EP0144600B1 - Manufacture of a plastic material - Google Patents

Manufacture of a plastic material Download PDF

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Publication number
EP0144600B1
EP0144600B1 EP84111886A EP84111886A EP0144600B1 EP 0144600 B1 EP0144600 B1 EP 0144600B1 EP 84111886 A EP84111886 A EP 84111886A EP 84111886 A EP84111886 A EP 84111886A EP 0144600 B1 EP0144600 B1 EP 0144600B1
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Prior art keywords
polymer
polar
polymer alloy
process according
polymers
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German (de)
French (fr)
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EP0144600A1 (en
Inventor
Gert Dr. Dipl.-Chem. Weddigen
Josef Dr. Dipl.-Chem. Flatz
Conrad Dr. Dipl.-Phys. Schmidt
Robert Dr. Dipl.-Phys. Huber
Gerhard Pohsner
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BBC Brown Boveri AG Germany
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Brown Boveri und Cie AG Germany
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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
    • H01B1/121—Charge-transfer complexes

Definitions

  • the invention relates to a method for producing a plastic according to the preamble of patent claim 1.
  • Such plastics are suitable for the manufacture of housings and protective covers for electrical devices and for coating cladding elements for walls and furniture.
  • the specific electric conductivity in relation to the cross-section of the plastic is within a range in which the plastics material acts not as an insulator between 10- 14 and 10- 7 (ohm cm) - 1 freely selected can be. This makes it possible to maintain a sufficient insulating effect and at the same time to avoid static charges.
  • Commercial plastics have in contrast only an electrical bulk conductivity of 10- 15 to 10- 18 (Ohm x cm) - to 1.
  • an electrically conductive synthetic polymer is known. It is a nitrogen-containing polymer in which the electrical conductivity is achieved by the formation of charge transfer complexes.
  • the specific conductivity of this plastic is greater than that of the commercially available plastics, but no specific conductivity can be achieved in the range given above. Furthermore, this plastic is not suitable for further processing since it is neither soluble nor fusible.
  • the invention is therefore based on the object of specifying a method which can be used to produce a plastic which can be used for further processing, in particular for injection molding and casting, and whose specific conductivity can be set to a defined value.
  • the polymer alloy is formed from at least one polar or non-polar insulating polymer and at least one polar or non-polar conductive polymer.
  • the polymer components forming the base material are mixed with one another in the liquid state at a predeterminable temperature. Depending on the starting materials used, the mixing takes place during a heat treatment, preferably under a nitrogen atmosphere.
  • the plastic thus formed can be processed immediately.
  • the plastic according to the invention can, for example, be dissolved in acetone or in a chlorinated hydrocarbon to form a spray painting solution.
  • the ratio between solvent and plastic is preferably chosen in a ratio of 2: 1 to a ratio of 10: 1.
  • the polymer alloy which forms the plastic can contain, for example, polyvinyl chloride, terephthalate, an epoxy resin composition, polycarbonate, a polyurethane resin composition or polyamide as the insulating component.
  • polyvinyl chloride, terephthalate, an epoxy resin composition, polycarbonate, a polyurethane resin composition or polyamide as the insulating component.
  • polar insulating polymers instead of these polymers, polyethylene, polybutadiene, polystyrene, butadiene styrene copolymers or acrylonitrile-butadiene-styrene copolymers and mixtures thereof can also be used. These are non-polar insulating polymers.
  • a conductive polymer is used as the second component in the manufacture of the polymer alloy.
  • Polymers whose conductivity is achieved by charge transfer complexes are preferably used in the formation of the polymer alloy. The formation of these charge transfer complexes is achieved by adding electron donors and / or electron acceptors during the manufacture or further processing of the polymers.
  • a special example of this is a plastic that has triaromatomethane units as basic building blocks and is doped with sulfur trioxide (S0 3 ).
  • S0 3 sulfur trioxide
  • a copolymer of acetylene or of acetylene derivatives can also be used as the second component for producing the polymer alloy.
  • Polar or non-polar isolated polymers as well as polar and non-polar conductive polymers can be used to form the polymer alloy. If the production is carried out using a first component, which consists of a non-polar insulating polymer, while the second component is formed by a polar conductive polymer, then at least one additive which has the property of chains of non-polar must be added to the polymer alloy during the production Linking polymers with chains of polar polymers. In this case, according to the invention, an addition of 0.1 to 1% by weight, based on the total amount of the polymer alloy, is added to the base material. Peroxide is used here as a preferred additive, since this enables a CC connection to be achieved between a polar and a non-polar chain.
