EP0802943A1 - Leitender, polymerer verbundwerkstoff - Google Patents
Leitender, polymerer verbundwerkstoffInfo
- Publication number
- EP0802943A1 EP0802943A1 EP96900206A EP96900206A EP0802943A1 EP 0802943 A1 EP0802943 A1 EP 0802943A1 EP 96900206 A EP96900206 A EP 96900206A EP 96900206 A EP96900206 A EP 96900206A EP 0802943 A1 EP0802943 A1 EP 0802943A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- conducting
- polymer
- thermoplastic
- particle
- composite
- 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.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229920001940 conductive polymer Polymers 0.000 title claims description 32
- 239000002322 conducting polymer Substances 0.000 title claims description 31
- 239000002245 particle Substances 0.000 claims abstract description 57
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 36
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 35
- 239000004800 polyvinyl chloride Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- -1 poly(vinyl chloride) Polymers 0.000 claims description 21
- 229920000767 polyaniline Polymers 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000012815 thermoplastic material Substances 0.000 claims description 9
- 229920006125 amorphous polymer Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229940100630 metacresol Drugs 0.000 claims description 4
- 238000005325 percolation Methods 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 3
- 239000003049 inorganic solvent Substances 0.000 claims description 3
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001020 plasma etching Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
- H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
Definitions
- the present invention relates generally to composite materials consisting of conventional thermoplastics and intrinsically conducting polymers (ICPs) and in particular to an electrically semi-conducting or conducting composite material and methods for forming same.
- the composite material has potential application in a wide range of devices including microwave devices, pressure sensors, temperature sensors, cable shielding, electromagnetic shielding, anti-static materials for computers and other applications, radar-absorbing materials, light weight battery electrodes, high-power junction devices, corrosion resistant electrodes and corrosion resistant cable termination coatings.
- a number of intrinsically conducting polymers have now been known for well over a decade.
- One of the most extensively characterised conducting polymers is polyacetylene. This polymer possesses a backbone with a high degree of unsaturation leading to ⁇ -orbital overlap and electron delocalisation. This delocalisation allows the polymer to possess a quite remarkable electrical conductivity when compared with traditional insulating polymers.
- the structure of this polymer is, however, quite unstable.
- polyheterocyclics such as polypyrrole and polythiophene.
- polypyrrole the repeat unit of this polymer is comprised of a 5-membered cyclic ring with two delocalised ⁇ bonds and a nitrogen heteroatom.
- Polypyrrole when produced using an electrochemical process can form a free standing film with an electrical conductivity as high as 100 S/cm.
- Polyheterocyclics have an improved stability in comparison to polyacetylene, the improved stability being provided by the aromatic nature of the heterocyclic ring which prevents loss of ⁇ bond unsaturation.
- thermoplastics With conventional thermoplastics with intrinsically conducting polymers, their use to date has been limited by poor environmental stability and poor mechanical properties. Poor processability and poor solubility have also prevented processing of the polymers using traditional polymer processing techniques.
- the blending of conventional thermoplastics with intrinsically conducting polymers leads to processable semi-conducting thermoplastics. Previously, this has been achieved by intimate mixing of thermoplastics with intrinsically conducting polymers either by solution processing (for example see A. Andreatta and P. Smith. Synthetic Metals (1993), 55-57. 1017) or by direct blending (for example see L.W. Shacklette, C.C. Han and M.H. Luly, Synthetic Metals ( 1993) 55-57, 3532).
- thermoplastic composite which requires at least 15% w/w intrinsic conducting polymer to achieve electrical conductivities comparable to that of the pure intrinsically conducting polymer. This is due to the nature of the microstructure of blends arising from these procedures. These methods of processing result in conduction through a dispersed phase consisting of flocculated structures. This behaviour results from what is termed a percolation network and is analogous to that observed when a thermoplastic is loaded with conventional conductors (such as silver particles) or semi-conductors (such as carbon black).
- polyethylene films the surface of which has been sulfonated, can be coated with pyrrole followed by a chemical oxidative polymerisation resulting in a conducting polymer coating on the surface of the film (for example see K. Yoshino, X.II. Yin. S. Morita, Y. Nakanishi. S. Nakagawa, S. Yamamoto. T. Watanuki and I. Isa, Japanese Journal of Applied Physics Part 1 (1993), 32, 979). Disclosure of the Invention
- the present invention consists in an electrically semi-conducting or conducting composite material comprising a plurality of electrically insulating thermoplastic particles coated with conducting or semiconducting polymer, the conducting or semiconducting polymer forming a network through the composite.
- the conducting or semiconducting polymer is soluble in organic or inorganic solvents and can comprise polyaniline or a polyaniline derivative.
