WO1990009027A1 - Use of electrically conducting polymer composites - Google Patents

Use of electrically conducting polymer composites Download PDF

Info

Publication number
WO1990009027A1
WO1990009027A1 PCT/FI1990/000027 FI9000027W WO9009027A1 WO 1990009027 A1 WO1990009027 A1 WO 1990009027A1 FI 9000027 W FI9000027 W FI 9000027W WO 9009027 A1 WO9009027 A1 WO 9009027A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
conducting
moulding
poly
products
Prior art date
Application number
PCT/FI1990/000027
Other languages
French (fr)
Inventor
Jan-Erik Österholm
Jukka Laakso
Per Nyholm
Tapani Taka
Sari Karjalainen
Pirjo Mononen
Original Assignee
Neste Oy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Neste Oy filed Critical Neste Oy
Publication of WO1990009027A1 publication Critical patent/WO1990009027A1/en

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0079—Electrostatic discharge protection, e.g. ESD treated surface for rapid dissipation of charges
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the invention relates to the use of such electrically con ⁇ ducting polymer composites, which are made of a polymer matrix or a polymer substrate, intrinsically conducting, doped or undoped poly(3-substituted thiophene) and possibly additives for plastics.
  • Electrically conducting polymer materials can be roughly divided into two different categories: filled electrically conducting polymer materials and intrinsically electrically conducting polymer materials.
  • the former are composites, which consist of an electrically nonconductive polymer matrix or substrate and into which has been mixed or onto which has been layered an electrically conducting material.
  • these composites have as elect ⁇ rically conducting material carbon black, carbon fibers, metal flakes or metal fibers, which have been mixed into the matrix material in the melt state or layered onto the surfa ⁇ ce of a polymer substrate.
  • the electrical conductivity depends on the contact between the filler particles. Usually 10 - 50 weight-% well dispersed filler is needed to achieve composites with high conductivi ⁇ ty. There are, however, many problems with composites of this kind.
  • the mechanical properties of the composites decrease as the portion of filler is increased, the electri ⁇ cal conductivity is difficult to control especially in the semiconducting region 10 "9 - 10 "3 S/cm and homogenous disper ⁇ sion of the filler in the matrix is difficult.
  • Intrinsically electrically conducting polymers are substan ⁇ ces, which as such are insulators, but can be made conduc ⁇ ting by adding to them certain doping or agents. They are polymers with long conjugated chains with double bonds. The pi electronic system of the double chains can be pertur ⁇ bed by adding the mentioned doping agents, which are either electron donors or acceptors. Through this process holes or excess electrons are created in the polymer chain which make the propagation of electricity possible.
  • the electrical conductivity of intrinsically conducting polymers can be controlled depending on the dopant concent ⁇ ration so that it spans almost the whole conductivity scale from insulators to metals.
  • Examples of polymers of this kind are poly(acetylene) , poly(p-phenylene) , poly(pyrrole) , poly(aniline) and poly(thiophene) .
  • plastic composites which are made of in addition, to a non-conducting polymer matrix or substrate of an intrinsically conducting polymer as men ⁇ tioned above.
  • Galvin and nek have in their publication in Polym. Commun., ,23., (1982), 795, proposed the polymerization of poly(acetylene) into a polyethene film impregnated with catalyst.
  • Lindsay and Street have in Synthetic Metals, 10:67, 1985, proposed the electrochemical polymerization of polypyrrole into a plastic matrix to make a conducting composite, whose mechanical properties are better than those of pure polypyrrole.
  • a plastic composite consisting of an intrinsically electri ⁇ cally conducting polymer and a non-conducting polymer matrix should be expected to have properties than a plastic com ⁇ posite with carbon or metal fillers.
  • the electrically con ⁇ ducting polymers mentioned are, however, insoluble and non- processable, i.e. thermoset, which prevents their melt processing and in this way hinders their use in different applications..
  • the purpose of the invention at hand is to achieve such use of an electrically non-conducting polymer matrix or substra ⁇ te and an intrinsically electrically conducting polymer, where it works as raw material for partly or wholly conduc ⁇ ting thermoplastic products.
  • The. aim is also to achieve thermoplastic conducting or semiconducting products that have practical processing properties in the melt, rubberlike and liquid suspended state. This has been achieved with use according to claim l and with conducting and semiconducting products as described in claim 6.
  • thermoplastic conducting or semiconducting product has accordingly been achieved with the kind of polymer composite mentioned containing poly(3-substituted thiophene) .
  • thermoplastic material and product is meant in this case a material or product processed in the melt, rubberlike or liquid suspended state. In the liquid suspended state the processing is done e.g. by paste moulding, where paste consisting of e.g.
  • PVC and poly(3-substituted thiophene) is moulded and hardened by heating.
  • Poly(3-substituted thiophe ⁇ ne) can also be added to latex intended for coating pur ⁇ poses. Processing in the rubberlike state can be done e.g. by vacuum moulding, pressure moulding or heat forging.
  • melt moulding and casting methods are extrusion by which e.g. profiles, sheets, blow moulded films and products are made, injection moulding by which formed pieces and blow moulded products are made, rotational moulding by which hollow small products are made, and melt calendering in which plastic coating films are made between heated cylinders.
  • melt processing methods are compression moulding and trans ⁇ fer moulding.
  • the electrically conducting polymer used in the invention poly(3-substituted thiophene) is exceptional compared to other conducting polymers in the respect that it has the properties of a thermoplastic. It can be solved in organic solvents as toluene, chloroform and tetrahydrofurane and it melts without decomposing between 170 and 195 °C, at which temperature it is melt processable and possible to mix into e.g. a matrix plastic. In the invention at hand it is advan ⁇ tageous to use poly(3-alkyl thiophene) and most advantageous to use poly(3-octyl thiophene) . The latter polymer is produ ⁇ ced by polymerizing 2,5-diiodide-3-octyl thiophene.
  • the electrically non-conducting plastic component can be any thermoplastic, which is melt processable and compatible with poly(3-substituted thiophene) .
  • Advantageous matrix or subst ⁇ rate plastics are homo- or copolymers of ethene or some other olefin, vinyl chloride or styrene.
  • ethene vinyl acetate copolymer can be mentioned.
  • the additives used in the polymer composite depend on the plastic component of the composite and they can in addition to other polymers be fillers, plasticisers, lubricants, stabilizers, antioxidants, antistatic agents, fire retar- dants, pigments, UV absorbants, expanders for cellular plastics or cross linking agents.