  • the method according to the invention can be used to produce polymer alloys which, when the mixing ratio between the two polymer components forming the polymer alloy described above is used, have a specific conductivity which is 3 ⁇ 10 ⁇ 9 (ohm ⁇ cm) ⁇ 1 .
  • the specific conductivity of these polymer alloys is thus about 5 orders of magnitude greater than that of the polymer components used for the production.
  • Plastics that are made from the polymer alloy according to the invention can also be processed into foils. They are also suitable for casting housings. Since the plastic according to the invention is not only meltable but also soluble If it is dissolved in acetone or a chlorinated hydrocarbon, it can be used to produce a spray painting solution. It can be used, for example, to produce coatings on housings for electrical devices. Another area of application for this plastic is in the area of record production. The plastic is also suitable as packaging material for integrated components.
  • the following example describes the production of the plastic according to the invention in the form of a film which has a specific conductivity of 3 ⁇ 10 ⁇ 9 (ohm ⁇ cm) ⁇ 1 .
  • Polyvinyl chloride is used as the polymer with insulating properties.
  • the conductive polymer used is one which has triaromatomethane units as the basic building blocks and which has been doped with sulfur trioxide in order to form charge-transfer complexes.
  • the production of this conductive polymer is described in DE-A1 - 3 248 088.
  • To produce a film from this plastic 2 kg of polyvinyl chloride and 0.2 kg of polytriaromatomethane doped with sulfur trioxide are dissolved in a solvent.
  • the solvent consists of 30 I tetrahydrofuran, 8 I acetone and 2 I ethanol.
  • the mixture of solutions is then heated and stirred at 35 degrees Celsius for 0.5 hours.
  • the liquid is then filtered. It can then be divided into several, for example 5, volumes from which the solvent is evaporated. After evaporation, films are formed which have a thickness of approximately 50 ⁇ m.
  • a liquid epoxy resin is used as the insulating polar polymer to produce the layer from the plastic according to the invention.
  • the conductive polymer component consists of polytriaromatomethane, which is doped with sulfur trioxide to form charge transfer complexes.
  • 1.3 kg of epoxy resin and 70 g of polytriaromatomethane doped with sulfur trioxide are mixed with one another under a nitrogen atmosphere at 50 degrees Celsius. After 20 minutes, the solid polytriaromatomethane is completely homogeneously dissolved in the liquid epoxy resin.
  • a second solution B is prepared in parallel with this solution A.
  • the hardener intended for the epoxy resin and polytriaromatomethane doped with sulfur trioxide are used for this.
  • the two substances are also mixed under a nitrogen atmosphere at 50 degrees Celsius.
  • the two solutions A and B are then mixed with one another with stirring at a temperature of 50 degrees Celsius.
  • the newly obtained solution C is poured between two graphite electrodes.
  • the polymer complex thus formed is then cured at a temperature of 110 degrees Celsius for 8 hours. After curing, a layer has formed from the plastic, which has the specific conductivity described above. This specific conductivity is 6 orders of magnitude greater than that of the pure epoxy resin molding material.
  • Polybutylene terephthalate is used here as the insulating polar polymer for the production of the plastic according to the invention.
  • 10 kg of polybutylene terephthalate and 0.5 kg of polar polytriaromatomethane doped with sulfur trioxide are mixed together under a nitrogen atmosphere.
  • the polymers are mixed at a temperature of 260 degrees Celsius, the mixture being constantly stirred.
  • the plastic formed in this way has a specific conductivity of 10- 11 (Ohm x cm) -1 . This specific conductivity is 5 orders of magnitude higher than that of pure polybutylene terephthalate.
  • the polyalloy is formed from 2 kg of a non-polar acetylene copolymer and 8 kg of a non-polar polyethylene. Both starting products are in powder or granule form. The two polymer components are heated to 200 to 300 degrees Celsius under a nitrogen atmosphere and mixed together by stirring. The solution thus formed is then cooled. To achieve the conductivity of the acetylene copolymer, 1 kg of iodine is added to the mixture. The iodine is added in a metal autoclave in which the polymer mixture is filled beforehand. The reaction with the iodine takes about 2 hours. The plastic obtained in this way has a specific conductivity of 10 -10 (Ohm x cm) - '.
  • Polar polyvinylchloride and polar polytriaromatomethane doped with sulfur trioxide are used for the production.
  • 6 kg of polyvinyl chloride in the form of granules are mixed with 1.5 kg of polytriaromatomethane doped with sulfur trioxide.
  • This mixture is then exposed to a temperature of 190 degrees Celsius under vacuum for 3 hours.
  • the melt that forms is very homogeneous. This homogeneity remains in the finished plastic even after cooling.
  • the specific conductivity of this plastic is 10- 9 (Ohm x cm) - '.

