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

Definitions

• the invention relates to organic polymers, such as plastics and paints, with increased electrical conductivity.
• This increased electrical conductivity is achieved by adding a sulfur-containing pyropolymer, which was obtained by pyrolysis of a sulfur-containing condensation product from aromatic compounds, which may contain heterocyclic rings with O, S or N as heteroatoms, and sulfur or sulfur-donating compounds.
• inorganic conductive fillers For example, metals, alloys, metal oxides, metal sulfides, metallized fillers or carbon, preferably in the form of carbon black or graphite, are used as inorganic conductive fillers.
• the conductivity-increasing fillers are used in the form of powders, beads, fibers or flakes. These conductive fillers ha ben, however, the disadvantage that they must be used in order to achieve the desired electrical conductivity in amounts that lead to an impairment of the mechanical properties of the organic polymers.
• this special polyacetylene modification With this special polyacetylene modification, a useful increase in the conductivity of the organic polymer is achieved even with additions of 0.1% by weight.
• this special polyacetylene modification has the disadvantage that it is not stable and that the conductivity decreases considerably when exposed to air and often when the polyacetylene is incorporated into the molten plastics.
• DE-OS 3 324 768 discloses condensation products of aromatic compounds with sulfur or sulfur-releasing compounds which have an electrical conductivity.
• the conductivity of these condensation products is not sufficient for use as conductive fillers in organic polymers.
• these condensation products have the disadvantage that the addition can lead to a sharp increase in the viscosity of the polymer melts, so that these melts can no longer be processed.
• organic polymers with increased electrical conductivity which remains unchanged even over long periods of time, are obtained, which also conduct under the influence of air, heat and shear forces Ability to remain unchanged if a sulfur-containing pyropolymer is added to these organic polymers, which was obtained by pyrolysis of a sulfur-containing condensation product from aromatic compounds, which may contain heterocyclic rings with O, S or N as heteroatoms, and sulfur or sulfur-donating compounds.
• the invention therefore relates to organic polymers with increased electrical conductivity, which are characterized in that they contain a sulfur-containing pyropolymer, which is obtained by pyrolysis of a sulfur-containing condensation product from aromatic compounds which optionally contain heterocyclic rings with O, S or N as heteroatoms, and sulfur or sulfur-donating compounds was obtained.
• the sulfur-containing pyropolymers to be used according to the invention are preferably obtained by condensing an aromatic compound with, sulfur or sulfur-releasing compounds such as polysulfides in a known manner, optionally in the presence of a solvent, at temperatures of 80-500 ° in a first reaction step and the sulfur-containing condensation product obtained is pyrolyzed in a second reaction stage at temperatures of 500-2000 ° C.
• This thermal treatment increases the electrical conductivity of the sulfur-containing condensation products by several powers of ten.
• the obtained sulfur-containing pyropolymers usually have an electrical conductivity of> 10 ⁇ 2S / cm without doping (i.e. without being oxidized or reduced). They are also extremely stable chemically and thermally.
• the sulfur-containing condensation products to be used as starting compounds for the preparation of the sulfur-containing pyropolymers and their preparation are known, e.g. from EP-A2-0131189 or EP-A1-0037829 and US Pat. No. 4,375,427. Because of their easy accessibility, the sulfur-containing condensation products described in EP-A2-0131189 are preferred.
• Aromatic compounds which contain 2 -9 carbocyclic rings and optionally 1 -3 heterocyclic rings with O, S or N as hetero atom are particularly suitable as starting compounds for the preparation of the sulfur-containing condensation products; preferred are the condensation products from the easily accessible, polycondensed aromatics, such as anthracene, chrysene, pyrene and the easily accessible heteroaromatics, such as carbazole.
• Mixtures of aromatic compounds, such as those present in the distillation residues of technical products, for example from the production of anthracene, antrachinone or bisphenol, and in the distillation residues from cracking processes or from petroleum processing, can also be used as starting compounds.
• the sulfur-containing pyropolymers are obtained in the form of shiny black masses. These are crushed to the desired grain size using conventional means; this is usually less than 600 ⁇ ; the grain size of the pyropolymers is preferably in the range from 0.1 to 100 ⁇ m.
• Suitable organic polymers whose conductivity can be increased by the addition of the sulfur-containing pyropolymers according to the invention are thermoplastics, thermosets, elastomers and paints.
• thermoplastics polymers and copolymers of monoolefinically unsaturated monomers, for example high-pressure or low-pressure polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, and also as a copolymer with vinyl acetate, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic
• thermosets e.g. Reaction products of formaldehyde with phenol, cresols, urea, melamine or their mixtures or casting resins made from unsaturated polyesters, epoxies, polyurethanes or silicones.
