 1 für Sensoren.6. Use of the polymers according to claim 1 for sensors.
DE19873721534 1986-08-02 1987-06-30 Polymers containing thiadiazole groups, and the use thereof in the electrical industry Withdrawn DE3721534A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19873721534 DE3721534A1 (en) 1986-08-02 1987-06-30 Polymers containing thiadiazole groups, and the use thereof in the electrical industry

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3626226 1986-08-02
DE19873721534 DE3721534A1 (en) 1986-08-02 1987-06-30 Polymers containing thiadiazole groups, and the use thereof in the electrical industry

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DE3721534A1 true DE3721534A1 (en) 1988-02-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6809107B1 (en) * 1999-07-09 2004-10-26 Ortho-Mcneil Pharmaceutical, Inc. Neurotrophic pyrrolidines and piperidines, and related compositions and methods
CN111304685A (en) * 2019-03-08 2020-06-19 长沙理工大学 Method for preparing 1,2,4-thiadiazole framework and fused rings thereof through electrocatalysis

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6809107B1 (en) * 1999-07-09 2004-10-26 Ortho-Mcneil Pharmaceutical, Inc. Neurotrophic pyrrolidines and piperidines, and related compositions and methods
CN111304685A (en) * 2019-03-08 2020-06-19 长沙理工大学 Method for preparing 1,2,4-thiadiazole framework and fused rings thereof through electrocatalysis
CN111304685B (en) * 2019-03-08 2021-10-08 长沙理工大学 Method for preparing 1,2,4-thiadiazole framework and fused rings thereof through electrocatalysis

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