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Abstract

Method for manufacturing a conductive plastic of a defined conductivity by forming a polymer alloy. A polar or nonpolar insulating polymer and a polar or nonpolar conductive polymer are used for forming the polymer alloy. The two polymers are mixed together and they are homogeneously distributed within the polymer alloy.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung eines Kunststoffes gemäss dem Oberbegriff des Patentanspruches 1.The invention relates to a method for producing a plastic according to the preamble of patent claim 1.

Solche Kunststoffe sind zur Herstellung von Gehäusen und Schutzüberzügen von elektrischen Geräten sowie zur Beschichtung von Verkleidungselementen für Wände und Möbel geeignet.Such plastics are suitable for the manufacture of housings and protective covers for electrical devices and for coating cladding elements for walls and furniture.

In der Elektrotechnik besteht ein grosser Bedarf an Polymeren, deren spezifische elektrische Leitfähigkeit bezogen auf den Querschnitt des Kunststoffes innerhalb eines Bereiches, in dem der Kunststoff noch als Isolator wirkt, zwischen 10-14 und 10-7 (Ohm x cm)-1 frei gewählt werden kann. Hierdurch ist es möglich, noch eine ausreichende lsolierwirkung aufrecht zu erhalten, und gleichzeitig statische Aufladungen zu vermeiden. Handelsübliche Kunststoffe weisen im Gegensatz dazu nur eine elektrische Volumenleitfähigkeit von 10-15 bis 10-18 (Ohm x cm)-1 auf.In electrical engineering, there is a great need for polymers, the specific electric conductivity in relation to the cross-section of the plastic is within a range in which the plastics material acts not as an insulator between 10- 14 and 10- 7 (ohm cm) - 1 freely selected can be. This makes it possible to maintain a sufficient insulating effect and at the same time to avoid static charges. Commercial plastics have in contrast only an electrical bulk conductivity of 10- 15 to 10- 18 (Ohm x cm) - to 1.

Aus der GB-PS 1 067 260 ist ein elektrisch leitendes synthetisches Polymer bekannt. Es handelt sich um ein stickstoffhaltiges Polymer, bei dem die elektrische Leitfähigkeit durch die Bildung von Charge-Transfer-Komplexen erzielt wird. Die spezifische Leitfähigkeit dieses Kunststoffes ist grösser als die der handelsüblichen Kunststoffe, jedoch kann hierbei noch keine spezifische Leitfähigkeit in dem oben angegebenen Bereich erzielt werden. Ferner ist dieser Kunststoff für die Weiterverarbeitung nicht geeignet, da er weder löslich noch schmelzbar ist.From GB-PS 1 067 260 an electrically conductive synthetic polymer is known. It is a nitrogen-containing polymer in which the electrical conductivity is achieved by the formation of charge transfer complexes. The specific conductivity of this plastic is greater than that of the commercially available plastics, but no specific conductivity can be achieved in the range given above. Furthermore, this plastic is not suitable for further processing since it is neither soluble nor fusible.

Der Erfindung liegt deshalb die Aufgabe zugrunde ein Verfahren anzugeben, mit dem ein Kunststoff hergestellt werden kann, der sich für die Weiterverarbeitung, insbesondere zum Spritzen und Giessen verwenden lässt, und dessen spezifische Leitfähigkeit auf einen definierten Wert eingestellt werden kann.The invention is therefore based on the object of specifying a method which can be used to produce a plastic which can be used for further processing, in particular for injection molding and casting, and whose specific conductivity can be set to a defined value.

Diese Aufgabe wird erfindungsgemäss durch die kennzeichnenden Merkmale des Patentanspruches 1 gelöst.According to the invention, this object is achieved by the characterizing features of patent claim 1.

