WO1992016950A1 - Method of preparation of a conductive polymer - Google Patents
Method of preparation of a conductive polymer Download PDFInfo
- Publication number
- WO1992016950A1 WO1992016950A1 PCT/FI1992/000059 FI9200059W WO9216950A1 WO 1992016950 A1 WO1992016950 A1 WO 1992016950A1 FI 9200059 W FI9200059 W FI 9200059W WO 9216950 A1 WO9216950 A1 WO 9216950A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conductive polymer
- mixture
- polymer
- ozone
- plastic
- Prior art date
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 2
- 239000004033 plastic Substances 0.000 claims abstract description 26
- 229920003023 plastic Polymers 0.000 claims abstract description 26
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000002019 doping agent Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000005611 electricity Effects 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 2
- 239000012803 melt mixture Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 poly(3-octylthiophene) Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012421 spiking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 229920000280 Poly(3-octylthiophene) Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009747 press moulding Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
Definitions
- the invention is concerned with a method of preparing a conductive polymer by doping of a conductive polymer or a mixture of a matrix plastic and a conductive polymer.
- the invention is concerned with a method of preparing conductive plastic products by doping of a conductive polymer or a plastic mixture contain ⁇ ing a conductive polymer.
- the good isolating properties of plastics have in some cases restricted their use, for example because static electricity has been collected in packages prepared of plastic. Static electricity has increased the adhesion of films to each other in the production processes of plastics and thus made the winding properties worse.
- the package products charged with static electricity can in the use cause situ ⁇ ations of danger for example a risk of explosion. Spiking may cause dangerous situations, especially in solvents to be held in plastic barrels and in other inflam ⁇ mable fluids.
- Static electricity in package materials also increases the contamination of the packages during storage. In packages with sensitive electronic components it is very important to avoid spiking and forming of static electricity.
- plastics to be conductive or antistatic Three methods are mainly used for treating plastics to be conductive or antistatic of which one way is to add metallic powder or soot among the isolating and non- conductive plastic to achieve conductivity.
- the problem with this is that there shall be so much added particles uniformly distributed that they touch each other. In this case also the conductivity curve will have bends, in other words, at low concentrations there is no conductivity and after a given threshold value the conductivity is high.
- Another possibility to treat plastics to be antistatic is to treat the surface of the plastic product either with corona charging or with given chemicals.
- the problem with the corona charging is that the effect is maintained only for a short time.
- the problem with the chemical surface treatment is its dependence on humidity. The surface resistance of a plastic product thus treated depends on the air humidity around the product.
- the third possibility is to coat the plastic product with a thin metallic layer.
- the problem with this method is that the product is very brittle, the surface is sensitive and the conductivity curve has bends.
- the best way is to make the plastic product of a polymer that is conductive in itself or from a mixture of such polymer and a matrix plastic. Then the conduc ⁇ tivity of the product can be exactly controlled in accordance with the wished use either by changing the composition of the polymeric mixture or by altering the doping degree.
- Polythiophene is one of those polymers that can be made electrically active on the above mentioned way.
- Polythiophene can be prepared for example by using catalysts of Ziegler-type and acid-inititators.
- the aim of this invention is a method wherein the doping can be carried out quickly and simply and in a way that saves the environment.
- the method of the invention is mainly characterized in that the doping is carried out by means of ozone.
- the doping can be carried out by adding dopant to the conductive polymer in melt state in which case the timing of the doping is made to happen in connec- tion with the working or after that or before the melting of the conductive polymer, in the connection with that or after that.
- the dopant is added for example to the extruder or after that before the mould pressing.
- the doping can be carried out in a way according to the invention for example in connection with some melt working method of plastics.
- Different working methods are for example extrusion, calandering, deepdrawing, coating and injection moulding, press moulding, film blowing etc.
- the dopant can in a way according to the invention be introduced to the melt mixture either so that it is mixed with the conductive polymer or with the matrix plastic or the dopant can be added directly to the conductive polymer or to a powder or a melt mixture of the conductive polymer and a matrix plastic. Then the mixing of the dopant with the plastic is carried out for example in the extruder before pressing of the product, in which case the doping begins in connection with the melt mixing and continues during the forming of the product and after that.
- the polymer used can be any polymer that can be doped and worked in melt state for example poly(3-octylthiophene) and the matrix material can be any polymer that can be worked.
- the invention can be used for preparing a polymer with any possible conductiv ⁇ ity, as it is characteristic for the invention that already small ozone amounts (ca 0,2%) are enough to achieve a degree of conductivity (10 ⁇ 6 - 10 "5 s/cm), which is enough for antistatic applications.
- the advantage with the invention is that no diffusion of dopant from the material exists. Further advantages are that the doping is quick, it is simple to carry out and the material doped with ozone does not cause any harm for the environment. In addition to that it can be adapted to the process.
- the doping of the conductive polymer was carried out with the device of figure 1.
- Oxygen was led from an oxygen bottle 1 via a control valve to ozonizer 3.
- ozonizer 3 In the gas stream coming from the ozonizer 5-7% was ozone and the rest of it was oxygen.