  • the mixing together of the electrically conducting polymer component and the non-conducting polymer component can be done with any known device in the field, e.g. with a Braben- der mixer or screw extruder.
  • the mixing is done in the temperature range 150 - 200 °C, advantageously in the range 160 - 185 °C.
  • Approximately 0.1 - 50 weight-% of polyp- substituted thiophene) is added to the melt mixture and accordingly 50 - 99.9 weight-% other polymer and/or additi ⁇ ves.
  • An advantageous amount of the electrically conducting polymer is 5 - 30 weight-%.
  • the composite can also be made by pressing a layer of poly(3-substituted thiophene) in melt, rubberlike or liquid suspended state on the surface of a non-conducting polymer substrate.
  • the doping of the polymer composite can be done before the thermoplastic moulding of the electrically conducting po ⁇ ly(3-substituted thiophene) with the matrix or substrate polymer, or advantageously so that the moulded thermoplastic composite is doped after processing.
  • Doping is achieved either chemically or electrochemically with electron donating or accepting agents. It is advanta ⁇ geous to treat the polymer composite with a medium con ⁇ taining FeCl 3 .
  • the medium can be a suitable organic solvent, e.g. nitro methane or any other solvent or suspension me ⁇ dium, that does not have a negative effect on the doping event for instance by solving the poly(3-substituted thio ⁇ phene) .
  • doping agent e.g. salt
  • Another favourable doping agent is iodine which is used as such to increase the conductivity of the poly(3-substituted thiophene) .
  • the different doping treatments can also be applied simultaneously.
  • the product is washed clean of doping agent with a suitable solvent, most favourably with the same solvent used in the doping of the material, and finally the composite is dried.
  • the conductivity of the composites in question can be controlled by varying the doping time, the dopant concentration or the amount of poly(3-substituted thiophene) in the composite. In this way the whole conductivity range, including low conductivities, can be covered. In addition only the amount needed of the poly(3-substituted thiophene) is only approximately a third of the amount of carbon black needed to achieve sufficient conductivity in composites containing carbon black. Accor ⁇ dingly the mechanical properties of the composites are hardly affected at all.
  • the conducting and semiconducting products in the invention in which poly(3-substituted thiophene) is used contain a polymer composite have depending on the doping conditions a conductivity in the range 10 "9 - 10 S/cm. Their shielding efficiency against electromagnetic interference (EMI) is also considerable. Their EMI shielding efficiency is clearly better than a surface painted with carbon paint.
  • EMI electromagnetic interference
  • Products in which poly(3-substituted thiophenes) subject to the invention are e.g. antistatic applications as floorings, interior coatings, different packing materials, conveyor belts, storage and transport containers for explosives and flammable substances and charging tubes for explosives.
  • the composite can also be used for electromagnetic shielding and it is applicable in power cables as a semiconducting shiel ⁇ ding layer. It can be made into electronic products such as sensors, circuit boards, switches, heating elements, moni ⁇ tors and components.
  • the polymer composite is also suited for battery applications, optical and photovoltaic applica ⁇ tions, and paraboloid antennae and radar reflectors.
  • the products subject to the invention are also electrical and are accordingly suited for electrical applications.
  • Fig. 1 shows the dependency of the electrical conductivity as a function of time in a composite as presented in example 1.
  • Fig. 2 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is EVA.
  • Fig. 3 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is PVC.
  • Fig. 2 shows the shows the EMI shielding efficiency for different products, where the polymer matrix is 80 weight-% EVA, PVC and polystyrene.
  • Fig. 2 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is polystyrene.
  • Example 1
  • a polymer composite was made by melt processing at 170 - 195 °C made of 10 % poly-3-octyl thiophene and 90 % ethylene vinyl acetate polymer. The melt processing was carried out in a Brabender mixer for 10 minutes and mixing speed 30 r/min. The obtained composite was doped for different lengths of time by submerging it in a FeCl 3 -nitro methane solution in dry Argon atmosphere. The conductivity of the composite varied depending on doping time between 10 "10 and 10 "1 S/cm as shown in fig.l. A polymer composite with a conductivity in this range is well suited for antistatic and semiconducting applications. After a doping time of 1 hour the conductivity was 0.6 S/cm.
  • Poly(3-octyl thiophene) was pressed in the melt state on the surface of a ethylene vinyl acetate substrate.
  • the pressing time was 5 minutes, the temperature 180 °C and the pressure 100 bar.
  • the in this way obtained polymer composite was doped with iodine in vacuum and in addition with FeCl 3 in nitro methane.
  • the achieved conductivity of the composite was 10 S/cm.
  • a polymer composite was made by melt processing at 170 - 195 "C made up of different amounts of poly(3-octyl thiophene) and ethylene vinyl acetate (EVA) , vinyl chloride (PVC) or styrene polymer.
  • EVA ethylene vinyl acetate
  • PVC vinyl chloride
  • styrene polymer The composite was doped by submerging into FeCl 3 -nitro methane solution.
  • the electromagnetic shielding efficiency of the composite was measured in the range 100 kHz - 1 GHz. By adjusting the mixture ratio of the composite described in examples 1 and 2 and the doping composites suitable for different applica ⁇ tions were achieved.
  • the shielding efficiency was measured according to standard ASTM ES-7/83 for different composites and e.g. a composite with 20 weight-% poly(3-octyl thiophe ⁇ ne) and 80% EVA and doped with FeCl 3 , the shielding effi ⁇ ciency in the near field was above 50 dB up to l MHz fre ⁇ quency.
  • the shielding efficiency of a PVC-poly(3-octyl thiophene) is above 40 dB up to a frequency as high as 50 MHz. At higher frequency the shielding efficiency of all the measured composites with 20 weight-% poly(3-octyl thiophene) decreases to 10 dB at 1 GHz frequency.
  • the shielding effi ⁇ ciency of poly(3-octyl thiophene) composites is noticeably higher than that of a surface treated with carbon paint (cf. fig. 2 - 5)
  • the shielding efficiency of the mate ⁇ rial is dependent on the ability of the material to reflect electromagnetic radiation (e.g. radio waves)
  • the material described in examples 1, 2 and 3 can also be used in parabo ⁇ loid antennae e.g. in the manufacture of satellite antennae.
  • a test for piezoelectrical activity was performed on a 0.2 mm thick poly(3-octyl thiophene) film. Pressure changes affected on the polymer induced an electric voltage across the samples.
  • the polymer can accordingly also be used in piezoelectrical applications, e.g. pressure sensor.