Erfindungsgemäss wird die Polymerlegierung aus wenigstens einem polaren oder nichtpolaren isolierenden Polymer und mindestens einem polaren oder nichtpolaren leitfähigen Polymer gebildet. Zur Herstellung der Polymerlegierung werden die das Basismaterial bildenden Polymerkomponenten im flüssigen Zustand bei einer vorgebbaren Temperatur miteinander vermischt. Das Vermischen erfolgt, je nachdem, welche Ausgangsstoffe verwendet werden, während einer Wärmebehandlung, und zwar bevorzugt unter einer Stickstoffatmosphäre. Der so gebildete Kunststoff kann sofort weiterverarbeitet werden. Es besteht andererseits auch die Möglichkeit, den Kunststoff für eine Zwischenlagerung zu verfertigen, so dass er zu einem späteren Zeitpunkt für die Weiterverarbeitung verwendet werden kann. Da der erfindungsgemässe Kunststoff sowohl löslich als auch schmelzbar ist, ist eine spätere Weiterverarbeitung problemlos möglich. Der erfindungsgemässe Kunststoff kann beispielsweise zur Bildung einer Spritzlackierlösung in Aceton oder in einem chlorierten Kohlenwasserstoff gelöst werden. Vorzugsweise wird hierbei das Verhältnis zwischen Lösungsmittel und Kunststoff in einem Verhältnis von 2 : 1 bis zu einem Verhältnis von 10 : 1 gewählt.According to the invention, the polymer alloy is formed from at least one polar or non-polar insulating polymer and at least one polar or non-polar conductive polymer. To produce the polymer alloy, the polymer components forming the base material are mixed with one another in the liquid state at a predeterminable temperature. Depending on the starting materials used, the mixing takes place during a heat treatment, preferably under a nitrogen atmosphere. The plastic thus formed can be processed immediately. On the other hand, it is also possible to manufacture the plastic for intermediate storage, so that it can be used for further processing at a later date. Since the plastic according to the invention is both soluble and meltable, subsequent processing is possible without any problems. The plastic according to the invention can, for example, be dissolved in acetone or in a chlorinated hydrocarbon to form a spray painting solution. The ratio between solvent and plastic is preferably chosen in a ratio of 2: 1 to a ratio of 10: 1.

Die Polymerlegierung, welche den Kunststoff bildet, kann als isolierende Komponente beispielsweise Polyvinylchlorid, Terephthalat, eine Epoxidharzmasse, Polycarbonat, eine Polyurethanharzmasse oder Polyamid enthalten. Es handelt sich hierbei insbesondere um polare isolierende Polymere. Anstelle dieser Polymere können auch Polyäthylen, Polybutadien, Polystyrol, Butadienstyrolcopolymere oder Acrylnitril-Butadien-Styrol-Copolymere und deren Gemische verwendet werden. Es handelt sich hierbei um nichtpolare isolierende Polymere.The polymer alloy which forms the plastic can contain, for example, polyvinyl chloride, terephthalate, an epoxy resin composition, polycarbonate, a polyurethane resin composition or polyamide as the insulating component. These are in particular polar insulating polymers. Instead of these polymers, polyethylene, polybutadiene, polystyrene, butadiene styrene copolymers or acrylonitrile-butadiene-styrene copolymers and mixtures thereof can also be used. These are non-polar insulating polymers.

Als zweite Komponente wird bei der Herstellung der Polymerlegierung ein leitfähiges Polymer benutzt. Bevorzugt werden bei der Bildung der Polymerlegierung Polymere verwendet, deren Leitfähigkeit durch Charge-Transfer-Komplexe erzielt wird. Die Bildung dieser Charge-Transfer-Komplexe wird durch die Zugabe von Elektronendonatoren und/oder Elektronenakzeptoren bei der Herstellung oder Weiterverarbeitung der Polymere erzielt. Ein spezielles Beispiel hierfür ist ein Kunststoff, der Triaromatmethaneinheiten als Grundbausteine aufweist und mit Schwefeltrioxid (S03) dotiert ist. Anstelle dieses Kunststoffes kann auch ein Copolymer aus Acetylen oder aus Acetylenderivaten als zweite Komponente zur Herstellung der Polymerlegierung verwendet werden.A conductive polymer is used as the second component in the manufacture of the polymer alloy. Polymers whose conductivity is achieved by charge transfer complexes are preferably used in the formation of the polymer alloy. The formation of these charge transfer complexes is achieved by adding electron donors and / or electron acceptors during the manufacture or further processing of the polymers. A special example of this is a plastic that has triaromatomethane units as basic building blocks and is doped with sulfur trioxide (S0 3 ). Instead of this plastic, a copolymer of acetylene or of acetylene derivatives can also be used as the second component for producing the polymer alloy.

