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
  • H01B1/14—Conductive material dispersed in non-conductive inorganic material
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

• the invention relates to composite materials made of electrically conductive materials and inorganic binders.
• Conductive polymers containing conjugated double bonds are known.
• Acetylene or acetylene compounds are polymerized under the action of certain Ziegler catalysts.
• Subsequent doping e.g. Electrically conductive polymers can be obtained electrochemically with electron acceptors or electron donors (US Pat. No. 4,204,216 and US Pat. No. 4,222,903).
• Electrically conductive polymers obtained by polymerizing 5-membered heterocycles which are pyrrole or thiophene, e.g. on A.F. Diaz et. al. J.C.S. Chem. Comm. 1979, page 634 ff and page 845 ff as well as from EP-OS 99 984.
• Another group of electrically conductive polymers are the conductive poly-p-phenylenes. These can e.g. are obtained by methods as described in J. Am. Chem. Soc. 1985 (1963) 454 ff and in J. Marcromol. SCI. C 5 (1971) page 295 ff.
• the task of the present inventions was to show composite materials made of electrically conductive materials and inorganic binders.
• composite materials which contain a p- or n-doped electrically conductive polymer as the electrically conductive material, which contains conjugated double bonds and forms a coherent phase.
• Such composite materials can preferably be used as heating elements, shielding materials or as probes.
• polymers which contain conjugated double bonds those polymers are particularly suitable which are obtained by electrochemical polymerization of compounds from the class of 5-membered heterocyclic compounds with conjugated ⁇ -electron system which contain nitrogen or sulfur as the hetero atom.
• Polymers from the class of pyrroles and thiophenes are advantageous.
• Substituted pyrroles such as n-alkyl pyrroles or monoalkyls or dihalogen substituted pyrroles, are also suitable.
• compounds from the class of thiophenes are also the 2- or the 3-, methylthiophene or the 2,3-diethylthiophene.
• the compounds can also be copolymerized together with other copolymerizable compounds, diazole or ocazole.
• the polymers are prepared by the known processes cited above. The polymerization is therefore advantageously carried out by anodic oxidation in an electrolyte solvent which contains conductive salts. Copolymers are obtained in which the conductive salt anions are bound; this is referred to as p-doped conductive polymers.
• the polymers of acetylene can be prepared in the same way. The method of preparation is described in the literature mentioned above. Those acetylene polymers which are described in EP 88 301 or in Synthetic Metals 5 (1982) p. 51 are advantageous. Stretched polymers are particularly suitable. Electrically conductive polymers such as poly-p-phenylenes are also suitable.
• the electrically conductive polymers are e.g. p-doped with conductive salt anions such as I ⁇ , ClO4 ⁇ , AsF6 ⁇ or n-doped with Li+, Na+, K+ or alkaline earth metal cations.
• the doping can be electrochemical or chemical.
• Inorganic binders are used to manufacture the composite materials.
• unhydraulic binders such as gypsum, Sorel cement or magnesia binders are used.
• Hydraulic binders such as cement, lime or water glass or other silicates, as well as borates, vanadates, titanates, ferates, cuprates or molybdates are advantageously used. Salts, selenium, sulfur or silicon are also suitable. More information on binders and cement can be found in Römpps Chemie Lexikon, 7th edition, pages 366 and 3 967.
• Coherent phases form, for example, foils, threads or wires, but it is also possible to use pressed moldings made from finely powdered polymers. It is also possible to use knitted fabrics, woven fabrics or disorderly poured layers of fibrous polymers. Also possible are: porous materials such as membranes with open cells or fleece. It is thus possible to produce composite materials that have a two-dimensional expansion and that contain the electrically conductive polymer as the core layer. However, it is also possible to produce composite materials that consist of only two layers, namely the polymer and the binder. Furthermore, many times layered composite materials are produced. However, it is also possible to produce composite materials that have a longitudinal expansion, the multiple of which relates to the transverse expansion. For example, these can be tapes, cables or ropes surrounded by the inorganic agent.
• the manufacturing conditions depend on the inorganic binder used. Care should be taken to ensure that temperatures during production are not exceeded at which the polymer may be damaged.
• the proportion of the electrically conductive polymer in the composite material is 0.001 to 0.1, preferably 0.001 to 0.1, part to 1 part of the binder.
• the composite materials can be used as probes, shielding materials or heating elements. However, they can also be used as electrical control elements or as electrodes.
• the film doped in this way has a conductivity of 2500 S / cm.
• the doped film is placed between 2 plates of potassium bromide, which have a thickness of 3 mm and are pressed at 300 bar.
• the acetylene film to be treated is placed between glass plates 3 mm thick and pressed at 300 bar and a temperature of 750 ° C.
• the composites obtained in this way can be used, for example, as probes.
• a polyacetylene film the doping of which is described in Example 1, is placed in water glass solution, removed from the solution and cured at 50 ° C. and a pressure of 0.1 tor. It forms a composite in which a polyacetylene film made of hardened water glass is embedded. This composite can be used as a control element.
• a compact is obtained in which the polypoly pyrrole particles are embedded in the sulfur and form a coherent phase. Such a compact can be used as a probe.
• Particles with a diameter of 1-2 mm are used, which consist of polypyrrole which is deposited on graphite particles.
• the conductivity of these particles is 1 S / cm.
• the particles are mixed with cement and water in a ratio of 1: 1: 3.
• the mixture is allowed to harden at 25 ° C for 3 days.
• the proportion of polypyrrole in the composite is 20% by weight.
• the polypyrrole particles form a coherent phase.
• polypyrrole fibers are embedded, which have a diameter of 1 mm, a length of 3 to 5 mm and a conductivity of 2 S / cm.
• a composite is obtained in which the polypropylene fibers form the coherent phase.
• a polypyrrole film with a thickness of 200 ⁇ m is placed in a cement mixture.
• the mixture is shaped so that the film is coated on both sides with a layer of 1 cm cement.
• the cement is allowed to harden and a composite is obtained in which the polypyrrole fraction has a conductivity of 10 -3 S / cm.
• Example 4 In a manner analogous to that described in Example 4, a polypropylene film with a thickness of 200 ⁇ m is embedded in plaster, so that the polypropylene film is coated on both sides with a layer of 5 mm. After curing, a composite is obtained. The conductivity of the polypyrrole film in the composite 150 S / cm.
• a composite element which contains a polyacetylene film which is n-doped with lithium anions.

Landscapes

• Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Conductive Materials (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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Publications (2)

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• 1986
  • 1986-04-26 DE DE19863614279 patent/DE3614279A1/de not_active Withdrawn
• 1987
  • 1987-04-08 US US07/035,729 patent/US4780246A/en not_active Expired - Fee Related
  • 1987-04-18 EP EP87105756A patent/EP0243830A3/fr not_active Withdrawn
  • 1987-04-22 JP JP62097668A patent/JPS63362A/ja active Pending

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