Abstract

The subject invention is direct towards novel use of a polymer composite as thermoplastic raw material for products with electrically conducting or semiconducting properties. In polymer composites known in the field electrically conducting fillers and polymers do not have thermoplastic properties and are accordingly ill suited for thermoplastic processing of conducting and semiconducting products. It has now been invented that a polymer composite made up of an electrically nonconducting polymer matrix or polymer substrate, doped or undoped poly(3-substituted thiophene) and possibly plastics additives, is well suited as raw material for thermoplastics with conducting or semiconducting properties. The invention is accordingly also directed towards antistatic and semiconducting applications, where good shielding against electromagnetic interference is required and applications where the discovered piezoelectric properties of this material can be used.

Description

Use of electrically conducting polymer composites
The invention relates to the use of such electrically con¬ ducting polymer composites, which are made of a polymer matrix or a polymer substrate, intrinsically conducting, doped or undoped poly(3-substituted thiophene) and possibly additives for plastics.
Electrically conducting polymer materials can be roughly divided into two different categories: filled electrically conducting polymer materials and intrinsically electrically conducting polymer materials.
The former are composites, which consist of an electrically nonconductive polymer matrix or substrate and into which has been mixed or onto which has been layered an electrically conducting material. Usually these composites have as elect¬ rically conducting material carbon black, carbon fibers, metal flakes or metal fibers, which have been mixed into the matrix material in the melt state or layered onto the surfa¬ ce of a polymer substrate. In this kind of composites the electrical conductivity depends on the contact between the filler particles. Usually 10 - 50 weight-% well dispersed filler is needed to achieve composites with high conductivi¬ ty. There are, however, many problems with composites of this kind. The mechanical properties of the composites decrease as the portion of filler is increased, the electri¬ cal conductivity is difficult to control especially in the semiconducting region 10"9 - 10"3 S/cm and homogenous disper¬ sion of the filler in the matrix is difficult.
Intrinsically electrically conducting polymers are substan¬ ces, which as such are insulators, but can be made conduc¬ ting by adding to them certain doping or agents. They are polymers with long conjugated chains with double bonds. The pi electronic system of the double chains can be pertur¬ bed by adding the mentioned doping agents, which are either electron donors or acceptors. Through this process holes or excess electrons are created in the polymer chain which make the propagation of electricity possible.
The electrical conductivity of intrinsically conducting polymers can be controlled depending on the dopant concent¬ ration so that it spans almost the whole conductivity scale from insulators to metals. Examples of polymers of this kind are poly(acetylene) , poly(p-phenylene) , poly(pyrrole) , poly(aniline) and poly(thiophene) .
Also known in the field are plastic composites which are made of in addition, to a non-conducting polymer matrix or substrate of an intrinsically conducting polymer as men¬ tioned above. Galvin and nek have in their publication in Polym. Commun., ,23., (1982), 795, proposed the polymerization of poly(acetylene) into a polyethene film impregnated with catalyst. Lindsay and Street have in Synthetic Metals, 10:67, 1985, proposed the electrochemical polymerization of polypyrrole into a plastic matrix to make a conducting composite, whose mechanical properties are better than those of pure polypyrrole. In the publication Bjόrklund R.B. and Lundstrόm I., Electronic Materials, Vol. 13 , no. 1, 1984, 211-230 and the DE patent application 3 321 281 pyrrole has been used as the electrically conducting component of poly- pyrrole-cellulose composites. The US patent publication 4 604427 presents the diffusion of pyrrole or aniline monomer into a matrix polymer, after which the impregnated matrix polymer is treated with FeCl3 in order to make an electrical¬ ly conducting composite, where the conductor is polypyrrole or polyaniline.
A plastic composite consisting of an intrinsically electri¬ cally conducting polymer and a non-conducting polymer matrix should be expected to have properties than a plastic com¬ posite with carbon or metal fillers. The electrically con¬ ducting polymers mentioned are, however, insoluble and non- processable, i.e. thermoset, which prevents their melt processing and in this way hinders their use in different applications..
The purpose of the invention at hand is to achieve such use of an electrically non-conducting polymer matrix or substra¬ te and an intrinsically electrically conducting polymer, where it works as raw material for partly or wholly conduc¬ ting thermoplastic products. The. aim is also to achieve thermoplastic conducting or semiconducting products that have practical processing properties in the melt, rubberlike and liquid suspended state. This has been achieved with use according to claim l and with conducting and semiconducting products as described in claim 6.