Zur Bildung der Polymerlegierung können polare oder nichtpolare isolierte Polymere sowie polare und nichtpolare leitende Polymere benutzt werden. Erfolgt die Herstellung unter Verwendung einer ersten Komponente, die aus einem nichtpolaren isolierenden Polymer besteht, während die zweite Komponente durch ein polares leitendes Polymer gebildet wird, so muss der Polymerlegierung bei der Herstellung mindestens ein Zusatz beigemischt werden, welcher die Eigenschaft besitzt, Ketten von nichtpolaren Polymeren mit Ketten von polaren Polymeren zu verknüpfen. Erfindungsgemäss wird in diesem Fall ein Zusatz von 0,1 bis 1 Gew.-% bezogen auf die Gesamtmenge der Polymerlegierung dem Basismaterial beigemischt. Als bevorzugter Zusatz wird hier Peroxid verwendet, da hierdurch eine C-C-Verbindung zwischen jeweils einer polaren und einer nichtpolaren Kette erzielt werden kann. Hierdurch wird das bei solchen unterschiedlichen Polymeren vorhandene Bestreben auseinanderdiffundieren zu wollen, vollständig ausgeschlossen. Mit dem erfindungsgemässen Verfahren können Polymerlegierungen hergestellt werden, die bei Anwendung des eingangs beschriebenen Mischungsverhältnisses zwischen den beiden die Polymerlegierung bildenden Polymerkomponenten eine spezifische Leitfähigkeit aufweisen, welche 3 x 10-9 (Ohm x cm)-1 beträgt. Die spezifische Leitfähigkeit dieser Polymerlegierungen ist damit um etwa 5 Zehnerpotenzen grösser als die der Polymerkomponenten, welche für die Herstellung verwendet werden.Polar or non-polar isolated polymers as well as polar and non-polar conductive polymers can be used to form the polymer alloy. If the production is carried out using a first component, which consists of a non-polar insulating polymer, while the second component is formed by a polar conductive polymer, then at least one additive which has the property of chains of non-polar must be added to the polymer alloy during the production Linking polymers with chains of polar polymers. In this case, according to the invention, an addition of 0.1 to 1% by weight, based on the total amount of the polymer alloy, is added to the base material. Peroxide is used here as a preferred additive, since this enables a CC connection to be achieved between a polar and a non-polar chain. This completely eliminates the desire to diffuse existing with such different polymers. The method according to the invention can be used to produce polymer alloys which, when the mixing ratio between the two polymer components forming the polymer alloy described above is used, have a specific conductivity which is 3 × 10 −9 (ohm × cm) −1 . The specific conductivity of these polymer alloys is thus about 5 orders of magnitude greater than that of the polymer components used for the production.

Kunststoffe, die aus der erfindungsgemässen Polymerlegierung gefertigt sind, können zu Folien mitverarbeitet werden. Ferner snd sie zum Giessen von Gehäusen geeignet. Da der erfindungsgemässe Kunststoff nicht nur schmelzbar sondern auch löslich ist, kann aus ihm, wenn er in Aceton oder einem chlorierten Kohlenwasserstoff gelöst wird, eine Spritzlackierlösung hergestellt werden. Mit ihr können, z.B. Überzüge auf Gehäuse von elektrischen Geräten hergestellt werden. Ein weiteres Anwendungsgebiet dieses Kunststoffes liegt im Bereich der Schallplattenherstellung. Als Verpackungsmaterial für integrierte Bausteine ist der Kunststoff ebenfalls geeignet.Plastics that are made from the polymer alloy according to the invention can also be processed into foils. They are also suitable for casting housings. Since the plastic according to the invention is not only meltable but also soluble If it is dissolved in acetone or a chlorinated hydrocarbon, it can be used to produce a spray painting solution. It can be used, for example, to produce coatings on housings for electrical devices. Another area of application for this plastic is in the area of record production. The plastic is also suitable as packaging material for integrated components.

Die Herstellung des erfindungsgemässen leitfähigen Kunststoffes wird nachfolgend anhand von Ausführungsbeispielen erläutert.The production of the conductive plastic according to the invention is explained below using exemplary embodiments.

Beispiel 1example 1

In dem nachfolgenden Beispiel wird die Herstellung des erfindungsgemässen Kunststoffes in Form einer Folie, die eine spezifische Leitfähigkeit von 3 x 10-9 (Ohm x cm)-1 aufweist, beschrieben. Als Polymer mit isolierenden Eigenschaften wird hier Polyvinylchlorid verwendet. Als leitfähiges Polymer wird ein solches benutzt, das Triaromatmethaneinheiten als Grundbausteine aufweist, und das zur Bildung von Charge-Transfer-Komplexen bei seiner Herstellung mit Schwefeltrioxid dotiert wurde. Die Herstellung dieses leitfähigen Polymers ist in DE-A1 - 3 248 088 beschrieben. Zur Herstellung einer Folie aus diesem Kunststoff werden 2 kg Polyvinylchlorid und 0,2 kg mit Schwefeltrioxid dotiertes Polytriaromatmethan in einem Lösungmittel gelöst. Das Lösungsmittel besteht aus 30 I Tetrahydrofuran, 8 I Aceton und 2 I Äthanol. Anschliessend wird das Lösungsgemisch bei 35 Grad Celsius 0,5 Stunden erwärmt und gerührt. Daraufhin wird die Flüssigkeit gefiltert. Sie kann anschliessend in mehrere, beispielsweise 5 Volumen aufgeteilt werden, aus denen das Lösungsmittel abgedampft wird. Nach dem Abdampfen kommt es zur Ausbildung von Folien, die eine Dicke von etwa 50 µm aufweisen.The following example describes the production of the plastic according to the invention in the form of a film which has a specific conductivity of 3 × 10 −9 (ohm × cm) −1 . Polyvinyl chloride is used as the polymer with insulating properties. The conductive polymer used is one which has triaromatomethane units as the basic building blocks and which has been doped with sulfur trioxide in order to form charge-transfer complexes. The production of this conductive polymer is described in DE-A1 - 3 248 088. To produce a film from this plastic, 2 kg of polyvinyl chloride and 0.2 kg of polytriaromatomethane doped with sulfur trioxide are dissolved in a solvent. The solvent consists of 30 I tetrahydrofuran, 8 I acetone and 2 I ethanol. The mixture of solutions is then heated and stirred at 35 degrees Celsius for 0.5 hours. The liquid is then filtered. It can then be divided into several, for example 5, volumes from which the solvent is evaporated. After evaporation, films are formed which have a thickness of approximately 50 μm.

