WO1997021228A1 - Electrically conducting polymers and their manufacture - Google Patents
Electrically conducting polymers and their manufacture Download PDFInfo
- Publication number
- WO1997021228A1 WO1997021228A1 PCT/GB1996/002954 GB9602954W WO9721228A1 WO 1997021228 A1 WO1997021228 A1 WO 1997021228A1 GB 9602954 W GB9602954 W GB 9602954W WO 9721228 A1 WO9721228 A1 WO 9721228A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chains
- conductive polymer
- groups
- reaction
- resonant
- Prior art date
Links
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
Definitions
- This invention relates to polymers that are inherently electrically conductive and to a method of making them.
- One of the applications for which the polymers may be used is in the control of electric fields in cable joints.
- a variety of electrically conducting polymers have been discovered and a number of them are now finding useful applications. Among them are polyaniline, polypyrrole, polyacetylene, polythiophene, poly-p-phenylene, poly- (p-phenylene sulfide) and poly-N-vinylcarbazole .
- All of these established conducting polymers have an essentially one-dimensional structure composed of resonant (aromatic and/or heterocydic) rings connected to form a single chain in which conjugation extends from end to end of the molecule. A consequence of this is that they conduct primarily along the length of the molecule and have relatively small conductivities unless the molecules are aligned by orientation, and then conduct well in only one direction.
- the polymers in accordance with the invention comprise chains composed of resonant (aromatic and/or heterocydic) rings in which conjugation extends from end to end of the molecule and crosslinks between these chains and is characterised in that such crosslinks consist of resonant groups conjugated to the chains that they link.
- the polymer chains are selected from polyaniline, polypyrrole, polythiophene, poly-p-phenylene, poly- (p-phenylene sulfide) and poly-N-vinylcarbazole.
- the resonant groups constituting the crosslinks may be carbocyclic or heterocydic aromatic groups, conjugated ⁇ -bonded aliphatic groups, or combinations of any of these. We prefer that (apart from any parts contributed by sidechains already present in the polymer chains) they are selected from p-phenylene groups, p-phenylene-vinylene groups and sequences of one or both of these.
- a process for making such polymers comprises a conjugative condensation reaction catalysed by a palladium compound.
- the Suzuki reaction requires the prior introduction into one of the aromatic molecules to be linked of a leaving group selected from halides (preferably bromine) and the triflate group (also called trifluoromethane sulfonate) .
- a leaving group selected from halides (preferably bromine) and the triflate group (also called trifluoromethane sulfonate) .
- these groups are introduced into the polymer chains .
- the other molecule to be linked preferably the relatively small molecule that is to provide the crosslinking groups
- the Heck reaction is a little different in that it requires a pendant alkene group in one of the molecules to be linked. This is reacted with an arylpalladium group introduced into the other molecule to be linked, and since this group is labile it is invariably generated in situ.
- reaction of a bromo- substituent with a palladium- triarylphosphine complex reaction of an iodo- substituent with palladium acetate in the presence of a base
- reaction of a substituent group selected from -HgR and -HgX (where R is an aromatic group and X is halide or triflate) with lithium palladium trichloride
- direct reaction of the unsubstituted aromatic molecule with palladium acetate (or metallic palladium and silver acetate) in acetic acid reaction of the unsubstituted aromatic molecule with palladium acetate (or metallic palladium and silver acetate) in acetic acid.
- the Heck reaction rather than the others, i ⁇ appropriate to forming p-phenylene-vinylene crosslinks.
- the crosslinking reaction is carried out in dilute solution, the product will normally be obtained as a powder which, because it is crosslinked, will be infusible, insoluble and generally difficult to use, except as a conductive filler in polymers and coating compositions.
- the crosslinking reaction is carried out in a concentrated solution from which solvent may evaporate during and/or after the reaction to deposit the crosslinked product as a continuous coating.
- At least some of the polymers in accordance with the invention have been found to have markedly non-linear electrical properties, with conductivities at even 10 -20V in some cases two or three orders of magnitude higher than in the oh ic region at low voltages; thus polymers whose conductivity as measured in the ohmic region appears quite inadequate may be usefully conductive at voltages in the kV range .