- the ozone was lead to a rotatable piston 4, inside which there was conductive polymer in form of powder.
- the gas stream coming from the piston was lead to a KJ-solution 5, to which the ozone that did not react with the conductive polymer was bound.
- the amount of the bound ozone to the conductive polymer could be determined.
- Samples of the conductive polymer was taken from the piston 4 during the test. Tablets were pressed from the samples from which the conductivity was determined.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention is concerned with a method of preparing a conductive polymer by doping a conductive polymer or a mixture containing a conductive polymer and a matrix plastic with ozone.
Description
Method of preparation of a conductive polymer
The invention is concerned with a method of preparing a conductive polymer by doping of a conductive polymer or a mixture of a matrix plastic and a conductive polymer.
More in detail, the invention is concerned with a method of preparing conductive plastic products by doping of a conductive polymer or a plastic mixture contain¬ ing a conductive polymer.
The good isolating properties of plastics have in some cases restricted their use, for example because static electricity has been collected in packages prepared of plastic. Static electricity has increased the adhesion of films to each other in the production processes of plastics and thus made the winding properties worse. The package products charged with static electricity can in the use cause situ¬ ations of danger for example a risk of explosion. Spiking may cause dangerous situations, especially in solvents to be held in plastic barrels and in other inflam¬ mable fluids.
Static electricity in package materials also increases the contamination of the packages during storage. In packages with sensitive electronic components it is very important to avoid spiking and forming of static electricity.
Three methods are mainly used for treating plastics to be conductive or antistatic of which one way is to add metallic powder or soot among the isolating and non- conductive plastic to achieve conductivity. The problem with this is that there shall be so much added particles uniformly distributed that they touch each other. In this case also the conductivity curve will have bends, in other words, at low concentrations there is no conductivity and after a given threshold value the conductivity is high.
Another possibility to treat plastics to be antistatic is to treat the surface of the plastic product either with corona charging or with given chemicals. The problem with the corona charging is that the effect is maintained only for a short time. The problem with the chemical surface treatment is its dependence on humidity. The surface resistance of a plastic product thus treated depends on the air humidity around the product.
The third possibility is to coat the plastic product with a thin metallic layer. The problem with this method is that the product is very brittle, the surface is sensitive and the conductivity curve has bends.
The best way is to make the plastic product of a polymer that is conductive in itself or from a mixture of such polymer and a matrix plastic. Then the conduc¬ tivity of the product can be exactly controlled in accordance with the wished use either by changing the composition of the polymeric mixture or by altering the doping degree.
Polythiophene is one of those polymers that can be made electrically active on the above mentioned way. Polythiophene can be prepared for example by using catalysts of Ziegler-type and acid-inititators.
The aim of this invention is a method wherein the doping can be carried out quickly and simply and in a way that saves the environment.
To achieve the objects the method of the invention is mainly characterized in that the doping is carried out by means of ozone.
The advantageous embodiments of the invention have the characteristics of the subclaims.
The doping can be carried out by adding dopant to the conductive polymer in melt state in which case the timing of the doping is made to happen in connec-
tion with the working or after that or before the melting of the conductive polymer, in the connection with that or after that.
When the doping is carried out in connection with the working of the product, for example in connection with extrusion, the dopant is added for example to the extruder or after that before the mould pressing.
The doping can be carried out in a way according to the invention for example in connection with some melt working method of plastics. Different working methods are for example extrusion, calandering, deepdrawing, coating and injection moulding, press moulding, film blowing etc.
The dopant can in a way according to the invention be introduced to the melt mixture either so that it is mixed with the conductive polymer or with the matrix plastic or the dopant can be added directly to the conductive polymer or to a powder or a melt mixture of the conductive polymer and a matrix plastic. Then the mixing of the dopant with the plastic is carried out for example in the extruder before pressing of the product, in which case the doping begins in connection with the melt mixing and continues during the forming of the product and after that.
The polymer used can be any polymer that can be doped and worked in melt state for example poly(3-octylthiophene) and the matrix material can be any polymer that can be worked.
The invention can be used for preparing a polymer with any possible conductiv¬ ity, as it is characteristic for the invention that already small ozone amounts (ca 0,2%) are enough to achieve a degree of conductivity (10~6 - 10"5 s/cm), which is enough for antistatic applications.
The advantage with the invention is that no diffusion of dopant from the material exists. Further advantages are that the doping is quick, it is simple to
carry out and the material doped with ozone does not cause any harm for the environment. In addition to that it can be adapted to the process.
In the following there is presented an embodiment example of the invention with reference to figures 1-2. The invention is not restricted to the details of the figures but they are presented to illustrate the invention.
Example
The doping of the conductive polymer was carried out with the device of figure 1.
Oxygen was led from an oxygen bottle 1 via a control valve to ozonizer 3. In the gas stream coming from the ozonizer 5-7% was ozone and the rest of it was oxygen. The ozone was lead to a rotatable piston 4, inside which there was conductive polymer in form of powder. The gas stream coming from the piston was lead to a KJ-solution 5, to which the ozone that did not react with the conductive polymer was bound.