- the polyaniline is preferably a doped polyaniline- camphorsulfonic acid in meta-cresol.
- the difference between the glass transition temperature and melting temperature of the thermoplastic material is preferably greater than 20°C thereby allowing pressing of the thermoplastic material in its rubbery state and avoiding melting and disruption of the morphology.
- the thermoplastic material is an amorphous polymer.
- the thermoplastic can comprise unplasticised or plasticised poly(vinyl chloride) (PVC).
- the plasticiser is preferably any additive which lowers the glass transition temperature of the material and can include internal plasticisers or an ester plasticiser such as dioctyl phthalate or dibutyl phthalate.
- the surface of the thermoplastic particles prior to coating with the conducting polymer is preferably treated to increase its wettability by the conducting or semiconducting polymer and so improve the adhesion between the coating and the particle.
- the surface treatment preferably comprises, plasma etching, chemical etching, or, most preferably, sulfonation in which sulfo groups. -SO3H, are bonded to the surface of the particles.
- the thermoplastic particles are preferably approximately spherical in geometry with a diameter less than 100 microns.
- the particles may also contain ferromagnetic particles to enhance electromagnetic shielding.
- the ratio of conducting polymer to thermoplastic material in the composite preferably lies in the range 0.1% w/w-20% w/w.
- the electrical conductivity of the composite preferably lies in the range 0.001-50 S/cm but can be varied over a larger range by appropriate doping of the conducting polymer.
- the percolation threshold of the composite is preferably less than 1% w/w of the conducting polymer.
- the present invention consists in an electrically insulating thermoplastic particle substantially coated with a layer of a soluble conducting polymer.
- the soluble polymer comprises a doped or undoped polyaniline or polyaniline derivative.
- the present invention consists in a method for preparing an electrically semi-conducting or conducting composite material comprising bringing together thermoplastic particles coated with conducting or semiconducting polymer under conditions of temperature such that the particles are bonded togetlier or coalesced without destroying the connectivity of the conductive coatings to produce a conductive network.
- thermoplastic particles can be substantially spherical sulfonated poly(vinyl chloride) particles coated with a layer of doped polyaniline.
- the temperature is preferably set between the glass transition temperature and the flow point of the thermoplastic.
- the temperature is preferably set in the range 145°C to 155°C.
- thermoplastic particles are also preferably brought together under pressure, the pressure being sufficiently low so as to prevent shear stress deforming the particles to a point where the conducting oi ⁇ semiconducting polymer coating is disrupted.
- the pressure may be applied by pressing or extrusion of the material.
- the present invention consists in a method for preparing a thermoplastic particle substantially coated with a layer of doped or undoped conducting polymer comprising the step of substantially coating the thermoplastic particle with a layer of doped or undoped conducting polymer.
- the particles are preferably coated by mixing the particles with a solution containing dissolved doped or undoped conducting polymer followed by a drying of the particles, if necessary, at an elevated temperature and under vacuum.
- the conducting polymer is preferably polyaniline.
- the polyaniline solution preferably comprising a doped polvaniline- camphorsulfonic acid in meta-cresol.
- the thermoplastic particles are preferably an amorphous polymer.
- poly(vinyl chloride) particles which have undergone a surface treatment prior to being mixed with the solution.
- the surface treatment preferably comprises a sulfonation process wherein sulfonate groups are bonded to the surface of the particles.
- the sulfonated particles are preferably soaked in a plasticiser prior to being mixed in the polyaniline solution.
- the plasticiser may comprise an ester plasticiser such as dioctyl phthalate or dibutyl phthalate.
- the addition of the plasticiser results in a composite having improved mechanical characteristics such as flexibility without lowering the electrical conductivity.
- the processability of the conducting thermoplastic composite improves its potential for use in a variety of applications.
- the composite can be utilised in a range of devices including microwave devices, pressure sensors, temperature sensors, cable shielding, magnetic shielding, anti-static materials for computers and other applications, radar-absorbing materials, light weight corrosion resistant electrodes, high-power junction devices and corrosion resistant cable termination coatings.
- Figure 1 is an optical micrograph of 4% PAn-CSA/PVC pressed at 150°C/28MPa;
- Figure 2 is an optical micrograph of 4% PAn-CSA PVC pressed at 200°C/28MPa;
- Figure 3 is a graph of electrical conductivity of the composite material as a function of loading of PAn-CSA/PVC
- Figure 4 is a graph of DMTA results for composite materials made according to the present invention having varying quantities of PAn- CS ⁇ /PVc:
- Figure 5 is a graph of DMTA results for composite materials made according to the present invention containing 4% PAn-CSA PVC and varying amounts of plasticiser. Best Method of Performing the Invention By way of example only, a preferred embodiment of the invention is described below.