- the screen is terminated in a plane normal to the cable axis, and as it is impracticable to make a cut with complete accuracy and total repeatability (and in most cases impossible to re-cut if anything goes wrong) this is achieved by removing the screen a little further than desired and restoring to the required position by applying a conductive coating based on carbon black.
- This coating is not of great strength and is at risk of damage when other cable components (especially the "stress cone") are slid into place. In the nature of the problem, the coating is inaccessible and cannot be inspected for such damage after the stress cone is in place, since removing it would multiply the risk. It is suspected that such damage may be responsible for a significant fraction of joint failures in service.
- a tougher conductive coating can be formed and the risk substantially reduced.
- each of equations 1-4 represents a step in the synthesis of one of the conducting polymers to be described and each of Figures 1-3 is a graph showing a current/voltage characteristic of one polymer in accordance with the invention.
- the final cross-linked polymer was produced by thoroughly mixing the whole of Solutions A and B and heating under reflux conditions for 24 hours.
- the product was obtained as a black insoluble powder, washed and dried; portions were pressed into circular plaques 20.1 mm in area and about 0.5 to 1 mm thick under a pressure of 25 tonnes; the plaques were sandwiched between electodes and current/voltage relationships plotted using a Keithley 617 Electrometer, each reading being taken after stabilising for 5 minutes.
- the ohms law region of each plaque was determined (for accuracy by determining the part of the characteristic in which the gradient of log V vs log I was 1) and the resistivity calculated and tabulated for that region. This procedure will be more fully described below, with reference to Figures 1-3
- Example 2 This was substantially the same as Example 1 Run 1 except that the volume of solvent in each of solutions A and B was reduced until the solution became very viscous and the final polymer was obtained by mixing the solutions and applying the mixture immediately to a dry surface of an inert polymer material and then heating to 50°C for 24 hours to cure the coating and remove the residual solvent from it .
- the final cross-linked polymer was a black insoluble solid.
- Example 3 This was similar to Example 1 except that it was based on a hompolymer of p-bromobenzaldehyde instead of the copolymer; in the first stage of synthesis, the benzaldehyde was (of course) omitted and the amount of p-bromobenzaldehyde doubled to 52.6 g; subsequent procedure was as before and the results were as follows: Table 2
- Figures 1-3 show data for Run 10 of this Example, respectively in log/log, linear/linear and enlarged log/log format .
- Figures 1 and 2 clearly demonstrate the highly non-linear characteristics of this polymer for voltages of each polarity
- Figure 3 shows how a log-log plot (here restricted to the relevant part of the "positive" polarity side of the graph) more clearly identifies the Ohm's law region in which the gradient of Figure 2 is constant and that of figures 1 and 3 is unity. Having identified the linear region of Figure 2 in this way, its gradient and thus the resistance of the plaque can be determined and conductivity (and/or resistivity) calculated in the usual way.
- Poly(3-phenyl-2, 5-thiophene) was synthesised in three stages via 3-phenyl-2-chlorothiophene as follows (Equations 2-4) .
- 2, 5-Dichlorothiophene (5.0 g) , dichloromethane (20 ml) and benzene (8.8 ml) were mixed together in a 2-necked round bottomed flask, cooled to 0°C and stirred for 10 minutes.
- Aluminium chloride (4.4 g) was then added slowly over a period of 5 minutes. The mixture was stirred at 0°C for 30 minutes, then at room temperature for 1 hour and then refluxed for 30 minutes.
- Example 5 This was also similar to Run 15 (or Run 16) of Example 3, except that in the poly eration reaction 10 mole % of the 3-phenyl-2, 5-dichlorothiophene was replaced by 2, 5-dichloro- thiophene .
- TetraJis(triphenylphosphine)palladium(0) (0.02 g) as catalyst and 4,4 ' -biphenyl diboronic acid (0.334 g) to form crosslinking groups were dissolved in tetrahydrofuran (10 ml) and the volume of the solvent reduced until the solution became very viscous and Examples 2 and 6 respectively were repeated except that this solution was used instead of the solution containing dichlorobis[1, 1 ' -bis(diphenylphosphino) ferrocene] palladium(II) ; results were similar.