• Suitable elastomers are, for example, natural rubber, optionally chlorinated or brominated polybutadiene, polyisoprene, isobutylene polymers, ethylene, propylene copolymers, sulfochlorinated polyethylene, elastomeric polyurethanes or silicone rubbers.
• Suitable varnishes whose conductivity can be increased by the addition of sulfur-containing pyropolymer according to the invention are both varnish systems which are drying or crosslinking at room temperature and stoving varnishes.
• the varnish systems to be used at room temperature include alkyd resins, unsaturated polyester resins, polyurethane resins, epoxy resins, modified fats and Oils, polymers or copolymers based on vinyl chloride, vinyl ether, vinyl ester, styrene, acrylic acid, acrylonitrile or acrylic ester, cellulose derivatives.
• the stoving lacquers are the lacquer systems which crosslink at higher temperatures, such as, for example, polyurethanes made of hydroxyl-containing polyethers, polyesters or Polyacrylates and masked polyisocyanates, melamine resins made of etherified melamine-formaldehyde resins and hydroxyl group-containing polyethers, polyesters or polyacrylates, epoxy resins made of polyepoxides and polycarboxylic acids, carboxyl group-containing polyacrylates and carboxyl group-containing polyesters, stoving lacquers made of polyester, polyester imides, polyester amide amides and polyamide imides, polyamideimides suitable. These stoving lacquers can usually be applied both as powder and from solution.
• the organic polymers to be finished according to the invention can also be in the form of copolymers, polymer blends or polymer alloys.
• the sulfur-containing pyropolymers can also be added to polymers that already show intrinsic electrical conductivity, e.g. Polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyphenylene vinylene, polyphthalocyanines or polyanilines.
• the intrinsically conductive polymers can be present in undoped or doped form. Suitable dopants are preferably oxidizing agents such as AsF5, SbCl5, FeCl3 or halogens, or reducing agents such as alkali metals, optionally as alkali naphthalide.
• the conductivity of the pyropolymers to be used according to the invention can be increased even further by treating the pyropolymers with chemical or physical methods.
• partial oxidation or reduction of the sulfur-containing pyropolymers can lead to high levels conductive intercalation connections are made.
• Suitable oxidizing agents are halogens such as fluorine, chlorine, bromine or iodine, metal chlorides such as FeCl3, AsF5, SbCl5, SbF5 or oxidizing acids such as HNO3 or H2SO4.
• the alkali and alkaline earth metals serve as reducing agents. Oxidation and reduction can also be carried out electrochemically in the presence of a suitable conductive salt.
• the pyropolymers to be used according to the invention can be incorporated into the organic polymers by methods customary for the incorporation of fillers into organic polymers.
• they can be mixed with thermoplastics by dry mixing and subsequent extrusion in a commercially available screw or directly in a screw by metering them in together.
• Pellets are preferably produced from the thermoplastic and the sulfur-containing pyropolymer in a first stage, which are then processed in a second stage to give the desired shaped articles.
• the pyropolymer can be stirred directly into the polymer solution and then homogenized, for example with a dissolver or a ball mill.
• the pyropolymer can also be dispersed in a suitable solvent and, if appropriate, additionally ground, and then the organic polymer, if appropriate dissolved in a suitable solvent, added and, if appropriate, homogenized again with suitable equipment.
• air that has been stirred in must be removed by suitable measures, for example applying a vacuum.
• Can be used to manufacture thermosets the pyropolymer is stirred directly into the liquid or melted mass and then comminuted and homogenized, for example with a dissolver or a ball mill. It is also possible to homogenize the pyropolymer and the thermosetting resin as a solution or suspension, the solvent having to be removed again, for example under reduced pressure, in a second operation.
• the organic polymers can contain conventional additives, such as fillers, pigments, antioxidants, UV stabilizers, hydrolysis stabilizers, plasticizers and / or other conductivity-increasing additives.
• the pyropolymers to be used according to the invention are usually used in amounts of 5-80% by weight, preferably 10-70% by weight, particularly preferably in amounts of 20-60% by weight, based on the total weight of the conductive polymer.
• a significant advantage of the pyropolymers to be used according to the invention over carbon black is the possibility of being able to incorporate even amounts above 30% by weight without any problems. Even the incorporation of 50% by weight of pyropolymer into thermoplastic materials does not pose any difficulties. Rather, the sulfur-containing pyropolymers to be used according to the invention have the surprising property that they not only improve the conductivity but - in contrast to carbon black, for example - also improve the mechanical properties of the organic polymers, for example of polyamides.
• the pyropolymer to be used according to the invention can also be used as a black pigment; if the temperature falls below a certain minimum amount, which may vary depending on the polymer system and processing conditions, the conductivity will no longer increase.
• the polymer compounds according to the invention show specific conductivities between 10 ⁇ 12 and 100 Siemens / cm. They can be used to manufacture antistatic, semiconducting or conductive plastic parts, foils or coatings. They are used as electrodes, for example in electrolysis cells or in batteries, as heat conductors, as non-rechargeable housings and for shielding electromagnetic waves.