The use of a composite made of a non-conducting polymer matrix or substrate and an intrinsically electrically con¬ ducting polymer as thermoplastic material has now been achieved by choosing poly(3-substituted thiophene) as the conducting polymer. In accordance with the subject invention a thermoplastic conducting or semiconducting product has accordingly been achieved with the kind of polymer composite mentioned containing poly(3-substituted thiophene) . With a thermoplastic material and product is meant in this case a material or product processed in the melt, rubberlike or liquid suspended state. In the liquid suspended state the processing is done e.g. by paste moulding, where paste consisting of e.g. PVC and poly(3-substituted thiophene) is moulded and hardened by heating. Poly(3-substituted thiophe¬ ne) can also be added to latex intended for coating pur¬ poses. Processing in the rubberlike state can be done e.g. by vacuum moulding, pressure moulding or heat forging.
The most advantageous is the use of such a polymer com¬ posite, where the conducting or semiconducting product is made by melt processing. Advantageous melt moulding and casting methods are extrusion by which e.g. profiles, sheets, blow moulded films and products are made, injection moulding by which formed pieces and blow moulded products are made, rotational moulding by which hollow small products are made, and melt calendering in which plastic coating films are made between heated cylinders. Among less common melt processing methods are compression moulding and trans¬ fer moulding.
The electrically conducting polymer used in the invention poly(3-substituted thiophene) is exceptional compared to other conducting polymers in the respect that it has the properties of a thermoplastic. It can be solved in organic solvents as toluene, chloroform and tetrahydrofurane and it melts without decomposing between 170 and 195 °C, at which temperature it is melt processable and possible to mix into e.g. a matrix plastic. In the invention at hand it is advan¬ tageous to use poly(3-alkyl thiophene) and most advantageous to use poly(3-octyl thiophene) . The latter polymer is produ¬ ced by polymerizing 2,5-diiodide-3-octyl thiophene.
The electrically non-conducting plastic component can be any thermoplastic, which is melt processable and compatible with poly(3-substituted thiophene) . Advantageous matrix or subst¬ rate plastics are homo- or copolymers of ethene or some other olefin, vinyl chloride or styrene. As a suitable polymer ethene vinyl acetate copolymer can be mentioned.
The additives used in the polymer composite depend on the plastic component of the composite and they can in addition to other polymers be fillers, plasticisers, lubricants, stabilizers, antioxidants, antistatic agents, fire retar- dants, pigments, UV absorbants, expanders for cellular plastics or cross linking agents.
The mixing together of the electrically conducting polymer component and the non-conducting polymer component can be done with any known device in the field, e.g. with a Braben- der mixer or screw extruder. The mixing is done in the temperature range 150 - 200 °C, advantageously in the range 160 - 185 °C. Approximately 0.1 - 50 weight-% of polyp- substituted thiophene) is added to the melt mixture and accordingly 50 - 99.9 weight-% other polymer and/or additi¬ ves. An advantageous amount of the electrically conducting polymer is 5 - 30 weight-%.
The production of a electrically conducting polymer com¬ posite has been described above, but the composite can also be made by pressing a layer of poly(3-substituted thiophene) in melt, rubberlike or liquid suspended state on the surface of a non-conducting polymer substrate.
The doping of the polymer composite can be done before the thermoplastic moulding of the electrically conducting po¬ ly(3-substituted thiophene) with the matrix or substrate polymer, or advantageously so that the moulded thermoplastic composite is doped after processing.
Doping is achieved either chemically or electrochemically with electron donating or accepting agents. It is advanta¬ geous to treat the polymer composite with a medium con¬ taining FeCl3. The medium can be a suitable organic solvent, e.g. nitro methane or any other solvent or suspension me¬ dium, that does not have a negative effect on the doping event for instance by solving the poly(3-substituted thio¬ phene) . Usually such solvents which solve doping agent (e.g. salt) in question and swell the composite to enable the doping event to take place. Another favourable doping agent is iodine which is used as such to increase the conductivity of the poly(3-substituted thiophene) . The different doping treatments can also be applied simultaneously.
After doping the product is washed clean of doping agent with a suitable solvent, most favourably with the same solvent used in the doping of the material, and finally the composite is dried.