Beispiel 2Example 2

Nachfolgend wird die Herstellung einer Schicht mit einer spezifischen Leitfähigkeit von 10-12 (Ohm x cm)-' beschrieben. Zur Herstellung der Schicht aus dem erfindungsgemässen Kunststoff wird als isolierendes polares Polymer ein flüssiges Epoxidharz verwendet. Die leitfähige Polymerkomponente besteht aus Polytriaromatmethan, das zur Bildung von Charge-Transfer-Komplexen mit Schwefeltrioxid dotiert ist. Erfindungsgemäss werden 1,3 kg Epoxidharz und 70 g mit Schwefeltrioxid dotiertes Polytriaromatmethan unter einer Stickstoffatmosphäre bei 50 Grad Celsius miteinander vermischt. Nach 20 Minuten ist das feste Polytriaromatmethan in dem flüssigen Epoxidharz vollständig homogen aufgelöst. Parallel zu dieser Lösung A wird einen zweite Lösung B angesetzt. Hierfür wird der für das Epoxidharz vorgesehene Härter und mit Schwefeltrioxid dotiertes Polytriaromatmethan verwendet. Vorzugsweise werden zur Ausbildung der Lösung 1 kg Härter und 50 g Polytriaromatmethan, das mit Schwefeltrioxid dotiert ist, verwendet. Die Vermischung der beiden Stoffe erfolgt ebenfalls unter einer Stickstoffatmosphäre bei 50 Grad Celsius. Anschliessend werden beide Lösungen A und B unter Rühren bei einer Temperatur von 50 Grad Celsius miteinander vermischt. Die neugewonnene Lösung C wird zwischen zwei Graphitelektroden gegossen. Anschliessend wird der so gebildete Polymerkomplex bei einer Temperatur von 110 Grad Celsius während einer Zeit von 8 Stunden ausgehärtet. Nach dem Aushärten hat sich aus dem Kunststoff eine Schicht gebildet, welche die eingangs beschriebene spezifische Leitfähigkeit aufweist. Diese spezifische Leitfähigkeit ist um 6 Zehnerpotenzen grösser als die des reinen Epoxidharzformstoffes.The following describes the production of a layer with a specific conductivity of 10-12 (Ohm x cm) - '. A liquid epoxy resin is used as the insulating polar polymer to produce the layer from the plastic according to the invention. The conductive polymer component consists of polytriaromatomethane, which is doped with sulfur trioxide to form charge transfer complexes. According to the invention, 1.3 kg of epoxy resin and 70 g of polytriaromatomethane doped with sulfur trioxide are mixed with one another under a nitrogen atmosphere at 50 degrees Celsius. After 20 minutes, the solid polytriaromatomethane is completely homogeneously dissolved in the liquid epoxy resin. A second solution B is prepared in parallel with this solution A. The hardener intended for the epoxy resin and polytriaromatomethane doped with sulfur trioxide are used for this. Preferably 1 kg of hardener and 50 g of polytriaromatomethane doped with sulfur trioxide are used to form the solution. The two substances are also mixed under a nitrogen atmosphere at 50 degrees Celsius. The two solutions A and B are then mixed with one another with stirring at a temperature of 50 degrees Celsius. The newly obtained solution C is poured between two graphite electrodes. The polymer complex thus formed is then cured at a temperature of 110 degrees Celsius for 8 hours. After curing, a layer has formed from the plastic, which has the specific conductivity described above. This specific conductivity is 6 orders of magnitude greater than that of the pure epoxy resin molding material.