- the resulting sulfonated poly(vinyl chloride) was then dried under vacuum for 24 hours.
- the degree of sulfonation was determined to be 1.0 x 10 ll, SO 3 groups/cm 2 .
- the particles were then suspended in petroleum spirit (80-100°C fraction) (200 millilitres) containing dioctyl phthalate (DOP) (10 grams) and the solvent was allowed to slowly evaporate.
- DOP dioctyl phthalate
- the composite material as prepared using the process described in Example 1 had a conductive network of PAn-CSA 10 around the poly(vinyl chloride) (PVC) particles 20 as is clearly depicted in Figure 1.
- Pressing an identically prepared sample of composite at a temperature exceeding the flowpoint of the PVC (ie. at 200°C) resulted in destruction of the network morphology in the composite as is clearly depicted in Figure 2.
- Further samples having varying weight fractions of PAn-CSA in PVC were prepared with the electrical conductivity of the composites being determined by the standard 4-probe measurement. The results are depicted in Figure 3. It can be readily seen from Figure 3 that the percolation threshold of the composite is less than 1% w/w PAn-CSA.
- the sample prepared using the method described in Example 1 was measured to have an electrical conductivity of 1.2 S/m using a standard 4-probe measurement.
- the conducting composite prepared using the method defined in Example 1 while not having mechanical properties identical to PVC does have improved mechanical properties in comparison to intrinsically conducting polymers.
- DMTA studies in bending mode on samples prepared as described in Example 1 but with varying quantities of PAn-CSA showed a substantial change in the softening temperature of the samples with increasing PAn-CSA loading. Softening occurs around 70°C for all samples (cf:90°C for PVC pressed in an identical manner). Notably, below 65°C there is almost no difference in modulus, the stiffness being comparable to that of
- the conductivity of the composite is effected when pressed at 150°C, due to the low softening temperature ( ⁇ 50°C).
- the high processing temperature relative to the 30% DOP softening temperature leads to the destruction of the connective morphology shown in Figure 1, and the formation of a morphology similar to that shown in Figure 2.
- the processability of the composite also allows the material to be employed in a wide range of applications as hereinbefore described.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPN046895 | 1995-01-10 | ||
AUPN0468/95 | 1995-01-10 | ||
PCT/AU1996/000009 WO1996021694A1 (en) | 1995-01-10 | 1996-01-10 | Conducting polymer composite |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0802943A1 true EP0802943A1 (de) | 1997-10-29 |
EP0802943A4 EP0802943A4 (de) | 1998-04-15 |
Family
ID=3784904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96900206A Withdrawn EP0802943A4 (de) | 1995-01-10 | 1996-01-10 | Leitender, polymerer verbundwerkstoff |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0802943A4 (de) |
WO (1) | WO1996021694A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5908898A (en) * | 1998-02-12 | 1999-06-01 | Monsanto Company | Intrinsically conductive polymer blends having a low percolation threshold |
FR2783524B1 (fr) * | 1998-09-22 | 2003-07-25 | Commissariat Energie Atomique | Materiau a resistance au vieillissement thermique amelioree et son procede de fabrication |
WO2009077349A1 (en) * | 2007-12-14 | 2009-06-25 | Basf Se | Process for the preparation of semiconducting layers |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0550349A1 (de) * | 1991-12-18 | 1993-07-07 | Rhone-Poulenc Films | Elektrisch leitfähige Polymerzusammensetzungen enthaltend amphiphile, polymerisierbare Pyrrolderivate, ihre Herstellung und Verwendung |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4517268A (en) * | 1983-09-12 | 1985-05-14 | Xerox Corporation | Process for magnetic image character recognition |
FR2616790A1 (fr) * | 1987-06-22 | 1988-12-23 | Rhone Poulenc Chimie | Dispersions de particules composites a base d'un polymere electroconducteur et leur procede de preparation |
-
1996
- 1996-01-10 WO PCT/AU1996/000009 patent/WO1996021694A1/en not_active Application Discontinuation
- 1996-01-10 EP EP96900206A patent/EP0802943A4/de not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0550349A1 (de) * | 1991-12-18 | 1993-07-07 | Rhone-Poulenc Films | Elektrisch leitfähige Polymerzusammensetzungen enthaltend amphiphile, polymerisierbare Pyrrolderivate, ihre Herstellung und Verwendung |
Non-Patent Citations (1)
Title |
---|
See also references of WO9621694A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1996021694A1 (en) | 1996-07-18 |
EP0802943A4 (de) | 1998-04-15 |
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