Depending on the application in question the conductivity of the composites in question can be controlled by varying the doping time, the dopant concentration or the amount of poly(3-substituted thiophene) in the composite. In this way the whole conductivity range, including low conductivities, can be covered. In addition only the amount needed of the poly(3-substituted thiophene) is only approximately a third of the amount of carbon black needed to achieve sufficient conductivity in composites containing carbon black. Accor¬ dingly the mechanical properties of the composites are hardly affected at all.
The conducting and semiconducting products in the invention in which poly(3-substituted thiophene) is used contain a polymer composite have depending on the doping conditions a conductivity in the range 10"9 - 10 S/cm. Their shielding efficiency against electromagnetic interference (EMI) is also considerable. Their EMI shielding efficiency is clearly better than a surface painted with carbon paint.
Products in which poly(3-substituted thiophenes) subject to the invention are e.g. antistatic applications as floorings, interior coatings, different packing materials, conveyor belts, storage and transport containers for explosives and flammable substances and charging tubes for explosives. The composite can also be used for electromagnetic shielding and it is applicable in power cables as a semiconducting shiel¬ ding layer. It can be made into electronic products such as sensors, circuit boards, switches, heating elements, moni¬ tors and components. The polymer composite is also suited for battery applications, optical and photovoltaic applica¬ tions, and paraboloid antennae and radar reflectors.
The products subject to the invention are also electrical and are accordingly suited for electrical applications.
In the following some products and applications of the subject invention are presented.
Fig. 1 shows the dependency of the electrical conductivity as a function of time in a composite as presented in example 1.
Fig. 2 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is EVA.
Fig. 3 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is PVC.
Fig. 2 shows the shows the EMI shielding efficiency for different products, where the polymer matrix is 80 weight-% EVA, PVC and polystyrene.
Fig. 2 shows the shows the EMI shielding efficiency for different products as presented in example 3, where the polymer matrix is polystyrene. Example 1
A polymer composite was made by melt processing at 170 - 195 °C made of 10 % poly-3-octyl thiophene and 90 % ethylene vinyl acetate polymer. The melt processing was carried out in a Brabender mixer for 10 minutes and mixing speed 30 r/min. The obtained composite was doped for different lengths of time by submerging it in a FeCl3-nitro methane solution in dry Argon atmosphere. The conductivity of the composite varied depending on doping time between 10"10 and 10"1 S/cm as shown in fig.l. A polymer composite with a conductivity in this range is well suited for antistatic and semiconducting applications. After a doping time of 1 hour the conductivity was 0.6 S/cm.
Example 2
Poly(3-octyl thiophene) was pressed in the melt state on the surface of a ethylene vinyl acetate substrate. The pressing time was 5 minutes, the temperature 180 °C and the pressure 100 bar. The in this way obtained polymer composite was doped with iodine in vacuum and in addition with FeCl3 in nitro methane. The achieved conductivity of the composite was 10 S/cm.
Example 3
A polymer composite was made by melt processing at 170 - 195 "C made up of different amounts of poly(3-octyl thiophene) and ethylene vinyl acetate (EVA) , vinyl chloride (PVC) or styrene polymer. The composite was doped by submerging into FeCl3-nitro methane solution.
The electromagnetic shielding efficiency of the composite was measured in the range 100 kHz - 1 GHz. By adjusting the mixture ratio of the composite described in examples 1 and 2 and the doping composites suitable for different applica¬ tions were achieved. The shielding efficiency was measured according to standard ASTM ES-7/83 for different composites and e.g. a composite with 20 weight-% poly(3-octyl thiophe¬ ne) and 80% EVA and doped with FeCl3, the shielding effi¬ ciency in the near field was above 50 dB up to l MHz fre¬ quency. The shielding efficiency of a PVC-poly(3-octyl thiophene) is above 40 dB up to a frequency as high as 50 MHz. At higher frequency the shielding efficiency of all the measured composites with 20 weight-% poly(3-octyl thiophene) decreases to 10 dB at 1 GHz frequency. The shielding effi¬ ciency of poly(3-octyl thiophene) composites is noticeably higher than that of a surface treated with carbon paint (cf. fig. 2 - 5)
Due to the fact that the shielding efficiency of the mate¬ rial is dependent on the ability of the material to reflect electromagnetic radiation (e.g. radio waves) the material described in examples 1, 2 and 3 can also be used in parabo¬ loid antennae e.g. in the manufacture of satellite antennae.
Example 4
An electrical heating test was performed on a sheet made of undoped and doped poly(3-octyl thiophene) The temperature of the polymer increased to 50 "C due to the current with a voltage of 5 V. The polymer can accordingly be used as a heating element and as a sensor.
Example 5
A test for piezoelectrical activity was performed on a 0.2 mm thick poly(3-octyl thiophene) film. Pressure changes affected on the polymer induced an electric voltage across the samples. The polymer can accordingly also be used in piezoelectrical applications, e.g. pressure sensor.