Beispiel 3Example 3

Für die Herstellung des erfindungsgemässen Kunststoffes wird hier als isolierendes polares Polymer Polybutylenterephthalat verwendet. Erfindungsgemäss werden 10 kg Polybutylenterephthalat und 0,5 kg mit Schwefeltrioxid dotiertes polares Polytriaromatmethan unter einer Stickstoffatmosphäre miteinandner vermischt. Das Vermischen der Polymere erfolgt bei einer Temperatur von 260 Grad Celsius, wobei die Mischung ständig gerührt wird. Der hierdurch gebildete Kunststoff weist eine spezifische Leitfähigkeit von 10-11 (Ohm x cm)-1 auf. Diese spezifische Leitfähigkeit liegt um 5 Zehnerpotenzen höher als die des reinen Polybutylenterephthalates.Polybutylene terephthalate is used here as the insulating polar polymer for the production of the plastic according to the invention. According to the invention, 10 kg of polybutylene terephthalate and 0.5 kg of polar polytriaromatomethane doped with sulfur trioxide are mixed together under a nitrogen atmosphere. The polymers are mixed at a temperature of 260 degrees Celsius, the mixture being constantly stirred. The plastic formed in this way has a specific conductivity of 10- 11 (Ohm x cm) -1 . This specific conductivity is 5 orders of magnitude higher than that of pure polybutylene terephthalate.

Beispiel 4Example 4

Die Polylegierung wird aus 2 kg eines nichtpolaren Acetylencopolymers und 8 kg eines nichtpolaren Polyäthylens gebildet. Beide Ausgangsprodukte liegen in Pulver- oder Granulatform vor. Die beiden Polymerkomponenten werden unter einer Stickstoffatmosphäre auf 200 bis 300 Grad Celsius erwärmt und miteinander durch Rühren vermischt. Anschliessend wird die so gebildete Lösung abgekühlt. Um die Leitfähigkeit des Acetylencopolymers zu erreichen, werden dem Gemisch 1 kg Jod zugesetzt. Die Zugabe des Jods erfolgt in einem Metallautoklaven, in welchen das Polymergemisch zuvor gefüllt wird. Die Umsetzung mit dem Jod dauert etwa 2 Stunden. Der so gewonnene Kunststoff weist eine spezifische Leitfähigkeit von 10-10 (Ohm x cm)-' auf.The polyalloy is formed from 2 kg of a non-polar acetylene copolymer and 8 kg of a non-polar polyethylene. Both starting products are in powder or granule form. The two polymer components are heated to 200 to 300 degrees Celsius under a nitrogen atmosphere and mixed together by stirring. The solution thus formed is then cooled. To achieve the conductivity of the acetylene copolymer, 1 kg of iodine is added to the mixture. The iodine is added in a metal autoclave in which the polymer mixture is filled beforehand. The reaction with the iodine takes about 2 hours. The plastic obtained in this way has a specific conductivity of 10 -10 (Ohm x cm) - '.

Beispiel 5Example 5

Für die Herstellung wird hierbei polares Polyvinylchlorid und mit Schwefeltrioxid dotiertes polares Polytriaromatmethan verwendet. Hierfür werden 6 kg Polyvinylchlorid in Form von Granulaten mit 1,5 kg mit Schwefeltrioxid dotiertem Polytriaromatmethan vermischt. Anschliessend wird dieses Gemisch unter Vakuum 3 Stunden lang einer Temperatur von 190 Grad Celsius ausgesetzt. Die sich bildende Schmelze ist sehr homogen. Diese Homogenität bleibt auch nach dem Abkühlen in dem fertigen Kunststoff erhalten. Die spezifische Leitfähigkeit dieses Kunststoffes beträgt 10-9 (Ohm x cm)-'.Polar polyvinylchloride and polar polytriaromatomethane doped with sulfur trioxide are used for the production. For this purpose, 6 kg of polyvinyl chloride in the form of granules are mixed with 1.5 kg of polytriaromatomethane doped with sulfur trioxide. This mixture is then exposed to a temperature of 190 degrees Celsius under vacuum for 3 hours. The melt that forms is very homogeneous. This homogeneity remains in the finished plastic even after cooling. The specific conductivity of this plastic is 10- 9 (Ohm x cm) - '.

