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WO1999024991A1 - Compositions polymeres conductrices - Google Patents

Compositions polymeres conductrices Download PDF

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Publication number
WO1999024991A1
WO1999024991A1 PCT/GB1998/003241 GB9803241W WO9924991A1 WO 1999024991 A1 WO1999024991 A1 WO 1999024991A1 GB 9803241 W GB9803241 W GB 9803241W WO 9924991 A1 WO9924991 A1 WO 9924991A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
solvent
fluid mixture
sulfonic acid
mixture
Prior art date
Application number
PCT/GB1998/003241
Other languages
English (en)
Inventor
Phillip Norman Adams
Andrew Paul Monkman
Stephen John Pomfret
Original Assignee
Corning Communications Limited
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
Priority claimed from GBGB9723464.5A external-priority patent/GB9723464D0/en
Priority claimed from GBGB9801159.6A external-priority patent/GB9801159D0/en
Application filed by Corning Communications Limited filed Critical Corning Communications Limited
Priority to JP2000519900A priority Critical patent/JP2001522898A/ja
Priority to AU96377/98A priority patent/AU9637798A/en
Priority to CA002309194A priority patent/CA2309194A1/fr
Priority to EP98950224A priority patent/EP1029329A1/fr
Publication of WO1999024991A1 publication Critical patent/WO1999024991A1/fr