Claims

Patent claims
1. The use of such a polymer composite that is made of a polymer matrix or polymer substrate, intrinsically electri¬ cally conducting poly(3-substituted thiophene) and possibly plastics additives as raw material for products with conduc¬ ting or semiconducting properties.
2. Use according to patent claim 1, where the products with conducting or seminconducting properties are made by melt processing, e.g. extrusion, injection moulding, melt spin¬ ning, rotational moulding, calendering, compression moulding or transfer moulding.
3. Use according to patent claim 1 where the products with conducting or semiconducting properties have been made by moulding in rubberlike state, e.g. vacuum moulding, pressure moulding or heat forging, or in suspension, e.g. by paste moulding or using latex technique.
4. Any use in the claims above where the poly(3-substituted thiophene) advantageously is poly(3-octylthiophene) .
5. Any use in the above claims where the polymer matrix or substrate is the polymer of ethylene or some other olefin, vinyl chloride or styren, or their copolymer, advantageously ethylene vinyl acetate copolymer.
6. A product with conducting or semiconducting properties, where its raw material i s a composite made of polymer matrix or substrate, an electrically conducting solid and possibly other additives, known for having as its electri¬ cally conducting solid intrinsically conducting, doped or undoped poly(3-substituted thiophene) .
7. A product according to claim 6, known to be an antistatic product, e.g. flooring, interior coating, package, conveyor belt or storage or transport container or transport tube for flammable or explosive substances.
8. A product according to claim 6, known to be a sensor, circuit board, switching device, heat element, monitor or elctronic component or protective or shielding layer for electric cables.
9. A product according to claim 6, known to be a part of a battery.
10. A product according to claim 6, known to be a part of a paraboloid antena or radar reflector.
11. A product according to claim 6, known to be a piezo electric element.
12. A product according to claim 6, known to be a photo- optical or photoelectrical element.
PCT/FI1990/000027 1989-01-27 1990-01-24 Use of electrically conducting polymer composites WO1990009027A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI890427A FI890427A (en) 1989-01-27 1989-01-27 BRUK AV EN ELLEDANDE POLYMER COMPOSITES.
FI890427 1989-01-27