Claims (10)

1. Process for the preparation of a plastic having a defined conductivity, characterized in that a fusible and/or soluble polymer alloy is formed from at least one insulating polymer and at least one conductive polymer in such a way that a homogeneous distribution of the two polymer components in the polymer alloy is obtained.
2. Process according to Claim 1, characterized in that the insulating polymers and the conductive polymers are mixed with one another in a liquid (molten) state and at a temperature near to their melting points, and that the polymer alloy is immediately processed further or solidified for temporary storage.
3. Process according to Claim 1 or 2, characterized in that the polymer alloy is formed from a polar or non-polar insulating polymer and a polar or non-polar conductive polymer.
4. Process according to Claim 3, characterized in that, to form the polymer alloy, polyvinyl chloride, a terephthalate, preferably polybutylene terephthalate, an epoxide resin composition, a polycarbonate, a polyurethane resin composition or a polyamide is used as the polar insulating polymer.
5. Process according to Claim 3, characterized in that, to form the polymer alloy, polyethylene, polybutadiene, polystyrene, butadiene/styrene copolymers or acrlyonitrile/butadiene/styrene copolymers are used as the non-polar insulating polymer.
6. Process according to one of Claims 1 to 3, characterized in that, to form the polymer alloy, conductive polymers are used, the conductivity of which is generated by charge transfer complexes.
7. Process according to Claim 6, characterized in that, to form the polymer alloy, polar triarylmethane polymers or non-polar copolymers of acetylene and/ or acetylene derivatives are used, which are in each case doped with electron donors and/or electron acceptors.
8. Process according to one of Claims 1 to 7, characterized in that, to form the polymer alloy, 5 to 10% by weight of a conductive polymer, relative to the total weight of the polymer alloy, are used and that the remainder consists of an insulating polymer.
9. Process according to one of Claims 1 to 8, characterized in that, during the preparation, and additive which links the chains of polar and non-polar polymers is admixed to the polymer alloy.
10. Process according to Claim 9, characterized in that, during the preparation, peroxides are admixed as an additive to the polymer alloy.
EP84111886A 1983-10-13 1984-10-04 Manufacture of a plastic material Expired EP0144600B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84111886T ATE26289T1 (en) 1983-10-13 1984-10-04 PROCESS FOR THE PRODUCTION OF A PLASTIC.

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DE3337245 1983-10-13
DE19833337245 DE3337245A1 (en) 1983-10-13 1983-10-13 METHOD FOR PRODUCING A PLASTIC

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EP0144600B1 true EP0144600B1 (en) 1987-04-01

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DE3422316C2 (en) * 1984-06-15 1986-11-20 Zipperling Kessler & Co (Gmbh & Co), 2070 Ahrensburg Process for the production of deformable polymer blends from electrically conductive organic polymers and / or organic conductors, device for carrying out the process and use of the polymer blends
DE3524516A1 (en) * 1985-07-09 1987-01-22 Gore W L & Co Gmbh BAND CABLE
DE3609137A1 (en) * 1986-03-19 1987-09-24 Basf Ag FILMS OF ELECTRICALLY CONDUCTIVE POLYMERS AND ELECTRODE MATERIALS COATED WITH THESE FILMS
GB8622752D0 (en) * 1986-09-22 1986-10-29 Shell Int Research Conductive polymer compositions
US5188783A (en) * 1990-02-20 1993-02-23 Hughes Aircraft Company Method of making articles containing an ion-conductive polymer
FI89377C (en) * 1990-03-30 1993-09-27 Neste Oy Process for preparing an conductive polymer product
JPH0826231B2 (en) * 1991-08-16 1996-03-13 インターナショナル・ビジネス・マシーンズ・コーポレイション Conductive polymer material and its use
FR2721747B1 (en) * 1991-09-27 1996-07-19 Thomson Csf Process for obtaining composite conductive materials based on conductive polymer, with controlled dielectric properties.
US5629050A (en) * 1995-08-30 1997-05-13 The Dow Chemical Company Process for preparing coated articles

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US3211714A (en) * 1960-11-25 1965-10-12 Air Reduction Polymerization of acetylenic compounds
US3256260A (en) * 1961-10-02 1966-06-14 Ethyl Corp Polymerization of acetylenic hydrocarbons
FR2017942A1 (en) * 1969-05-13 1970-05-29 Eastman Kodak Co
US3904929A (en) * 1972-11-10 1975-09-09 Kohkoku Chemical Ind Co Electro-discharging sheet, and an electro-discharging apparatus provided with an electro-discharging electrode composed of the said sheet, and a process for electro-discharging with the said apparatus
NL7407437A (en) * 1973-07-20 1975-01-22 Hercules Inc PROCEDURE FOR MANUFACTURE OF A MOLDED PRODUCT.
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DE3113329A1 (en) * 1981-04-02 1982-12-30 Bayer Ag, 5090 Leverkusen CLIMBED OR FIBER-SHAPED, DOPED POLYACETYLENE PARTICLES CONTAINING SURFACES AND FIBERS, AND METHOD FOR THEIR PRODUCTION

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ATE26289T1 (en) 1987-04-15
DE3337245A1 (en) 1985-04-25
EP0144600A1 (en) 1985-06-19
JPS60101150A (en) 1985-06-05
DE3462908D1 (en) 1987-05-07

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