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
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • Conductive Polymer Compositions This invention relates to conductive polymer compositions and more particularly to fluid compositions based on polyaniline from which conductive fibres, films and coatings can be made.
  • the emeraldine base form of polyaniline, doped with a sulfonic acid, is now well-established as a useful air-stable conductive polymer (and the leuco base form may also be useful) , but conventional fluid compositions only form good films if their solids content is rather small, and even then the films do not draw well.
  • the present invention provides compositions which are capable of use in a wet-spinning process for the manufacture of drawn fibres; they are also useful for the manufacture of drawable films and of coatings by processes in which a competitive solvent is used to achieve solidification faster than is possible by solvent evaporation alone.
  • the polymer composition in accordance with the invention is the reaction product of: (a) a polyaniline in base form;
  • the sulfonic acid not only acts as a dopant to make the polyaniline conductive but also as a solvating agent to increase the "solubility" of the polymer (the word has been put in inverted commas because the mixtures are sometimes considered to be, at least partly, stable dispersions rather than true (fully solvated) solutions: a homogenising step will usually be required in forming them) .
  • polyaniline is preferably as free of branching and other defects as possible, and polyanilines of the kind showing only two substantial peaks in their 13 C NMR spectra in the leuco base form, in accordance with W095/23822, are preferred.
  • high molecular weight is normally also desirable, but this may not always be so if the mixture is for use in making coatings.
  • the polyaniline is in its emeraldine base form; alternatively it is possible to use the leuco base form, though for most applications this will eventually need to be oxidised to the emeraldine form.
  • the aliphatic sulfonic acid is preferably wholly free of ring structures (especialy aromatic ones), and ideally also free of bulky substituents .
  • Polymerised or polymerisable aliphatic sulfonic acids have the advantage that they are less likely to migrate away from the polyaniline, and may therefore be preferred. High molecular weights are undesirable.
  • Preferred functional groups are carbonyl, amido, amino and hydroxy, especially amido and carbonyl.
  • ACES and most especially AMPSA (and its oligomers) are preferred.
  • pK a values of aliphatic sulfonic acids are difficult to measure and not readily acessible, but it may be assumed that they all have pK a values lower than 1, and in many cases below 0.
  • the proportion of sulfonic acid in the mixture may vary in the usual ranges; mostly a proportion in the range from
  • the acid solvent has a pK a not greater than 4 and more especially not greater than 3 or better still 2 or even 1.5; preferably it is at least 0.5 units larger (more positive) than that of the sulfonic acid.
  • carboxylic acids that meet these criteria and especially those with halogeno- substituents (meaning -Cl, -F or -CN) .
  • the mixtures in accordance with the invention may include more than one such acid solvent; they may also include additional solvents (diluents) and/or host polymers that may become incorporated into the fibres, films or coatings; we prefer that they do not contain lithium chloride (or any inorganic electrolytes) .
  • the fluid mixtures in accordance with the invention are green, indicating protonation of the polyaniline.
  • the invention includes processes for making fibres, films and coatings characterised by the step of removing the acid solvent from the mixtures described by exposing the mixture to the action of a competitive solvent, by which is meant a liquid in which the acid solvent in the mixture is readily soluble but polyaniline is substantially insoluble.
  • esters and ketones including in particular acetone, methylisobutyl ketone and butyl acetate are effective and suitable competitive solvents.
  • Water may be too effective for some processes, as it is usually desirable for some of the acid solvent to remain as an aid to subsequent drawing (a plasticiser) and over-rapid solidification may not be conducive to optimum structure; but aqueous solutions of alcohols, ketones and esters may prove usable.
  • the invention includes l.a process for the manufacture of polyaniline fibre which is a wet-spinning process in which the mixture described is caused to pass through the opening (s) of a spinneret into a bath of competitive solvent and the resulting filament optionally drawn simultaneously or subsequently;
  • Both fibres and films can be cold-drawn (at room temperature) or drawn at elevated temperatures, up to about
  • the polyaniline starting material for these examples is an emeraldine base prepared according to the teaching of W095/23822 and having a molecular weight (M p ) measured as described in that application of about 150,000 Daltons.
  • M p molecular weight
  • Polyaniline (3.467g) was ground by a pestle and mortar with AMPSA (4.533g, 57 molecules per hundred nitrogen atoms in the polyaniline) using a glove box with dry nitrogen atmosphere to avoid gelation.
  • the ground mixture was added to dichloroacetic acid (92.0g) to give a mixture with a solids content of 8% by weight (or about 12%w/v, as the acid has a specific gravity of about 1.5).
  • the mixture was homogenised for 10 minutes in a Ultraturrax homogeniser running at 20,000 rpm. The homogenisation/protonation is appreciably exothermic .
  • a portion of the resulting dark green mixture was cast onto a 125 mm diameter polished silicon wafer and dried in an oven at 80 2 C for about 24 hours.
  • the dried film was peeled from the substrate and found to be 0.202 ⁇ 0.004 mm thick; its electrical conductivity was measured using a 4- wire probe and found to be 177 ⁇ 6 S/cm.
  • a dumbbell with a bar section 25 mm long and 4.0 mm wide was die-cut from this film and clamped in a stretching rig; it was heated to 110 2 C and then stretched slowly until the applied force reached 6.0 N. 5
  • the bar portion of the sample was then 58 mm long (elongation 130%), 0.114 ⁇ 0.004 mm thick and 2.7 mm wide; its longitudinal conductivity was 540 S/cm.
  • Polyaniline (0.632 g) was ground with AMPSA (0.868 g, 60
  • Polyaniline (1.517 g) was ground with AMPSA (2.083 g, 60 molecules per hundred nitrogen atoms) and then added under nitrogen to dichloroacetic acid (36.4 g) over a 5-minute period while homogenising at 20,000 rpm, generally as in the preceding examples. Homogenising was continued for a further 10 minutes to obtain a 9%-solids mixture (by weight - about 15% w/v) .
  • the mixture was transferred immediately, without cooling, to a cylindrical dope-pot 25 mm in diameter having at its bottom end a 140-micrometre filter and a spinneret consisting of a single hole with a diameter of 150 ⁇ m. The pot was removed from the glove box and promptly connected at its top end to a nitrogen gas supply.
  • An electric heating tape was wrapped round the pot to enable it to be brought to and held at a temperature of 50 ⁇ 5 2 C, and its bottom end was dipped into two litres of cold butyl acetate in a measuring cylinder.
  • the nitrogen pressure in the pot was raised to 0.7 MPa (100 psi) to spin a continuous filament, which was left in the butyl acetate for up to 10 minutes and then dried in air.
  • the filament was measured with a micrometer and found to have a diameter of 0.30 ⁇ 0.01 mm, and examination with a scanning electron microscope (including examination of a surface formed by fracture at liquid nitrogen temperature) showed it to be smoothly cylindrical and without apparent voids or granules. Longitudinal conductivity of the filament was 70 ⁇ 9 S/cm.
  • a ten-millimetre length of the filament was stretched at room temperature at a rate of about 10mm/sec, and was thus elongated into a fibre 50 mm long and with a uniform cross- section of 0.10 ⁇ 0.01 mm. Its conductivity was 810 ⁇ 200 S/cm and tensile strength at break about 45 MPa (breaking load 0.4 N) .
  • Example 3 This was substantially the same as Example 3 except that the butyl acetate was replaced by acetone.
  • the filament diameter (as formed) was 0.26 ⁇ 0.01 mm and
  • a filament was made by the same procedure as in Example 4 but in this case the diameter of the filament as formed (which is very sensitive to precise conditions) was 15 found to be 0.15 mm; its conductivity was still about 90 S/cm.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un mélange polymère conducteur fluide destiné à être utilisé dans la préparation de revêtements de films et de fibres est principalement constitué d'une polyaniline sous forme de base (de préférence d'émeraldine sous forme de base). Dans cette invention on dope la polyaniline avec un acide sulfonique comprenant en plus d'au moins un groupe acide sulfonique, un deuxième groupe fonctionnel à liaison hydrogène et on disperse cette aniline dopée dans un solvant acide présentant une valeur pKa inférieure à 4,5 mais sensiblement supérieure (plus positive) à celle de l'acide sulfonique. L'acide sulfonique fonctionnel semble agir en tant qu'agent de solvatation ainsi qu'en tant que dopant et permet de former des mélanges à forte teneur en solides dans les solvants acides (jusqu'à environ 15 % en poids si on le compare avec un maximum d'environ 10 % dans des mélanges classiques à base de NMP) desquels on peut extraire le solvant avec un solvant concurrent (par exemple dans un procédé de filage au mouillé); ceci permettant de produire des films et des fibres étirables à froid (et à chaud). L'acide sulfonique préféré est le 2-acrylamido-2-méthyle-1-acide propane sulfonique (AMPSA) ou son oligomère et le solvant acide préféré est l'acide dichloroacétique. Le solvant concurrent peut être l'acétone, le méthyle isobutyle cétone ou l'acétate de butyle.
PCT/GB1998/003241 1997-11-07 1998-10-30 Compositions polymeres conductrices WO1999024991A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2000519900A JP2001522898A (ja) 1997-11-07 1998-10-30 導電性ポリマー組成物
AU96377/98A AU9637798A (en) 1997-11-07 1998-10-30 Conductive polymer compositions
CA002309194A CA2309194A1 (fr) 1997-11-07 1998-10-30 Compositions polymeres conductrices
EP98950224A EP1029329A1 (fr) 1997-11-07 1998-10-30 Compositions polymeres conductrices