Publications (1)

Publication Number Publication Date
WO1990009027A1 true WO1990009027A1 (en) 1990-08-09

Family

ID=8527796

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1990/000027 WO1990009027A1 (en) 1989-01-27 1990-01-24 Use of electrically conducting polymer composites

Country Status (2)

Country Link
FI (1) FI890427A (en)
WO (1) WO1990009027A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991015859A1 (en) * 1990-03-30 1991-10-17 Neste Oy A method for preparing a conductive polymer
WO1992016950A1 (en) * 1991-03-14 1992-10-01 Neste Oy Method of preparation of a conductive polymer
EP0507676A2 (en) * 1991-04-02 1992-10-07 Alcatel Cable Material for semiconductor screen
EP0536915A2 (en) * 1991-10-08 1993-04-14 Americhem, Inc. Process for preparing an intrinsically conductive polymer and articles of a thermoplastic polymer blend containing it
US5543128A (en) * 1992-09-15 1996-08-06 Neste Oy Regeneration method for process waste containing sulfur and phosphorus
WO2001013087A2 (en) * 1999-08-18 2001-02-22 California Institute Of Technology Sensors and sensor arrays of conducting and insulating composites and methods of use thereof
EP1500938A1 (en) * 2003-07-25 2005-01-26 Hitachi Unisia Automotive Ltd. Rotation sensor with antistatic housing
US6890715B1 (en) 1999-08-18 2005-05-10 The California Institute Of Technology Sensors of conducting and insulating composites
US6962675B2 (en) 1999-05-10 2005-11-08 California Institute Of Technology Use of spatiotemporal response behavior in sensor arrays to detect analytes in fluids
US7122152B2 (en) 1999-05-10 2006-10-17 University Of Florida Spatiotemporal and geometric optimization of sensor arrays for detecting analytes fluids
US8394330B1 (en) 1998-10-02 2013-03-12 The California Institute Of Technology Conductive organic sensors, arrays and methods of use
US9620259B2 (en) 2012-03-30 2017-04-11 University Of Washington Through Its Center For Commercialization Composites incorporated a conductive polymer nanofiber network

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985005728A1 (en) * 1984-05-26 1985-12-19 Battelle-Institut E.V. COPOLYMERS AND MIXTURES OF POLYMERS WITH A CONJUGATED pi-SYSTEM
EP0203438A1 (en) * 1985-05-31 1986-12-03 Corporation Allied Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
WO1987000677A1 (en) * 1985-07-24 1987-01-29 Neste Oy Electrically conductive polythiophene and procedure for its manufacturing, and its use
EP0240063A1 (en) * 1986-04-01 1987-10-07 Solvay Electrically conductible polymers derived from 3-alkylthiophene, process for their preparation and electrical devices containing them
EP0246931A2 (en) * 1986-05-23 1987-11-25 Sumitomo Chemical Company, Limited The use as light-polarizing films of unsaturated cyclic polymers
EP0257573A1 (en) * 1986-08-26 1988-03-02 Hoechst Aktiengesellschaft Soluble electrically conductive polymers, method of producing them and their use
EP0294231A1 (en) * 1987-06-03 1988-12-07 Montclair State College Method for preparing conducting polymer films

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985005728A1 (en) * 1984-05-26 1985-12-19 Battelle-Institut E.V. COPOLYMERS AND MIXTURES OF POLYMERS WITH A CONJUGATED pi-SYSTEM
EP0203438A1 (en) * 1985-05-31 1986-12-03 Corporation Allied Solution processible forms of neutral and electrically conductive poly(substituted heterocycles)
WO1987000677A1 (en) * 1985-07-24 1987-01-29 Neste Oy Electrically conductive polythiophene and procedure for its manufacturing, and its use
EP0240063A1 (en) * 1986-04-01 1987-10-07 Solvay Electrically conductible polymers derived from 3-alkylthiophene, process for their preparation and electrical devices containing them
EP0246931A2 (en) * 1986-05-23 1987-11-25 Sumitomo Chemical Company, Limited The use as light-polarizing films of unsaturated cyclic polymers
EP0257573A1 (en) * 1986-08-26 1988-03-02 Hoechst Aktiengesellschaft Soluble electrically conductive polymers, method of producing them and their use
EP0294231A1 (en) * 1987-06-03 1988-12-07 Montclair State College Method for preparing conducting polymer films

