EP0121289A1 - Dispositif électrique à coefficient de température négatif - Google Patents
Dispositif électrique à coefficient de température négatif Download PDFInfo
- Publication number
- EP0121289A1 EP0121289A1 EP19840300084 EP84300084A EP0121289A1 EP 0121289 A1 EP0121289 A1 EP 0121289A1 EP 19840300084 EP19840300084 EP 19840300084 EP 84300084 A EP84300084 A EP 84300084A EP 0121289 A1 EP0121289 A1 EP 0121289A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pyrrole
- substituted
- substituent
- electrically conductive
- lower alkyl
- 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- Withdrawn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
- -1 2-substituted pyrroles Chemical class 0.000 claims abstract description 16
- 239000004020 conductor Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 42
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000003233 pyrroles Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical compound CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 description 8
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- OUYLXVQKVBXUGW-UHFFFAOYSA-N 2,3-dimethyl-1h-pyrrole Chemical compound CC=1C=CNC=1C OUYLXVQKVBXUGW-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/049—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of organic or organo-metal substances
Definitions
- NTC negative temperature coefficient
- thermistors may be made from the oxides of such materials as iron, chromium, manganese, cobalt and nickel doped by the addition of small quantities of a metal with a different valency.
- the invention provides an NTC electrical device having as an NTC element an electrically conductive material produced by oxidative doping of a 2-substituted pyrrole.
- electrically conductive materials can be produced by oxidation of pyrrole which results in the formation of an electrically charged polymer or oligomer inherently capable of conducting electricity.
- a negative counter-ion is required to balance the positive electrical charge on the oxidised electrically conductive pyrrole material.
- This counter-ion will be hereinafter referred to as a "dopant”, and the process of oxidation and introduction of the dopant will be referred to as "oxidative doping", regardless of whether the doping is performed together with, or after, the oxidation.
- dopants include BF 4 , Br-, p-toluenesulphonate.
- the preferred 2-substituents are electron-releasing groups, preferably lower alkyl groups, especially methyl, although other (more expensive) substituents may be useful. Further substitution in the 3-, 4- or 5- positions of the pyrrole also produces high negative temperature coefficients compared with 3,4-disubstitution or unsubstituted pyrrole, the preferred 3-, 4-, or 5-substituents also being electron-donating groups, preferably lower alkyl groups, especially methyl.
- Electrically conductive materials produced from pyrroles tend to have advantageous oxidation resistance over other conductive polymers such as polyacetylenes. To obtain a conductive polymer, sufficient positions must be left unsubstituted to permit polymerisation. Electrically conductive polymers are generally believed to operate by way of a conjugated pi-electron system, and it will be understood that some substituents or combinations of substituents may interfere with the conjugated system so as to detract from or destroy the desired electrical conductivity, acceptable substituents being readily determinable by simply testing the conductivity of the resulting polymer. It is however not essential that the conductive material be a true polymer or oligomer, provided that it displays the required NTC effect.
- oxidative doping of 2,5-dimethyl pyrrole can produce a black powder which is not readily identifiable as a polymer, but has the strong NTC effect aforementioned.
- the products of oxidative doping of 2,3-dimethyl pyrrole, 2,4-dimethyl pyrrole and 2-methyl pyrrole have the aforementioned NTC effect are believed to be new materials which are accordingly claimed per se together with their lower alkyl homologues as part of the present invention.
- the 2-substituted pyrrole and the dopant are mixed with an oxidising agent in a suitable liquid vehicle.
- the oxidising agent can advantageously be carried by the dopant, for example by forming the ferric salt of a dopant such as p-toluenesulphonate or halide ions, thereby bringing about simultaneous oxidative polymerisation and doping with the negatively charged dopant.
- Some oxidation reactions tend to produce an insoluble product, which is relatively non-conductive, and a soluble product which, alone or in a mixture with the insoluble product, displays the marked NTC behaviour on which the present invention is based.
- 2,5-dimethyl pyrrole is commercially available.
- the remaining methyl pyrroles: 2-methyl; 2,3-dimethyl; 2,4-dimethyl and 3,4-dimethyl were synthesised by known literature methods.
- methyl pyrroles can be oxidised by metal salt oxidants such as ferric perchlorate to brown or black conductive powders. With the exception of 2,5-dimethyl pyrrole, chlorine can also be used to oxidise the methyl pyrroles.
- Example 2 was repeated substituting 2-methyl pyrrole for the 2,4-dimethylpyrrole.
- Example 2 was repeated substituting 2,3-dimethylpyrrole for the 2,4-dimethylpyrrole.