By measuring the gas streams and by titration of the KJ-solution the amount of the bound ozone to the conductive polymer could be determined. Samples of the conductive polymer was taken from the piston 4 during the test. Tablets were pressed from the samples from which the conductivity was determined.
About 100 g of polyoctylthiophene was to be doped in the test. The results are in Table 1. The conductivity as a function of the ozone bound to the conductive polymer is presented in that. The same thing is presented in figure 2.
Table 1
Amount of absorbed ozone The conductivity of the
% of weight polymer 10 S/cm
0,2 8
0,4 10
0,6 12
0,8 15 1,0 16
In the following the patent claims are presented which are not meant to restrict the invention.
Claims
1. Method of preparing a conductive plastic product by doping a conductive polymer or a mixture of a matrix plastic and a conductive polymer, character- ized in that the doping is carried out with ozone.
2. Method of claim 1, characterized in that the conductive polymer or the mixture of the conductive polymer and a matrix plastic is brought into contact with ozone gas after which the mixture is worked to a product in a way known in itself.
3. Method of claim 1-2, characterized in that the dopant is added to the conductive polymer or to a mixture of the conductive polymer and the matrix plastic before melting.
4. Method of claim 1, characterized in that the conductive polymer or the mixture of the matrix plast and the conductive polymer is brought into contact with the ozone gas during the working or after that.
5. Method of any of claims 4, characterized in that the dopant is added to the conductive polymer or to a mixture of a conductive polymer and the matrix plastic in connection with the melting.
6. Method of claim 4, characterized in that the dopant is added to the conduc- tive polymer or to a mixture containing the conductive polymer and the matrix plastic after the melting.
7. Method of any of claims 1-6, characterized in that the conductivity of the polymer is regulated by the amount of the ozone or by the amount of the conductive polymer in the composite.
8. Method of claims 1-7, characterized in that the amount of the ozone in the polymer to be doped is 0,01-1 % of weight, preferably 0,2-1,2 % of weight, most preferably ca 0,2 % of weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI911271 | 1991-03-14 | ||
| FI911271A FI89720C (en) | 1991-03-14 | 1991-03-14 | FRAMSTAELLNINGSFOERFARANDE FOER ELLEDANDE POLYMER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992016950A1 true WO1992016950A1 (en) | 1992-10-01 |
Family
ID=8532118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FI1992/000059 WO1992016950A1 (en) | 1991-03-14 | 1992-02-28 | Method of preparation of a conductive polymer |
Country Status (2)
| Country | Link |
|---|---|
| FI (1) | FI89720C (en) |
| WO (1) | WO1992016950A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150228902A1 (en) * | 2012-09-25 | 2015-08-13 | Merck Patent Gmbh | Formulations containing conductive polymers and use thereof in organic electronic devices |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062211A2 (en) * | 1981-04-02 | 1982-10-13 | Bayer Ag | Sheets and fibres containing particles of doped polyactylene in the form of adhesives or fibres, and method for their preparation |
| EP0214506A1 (en) * | 1985-08-29 | 1987-03-18 | Bayer Ag | Electrically conductive polymers and process for their manufacture |
| WO1989001015A1 (en) * | 1987-07-29 | 1989-02-09 | Neste Oy | Conductive plastic composites |
| WO1990009027A1 (en) * | 1989-01-27 | 1990-08-09 | Neste Oy | Use of electrically conducting polymer composites |
| WO1991015859A1 (en) * | 1990-03-30 | 1991-10-17 | Neste Oy | A method for preparing a conductive polymer |
-
1991
- 1991-03-14 FI FI911271A patent/FI89720C/en not_active IP Right Cessation
-
1992
- 1992-02-28 WO PCT/FI1992/000059 patent/WO1992016950A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062211A2 (en) * | 1981-04-02 | 1982-10-13 | Bayer Ag | Sheets and fibres containing particles of doped polyactylene in the form of adhesives or fibres, and method for their preparation |
| EP0214506A1 (en) * | 1985-08-29 | 1987-03-18 | Bayer Ag | Electrically conductive polymers and process for their manufacture |
| WO1989001015A1 (en) * | 1987-07-29 | 1989-02-09 | Neste Oy | Conductive plastic composites |
| WO1990009027A1 (en) * | 1989-01-27 | 1990-08-09 | Neste Oy | Use of electrically conducting polymer composites |
| WO1991015859A1 (en) * | 1990-03-30 | 1991-10-17 | Neste Oy | A method for preparing a conductive polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150228902A1 (en) * | 2012-09-25 | 2015-08-13 | Merck Patent Gmbh | Formulations containing conductive polymers and use thereof in organic electronic devices |
| US9972782B2 (en) * | 2012-09-25 | 2018-05-15 | Merck Patent Gmbh | Formulations containing conductive polymers and use thereof in organic electronic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| FI911271A0 (en) | 1991-03-14 |
| FI89720C (en) | 1993-11-10 |
| FI89720B (en) | 1993-07-30 |
| FI911271L (en) | 1992-09-15 |
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