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991015859A1 (en) * 1990-03-30 1991-10-17 Neste Oy A method for preparing a conductive polymer
WO1992016950A1 (en) * 1991-03-14 1992-10-01 Neste Oy Method of preparation of a conductive polymer
EP0507676A2 (en) * 1991-04-02 1992-10-07 Alcatel Cable Material for semiconductor screen
WO1992017995A1 (en) * 1991-04-02 1992-10-15 Alcatel Cable Material for semiconductor screen
EP0507676A3 (en) * 1991-04-02 1992-11-25 Alcatel Cable Material for semiconductor screen
US5416155A (en) * 1991-04-02 1995-05-16 Alcatel Cable Material for semiconductive screening
EP0536915A2 (en) * 1991-10-08 1993-04-14 Americhem, Inc. Process for preparing an intrinsically conductive polymer and articles of a thermoplastic polymer blend containing it
EP0536915A3 (en) * 1991-10-08 1993-07-14 Americhem, Inc. Process for preparing an intrinsically conductive polymer and articles of a thermoplastic polymer blend containing it
US5543128A (en) * 1992-09-15 1996-08-06 Neste Oy Regeneration method for process waste containing sulfur and phosphorus
US8394330B1 (en) 1998-10-02 2013-03-12 The California Institute Of Technology Conductive organic sensors, arrays and methods of use
US6962675B2 (en) 1999-05-10 2005-11-08 California Institute Of Technology Use of spatiotemporal response behavior in sensor arrays to detect analytes in fluids
US7122152B2 (en) 1999-05-10 2006-10-17 University Of Florida Spatiotemporal and geometric optimization of sensor arrays for detecting analytes fluids
US7595023B2 (en) 1999-05-10 2009-09-29 The California Institute Of Technology Spatiotemporal and geometric optimization of sensor arrays for detecting analytes in fluids
WO2001013087A2 (en) * 1999-08-18 2001-02-22 California Institute Of Technology Sensors and sensor arrays of conducting and insulating composites and methods of use thereof
WO2001013087A3 (en) * 1999-08-18 2001-09-07 California Inst Of Techn Sensors and sensor arrays of conducting and insulating composites and methods of use thereof
US6890715B1 (en) 1999-08-18 2005-05-10 The California Institute Of Technology Sensors of conducting and insulating composites
EP1500938A1 (en) * 2003-07-25 2005-01-26 Hitachi Unisia Automotive Ltd. Rotation sensor with antistatic housing
US6968748B2 (en) 2003-07-25 2005-11-29 Hitachi Inisia Automotive, Ltd. Rotation sensor
US9620259B2 (en) 2012-03-30 2017-04-11 University Of Washington Through Its Center For Commercialization Composites incorporated a conductive polymer nanofiber network

Also Published As

Publication number Publication date
FI890427A0 (en) 1989-01-27
FI890427A (en) 1990-07-28

Similar Documents

Publication Publication Date Title
Jagur‐Grodzinski Electronically conductive polymers
Trivedi et al. Shielding of electromagnetic interference using polyaniline
Koul et al. Conducting polyaniline composite for ESD and EMI at 101 GHz
Pud et al. Some aspects of preparation methods and properties of polyaniline blends and composites with organic polymers
Bhadra et al. Dielectric properties and EMI shielding efficiency of polyaniline and ethylene 1-octene based semi-conducting composites
WO1990009027A1 (en) Use of electrically conducting polymer composites
EP0324842A1 (en) Conductive plastic composites
US5993696A (en) Electrically conductive thermoplastic elastomeric composition and its use
Courric et al. The electromagnetic properties ofpoly (p-phenylene-vinylene) derivatives
Bhadra et al. Semiconductive composites from ethylene 1‐octene copolymer and polyaniline coated nylon 6: Studies on mechanical, thermal, processability, electrical, and EMI shielding properties
Fu et al. Conductive elastomeric foams prepared by in situ vapor phase polymerization of pyrrole and copolymerization of pyrrole and N‐methylpyrrole
Bloor et al. Conducting polymers
FI86880C (en) ELLEDANDE PLASTKOMPOSIT, DESS ANVAENDNING OCH FRAMSTAELLNING
JP2515218B2 (en) Semiconductor shielding material
US4765928A (en) Intrinsically conductive doped polymers of enhanced stability
Yang et al. Preparation and mechanical properties of electrically conductive polypyrrole-poly (ethylene-co-vinyl acetate) composites
Seema et al. Dielectric spectroscopy of nanostructured polypyrrole-NiO composites
CA1168859A (en) Thermoplastic conductive polymers
US5929137A (en) Process for the production of improved dielectric strength materials and the use of materials obtained by this process in the manufacture of power transmission cables
De Chanterac et al. Electromagnetic absorption of polyanilines at microwave frequencies
Ajekwene et al. Sodium salt of polyethylene-co-methacrylic acid ionomer/polyaniline binary blends for EMI shielding applications
Friend Conductive Polymers II: From Science to Applications
Bandara ELECTRICALLY CONDUCTING PLASTICS
Passiniemi et al. Electrically conducting polymer blends based on polyaniline
Bandara Conducting fillers for plastics:(2) Conducting polymer additives

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE