EP0144600B1 - Fabrication d'une matière plastique - Google Patents

Fabrication d'une matière plastique 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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EP
European Patent Office
Prior art keywords
polymer
polar
polymer alloy
process according
polymers
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.)
Expired
Application number
EP84111886A
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German (de)
English (en)
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EP0144600A1 (fr
Inventor
Gert Dr. Dipl.-Chem. Weddigen
Josef Dr. Dipl.-Chem. Flatz
Conrad Dr. Dipl.-Phys. Schmidt
Robert Dr. Dipl.-Phys. Huber
Gerhard Pohsner
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.)
BBC Brown Boveri AG Germany
Original Assignee
Brown Boveri und Cie AG Germany
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Application filed by Brown Boveri und Cie AG Germany filed Critical Brown Boveri und Cie AG Germany
Priority to AT84111886T priority Critical patent/ATE26289T1/de
Publication of EP0144600A1 publication Critical patent/EP0144600A1/fr
Application granted granted Critical
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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
    • H01B1/121—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) - '.

Claims (10)

1. Procédé pour la préparation d'une matière plastique qui présente une conductivité définie, caractérisé par le fait qu'un alliage de polymères fusible et/ou soluble, composé d'au moins un polymère isolant et au moins un polymère conducteur, est formé de telle façon qu'une distribution homogène des deux composants polymères est obtenue dans l'alliage de polymères.
2. Procédé selon la revendication 1, caractérisé par le fait que le polymère isolant et le polymère conducteur sont mélangés l'un avec l'autre à un état fluide (fondu) et à une température qui se situe au voisinage de leurs températures de fusion, et que l'alliage de polymères est soumis immédiatement à la suite du traitement, ou est solidifié pour le stockage intermédiaire.
3. Procédé selon la revendication 1 ou 2, caractérisé par le fait que l'alliage de polymères est formé à partir d'un polymère isolant polaire ou non polaire et d'un polymère conducteur polaire ou non polaire.
4. Procédé selon la revendication 3, caractérisé par le fait que pour la formation de l'alliage de polymères, on utilise, en tant que polymère isolant polaire, du poly(chlorure de vinyle), du téréphta- late, de préférence du poly(téréphtalate de butylène), une matière résineuse époxyde, du polycarbonate, une matière résineuse polyuréthanne ou du polyamide.
5. Procédé selon la revendication 3, caractérisé par le fait que pour la formation de l'alliage de polymères, on utilise, en tant que polymère isolant non polaire, du polyéthylène, du polybutadiène, du polystyrène, des copolymères styrène/butadiène ou des copolymères styrène/butadiène/acrylonitrile.
6. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que pour la formation de l'alliage de polymères, on utilise des polymères conducteurs dont la conductivité est produite par des complexes de transfert de charge.
7. Procédé selon la revendication 6, caractérisé par le fait que pour la formation de l'alliage de polymères, on utilise des polymères polaires triarylmé- thane ou des copolymères non polaires à base d'acétylène et/ou de dérivés de l'acétylène, dopés avec des donneurs d'électrons et/ou des accepteurs d'électrons.
8. Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que pour la formation de l'alliage de polymères, on utilise de 5 à 10% en poids d'un polymère conducteur, par rapport au poids total de l'alliage de polymères, et que le reste est constitué d'un polymère isolant.
9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que lors de la préparation, on ajoute à l'alliage de polymères un additif reliant les chaînes des polymères polaires et des polymères non polaires.
10. Procédé selon la revendication 9, caractérisé par le fait que lors de la préparation, on ajoute à l'alliage de polymères des peroxydes en tant qu'additif.
EP84111886A 1983-10-13 1984-10-04 Fabrication d'une matière plastique Expired EP0144600B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84111886T ATE26289T1 (de) 1983-10-13 1984-10-04 Verfahren zur herstellung eines kunststoffes.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3337245 1983-10-13
DE19833337245 DE3337245A1 (de) 1983-10-13 1983-10-13 Verfahren zur herstellung eines kunststoffes

Publications (2)

Publication Number Publication Date
EP0144600A1 EP0144600A1 (fr) 1985-06-19
EP0144600B1 true EP0144600B1 (fr) 1987-04-01

Family

ID=6211732

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84111886A Expired EP0144600B1 (fr) 1983-10-13 1984-10-04 Fabrication d'une matière plastique

Country Status (5)

Country Link
US (1) US4670511A (fr)
EP (1) EP0144600B1 (fr)
JP (1) JPS60101150A (fr)
AT (1) ATE26289T1 (fr)
DE (2) DE3337245A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3422316C2 (de) * 1984-06-15 1986-11-20 Zipperling Kessler & Co (Gmbh & Co), 2070 Ahrensburg Verfahren zur Herstellung von verformbaren Polymerblends aus elektrisch leitfähigen organischen Polymeren und/oder organischen Leitern, Vorrichtung zur Durchführung des Verfahrens sowie Verwendung der Polymerblends
DE3524516A1 (de) * 1985-07-09 1987-01-22 Gore W L & Co Gmbh Bandkabel
DE3609137A1 (de) * 1986-03-19 1987-09-24 Basf Ag Filme aus elektrisch leitfaehigen polymeren sowie mit diesen filmen beschichtete elektrodenmaterialien
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 (fi) * 1990-03-30 1993-09-27 Neste Oy Foerfarande foer framstaellning av en elledande polymerprodukt
JPH0826231B2 (ja) * 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 導電性ポリマー材料及びその使用
FR2721747B1 (fr) * 1991-09-27 1996-07-19 Thomson Csf Procédé d'obtention de matériaux conducteurs composites à base de polymère conducteur, à propriétés diélectriques contrôlées.
US5629050A (en) * 1995-08-30 1997-05-13 The Dow Chemical Company Process for preparing coated articles

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (fr) * 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 (nl) * 1973-07-20 1975-01-22 Hercules Inc Werkwijze voor het vervaardigen van een gevormd voortbrengsel.
FI318074A (fr) * 1973-11-16 1975-05-17 Calgon Corp
US4033905A (en) * 1975-11-05 1977-07-05 Rca Corporation Method for increasing the conductivity of electrically resistive organic materials
DE3113331A1 (de) * 1981-04-02 1982-10-28 Bayer Ag, 5090 Leverkusen Kletten- bzw. faserfoermige, dotierte polyacetylenteilchen enthaltende thermoplastische kunststoffe und verfahren zu ihrer herstellung
DE3113329A1 (de) * 1981-04-02 1982-12-30 Bayer Ag, 5090 Leverkusen Kletten- oder faserfoermige, dotierte polyacetylenteilchen enthaltende flaechengebilde und fasern, und verfahren zu ihrer herstellung

Also Published As

Publication number Publication date
US4670511A (en) 1987-06-02
DE3462908D1 (en) 1987-05-07
DE3337245A1 (de) 1985-04-25
EP0144600A1 (fr) 1985-06-19
ATE26289T1 (de) 1987-04-15
JPS60101150A (ja) 1985-06-05

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