- a 250kV power cable insulated with cross-linked polyethylene was prepared for jointing in the usual way and the dielecric screen trimmed normal to the cable axis some 5 mm beyond the design position of the screen end. At the latter position, an accurate square edge was defined by temporary application of a masking tape.
- the mixed solution from Example 2 was painted on the bare area of dielectric between the masking tape and the cut edge of the screen and for a few millimetres onto the screen.
- the coated area was heated to a temperature of about 50°C by a portable gas heater for 24 hours while work continued on other parts of the joint (the completion of a complete cable joint at such supertension voltages takes several days, and the reaction time is not unacceptable) .
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96940028A EP0864163A1 (en) | 1995-12-02 | 1996-11-29 | Electrically conducting polymers and their manufacture |
GB9811694A GB2322136A (en) | 1995-12-02 | 1996-11-29 | Electrically conducting polymers and their manufacture |
AU77034/96A AU7703496A (en) | 1995-12-02 | 1996-11-29 | Electrically conducting polymers and their manufacture |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9524705.2 | 1995-12-02 | ||
GBGB9524705.2A GB9524705D0 (en) | 1995-12-02 | 1995-12-02 | Electrically conducting polymers and their manufacture |
GBGB9525014.8A GB9525014D0 (en) | 1995-12-07 | 1995-12-07 | Electrically conducting polymers and their manufacture |
GB9525014.8 | 1995-12-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1997021228A1 true WO1997021228A1 (en) | 1997-06-12 |
WO1997021228A9 WO1997021228A9 (en) | 1997-08-07 |
Family
ID=26308215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1996/002954 WO1997021228A1 (en) | 1995-12-02 | 1996-11-29 | Electrically conducting polymers and their manufacture |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0864163A1 (en) |
AU (1) | AU7703496A (en) |
WO (1) | WO1997021228A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007018439A1 (en) * | 2005-08-11 | 2007-02-15 | Auckland Uniservices Limited | Conducting polymers and uses thereof |
US7404914B2 (en) * | 1995-11-29 | 2008-07-29 | International Business Machines Corporation | Polycrystalline conducting polymers having adjustable morphology and properties |
US7508650B1 (en) | 2003-06-03 | 2009-03-24 | More Energy Ltd. | Electrode for electrochemical capacitor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0432104A (en) * | 1990-05-25 | 1992-02-04 | Fuji Photo Film Co Ltd | New conductive high polymer and conductive material thereof |
US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
WO1995000882A1 (en) * | 1993-06-22 | 1995-01-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Soluble, conductive copolymer, the preparation and use thereof |
-
1996
- 1996-11-29 AU AU77034/96A patent/AU7703496A/en not_active Abandoned
- 1996-11-29 WO PCT/GB1996/002954 patent/WO1997021228A1/en not_active Application Discontinuation
- 1996-11-29 EP EP96940028A patent/EP0864163A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0432104A (en) * | 1990-05-25 | 1992-02-04 | Fuji Photo Film Co Ltd | New conductive high polymer and conductive material thereof |
US5254627A (en) * | 1993-01-07 | 1993-10-19 | Ford Motor Company | Electrically conductive polypyrroleamine polymer networks |
WO1995000882A1 (en) * | 1993-06-22 | 1995-01-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Soluble, conductive copolymer, the preparation and use thereof |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 016, no. 200 (E - 1201) 13 May 1992 (1992-05-13) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7404914B2 (en) * | 1995-11-29 | 2008-07-29 | International Business Machines Corporation | Polycrystalline conducting polymers having adjustable morphology and properties |
US7508650B1 (en) | 2003-06-03 | 2009-03-24 | More Energy Ltd. | Electrode for electrochemical capacitor |
WO2007018439A1 (en) * | 2005-08-11 | 2007-02-15 | Auckland Uniservices Limited | Conducting polymers and uses thereof |
US8378058B2 (en) | 2005-08-11 | 2013-02-19 | Auckland Uniservices Limited | Conducting polymers and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
AU7703496A (en) | 1997-06-27 |
EP0864163A1 (en) | 1998-09-16 |
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