• This condensation product is heated to 1000 ° C. in the face grinding cup described in Example 1 within 12 hours and kept at this temperature for 10 hours. 1461 g of pyropolymer containing sulfur are obtained in the form of a shiny metallic mass (specific conductivity: 14.3 S / cm; sulfur content: 7.4% by weight).
• This condensation product is heated for 7 hours at 350 ° C. in the flat ground cup made of quartz glass described for the heart position of the pyropolymer A. The mixture is then heated to 1000 ° C. in the course of 6 hours and kept at this temperature for 10 hours. 1364 g of pyropolymer containing sulfur are obtained in the form of a shiny metallic mass (conductivity: 12.8 S / cm; sulfur content: 7.8% by weight.)
• the table below shows the amounts of pyropolymer A used and the surface resistance of the polycarbonate films finished with the stated amounts of pyropolymer A.
• Elastomer's vinyl polybutadiene (made from butadiene1.2) is cooled to -80 ° C and comminuted in a granulating machine. 55 parts by weight of this granulate are mixed with 45 parts by weight of pyropolymer E (particle size: 5 - 25 ⁇ ). The mixture is pressed into a plate under a pressure of 450 kg / cm2. The elastomeric plate has a specific conductivity of 2.4 ⁇ 10 ⁇ 1 S / cm.
• 250 parts by weight of polypropylene are mixed with 750 parts by weight of pyropolymer A (particle size: ⁇ 65 ⁇ ) and processed into a strand in an extruder at 220 ° C.
• a plate made from this strand at 200 ° C and a pressure of 500 Kp / cm2 has a specific conductivity of 6.9 ⁇ 10 ⁇ 4 S / cm.
• 300 parts by weight of polymerized methyl methacrylate are mixed with 250 parts by weight of pyropolymer C (particle size: ⁇ 500 ⁇ ) mixed with 100 mg of bis (4-chlorobenzoyl) peroxide and then at 160 ° C. and a pressure of 570 Kp / cm2 pressed.
• the plate thus obtained has a specific conductivity of 8.7 ⁇ 10 ⁇ 1 S / cm.
• the table below shows the amounts of copolymer and pyropolymer used in the individual experiments and the specific conductivities of the polymer plates obtained from these components.
• the table below shows the amounts of pyropolymer A added and the surface resistance of the coatings obtained with these amounts.
• a plate made of 100 parts by weight of polyparaphenylene sulfide and 100 parts by weight of pyropolymer A (particle size: ⁇ 63 ⁇ ) (dimensions: 25 ⁇ 25 ⁇ 2 mm) was provided with 2 electrical contacts, coated with a polyhydantoin varnish and in a vessel covered with 50 g of water. After applying a DC voltage of 24 V / 30 V / 36 V, the water warms up to 47 ° C / 53 ° C / 56 ° C. I.e. the plate acted as a heating plate.
• 100 g of a liquid epoxy resin made from technical bisglycidyl hexahydrophthalate (epoxy value: 0.58) and 100 g of melted hexahydrophthalic anhydride are mixed with 100 g of pyropolymer C (particle size: ⁇ 63 ⁇ ) and mixed with 2 g of dimethylbenzylamine as a catalyst. After degassing, the mass is poured into a mold and heated to 80 ° C for 4 hours and then to 160 ° C for 16 hours.
• the cast resin molded body obtained in this way has a specific conductivity of 1.8 ⁇ 10 ⁇ 5 S / cm.
• 50 parts by weight of powdered pyropolymer A (particle size: ⁇ 63 ⁇ ) and 50 parts by weight of polyphenylene sulfide (Ryton P 4 from Phillips Petroleum Comp.) are first mixed mechanically with one another. This mixture is dried in vacuo at 130 ° C. and then melt-compounded at 330 ° C. using a twin-screw extruder (ZSK 32 from Werner & Pfleiderer). The melt strand emerging from the extruder is granulated after cooling. After predrying at 130 ° C. at a melt temperature of 340 ° C.
• round plates (diameter: 800 mm, thickness: 2 mm) are injected from the granules obtained in this way.
• the electrical resistance values of the round plates obtained in this way are: volume resistivity: 110 ⁇ ⁇ cm specific surface resistance: 560 ⁇

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 1985
  • 1985-11-29 DE DE19853542231 patent/DE3542231A1/de not_active Withdrawn
• 1986
  • 1986-11-18 US US06/932,077 patent/US4798686A/en not_active Expired - Fee Related
  • 1986-11-18 EP EP86115947A patent/EP0224174A3/fr not_active Withdrawn
  • 1986-11-25 JP JP61278896A patent/JPS62131068A/ja active Pending

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