- the pyrrole samples were compressed into pellets 1.3cm diameter using a SPECAC Powder Jig.
- the powder was preheated in the jig to about 140°C then loaded under pressure (ca. 40 kgcm ) for 5 minutes.
- the compressed sample was removed, checked for quality, and measured on a digital multimeter by locating the pellet between spring-loaded circular copper electrodes in a 2 probe configuration.
- Conductivity vs. temperature curves were obtained by placing the device in a temperature programmable oven. The results are shown in the accompanying drawing.
- NTC effect of oxidatively doped 2-methyl pyrrole, 2,4-dimethyl pyrrole and 2,5-dimethyl pyrrole is shown graphically compared with the very much less significant NTC effect of oxidatively doped 3,4-dimethyl pyrrole.
- Unsubstituted pyrrole produces a substantially zero temperature coefficient, which could be plotted as a substantially horizontal line on this graph.
- mixtures of the 2-substituted pyrroles may be advantageous to use mixtures of the 2-substituted pyrroles with one another or with other pyrroles.
- oxidative doping of a mixture of a 2-substituted pyrrole with unsubstituted pyrrole has been found to achieve an NTC effect comparable with that of the 2-substituted pyrrole itself, while considerably raising the conductivity (lowering the resistivity) of the resulting material.
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Thermistors And Varistors (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB838300352A GB8300352D0 (en) | 1983-01-07 | 1983-01-07 | Ntc electrical device |
GB8300352 | 1983-01-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0121289A1 true EP0121289A1 (fr) | 1984-10-10 |
Family
ID=10536020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19840300084 Withdrawn EP0121289A1 (fr) | 1983-01-07 | 1984-01-06 | Dispositif électrique à coefficient de température négatif |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0121289A1 (fr) |
JP (1) | JPS59135704A (fr) |
CA (1) | CA1200614A (fr) |
GB (1) | GB8300352D0 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7161463B2 (en) | 2001-12-14 | 2007-01-09 | Shin-Etsu Polymer Co., Ltd. | Organic NTC composition, organic NTC device and production method of the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0618863B2 (ja) * | 1986-03-28 | 1994-03-16 | 三菱化成株式会社 | 有機半導体 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3574072A (en) * | 1968-04-03 | 1971-04-06 | Universal Oil Prod Co | Polymerization of heterocyclic compounds |
EP0037924A2 (fr) * | 1980-04-11 | 1981-10-21 | BASF Aktiengesellschaft | Procédé de préparation de polycondensats électriquement conducteurs et leur utilisation dans le domaine électrotechnique et comme additifs antistatiques pour des matériaux plastiques |
EP0055358A1 (fr) * | 1980-12-31 | 1982-07-07 | BASF Aktiengesellschaft | Dérivés électro-conducteurs de polypyrrole |
-
1983
- 1983-01-07 GB GB838300352A patent/GB8300352D0/en active Pending
-
1984
- 1984-01-06 EP EP19840300084 patent/EP0121289A1/fr not_active Withdrawn
- 1984-01-06 CA CA000444821A patent/CA1200614A/fr not_active Expired
- 1984-01-07 JP JP123284A patent/JPS59135704A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3574072A (en) * | 1968-04-03 | 1971-04-06 | Universal Oil Prod Co | Polymerization of heterocyclic compounds |
EP0037924A2 (fr) * | 1980-04-11 | 1981-10-21 | BASF Aktiengesellschaft | Procédé de préparation de polycondensats électriquement conducteurs et leur utilisation dans le domaine électrotechnique et comme additifs antistatiques pour des matériaux plastiques |
EP0055358A1 (fr) * | 1980-12-31 | 1982-07-07 | BASF Aktiengesellschaft | Dérivés électro-conducteurs de polypyrrole |
Non-Patent Citations (1)
Title |
---|
"ORGANIC CONDUCTORS", Emerging Technologies no. 8; Published by Technical Insights, Inc,; Fort Lee, N.J., October 1982 *pages 21-24* * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7161463B2 (en) | 2001-12-14 | 2007-01-09 | Shin-Etsu Polymer Co., Ltd. | Organic NTC composition, organic NTC device and production method of the same |
Also Published As
Publication number | Publication date |
---|---|
JPS59135704A (ja) | 1984-08-04 |
CA1200614A (fr) | 1986-02-11 |
GB8300352D0 (en) | 1983-02-09 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19840130 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR IT LI NL SE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19860228 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BAIGRIE, STEPHEN Inventor name: HARDY, JUDITH Inventor name: LINES, ROBERT |