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9723464.5A GB9723464D0 (en) 1997-11-07 1997-11-07 Conductive polymer compositions
GB9723464.5 1997-11-07
GB9801159.6 1998-01-21
GBGB9801159.6A GB9801159D0 (en) 1998-01-21 1998-01-21 Conductive polymer compositions

Publications (1)

Publication Number Publication Date
WO1999024991A1 true WO1999024991A1 (fr) 1999-05-20

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Application Number Title Priority Date Filing Date
PCT/GB1998/003241 WO1999024991A1 (fr) 1997-11-07 1998-10-30 Compositions polymeres conductrices

Country Status (5)

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EP (1) EP1029329A1 (fr)
JP (1) JP2001522898A (fr)
AU (1) AU9637798A (fr)
CA (1) CA2309194A1 (fr)
WO (1) WO1999024991A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0923083A1 (fr) * 1997-12-09 1999-06-16 Kemet Electronics Corporation Solution de polyaniline avec solvant à base de terpène bicyclique
JP2003504459A (ja) * 1999-07-13 2003-02-04 コミツサリア タ レネルジー アトミーク 導電性ポリアニリン膜のドーパントとしてのスルホン酸及びホスホン酸の用途及びポリアニリンをベースにした導電性複合材料
WO2003033747A1 (fr) * 2001-10-16 2003-04-24 University Of Wollongong Separation et recuperation de metaux precieux a l'aide de materiaux polymeres
KR100401349B1 (ko) * 2000-09-20 2003-10-17 스마트텍 주식회사 전도성 폴리아닐린 방사용액의 제조 방법
WO2004042743A1 (fr) * 2002-10-30 2004-05-21 Santa Fe Science & Technology, Inc. Filage, dopage, dedopage et redopage d'une fibre de polyaniline
WO2004051672A3 (fr) * 2002-12-02 2004-10-28 Santa Fe Science And Technolog Chauffage ohmique faisant appel a des fibres de polyaniline
WO2005011415A1 (fr) * 2003-08-01 2005-02-10 Santa Fe Science And Technology, Inc. Structures polymeres conductrices multifonctionnelles
US6936955B1 (en) 2000-08-04 2005-08-30 Santa Fe Science And Technology, Inc. Conjugated polymer actuator responsive to electrical stimulation
US6982514B1 (en) 2000-05-22 2006-01-03 Santa Fe Science And Technology, Inc. Electrochemical devices incorporating high-conductivity conjugated polymers
US7288871B1 (en) 2003-07-03 2007-10-30 Santa Fe Science And Technology, Inc. Solid-in-hollow polymer fiber electrochemical devices
US8481849B2 (en) 2004-03-31 2013-07-09 The Yokohama Rubber Co., Ltd. Electrolyte for photovoltaic device as well as photovoltaic device and dye-sensitized solar cell including that electrolyte
US8691028B2 (en) * 2006-05-10 2014-04-08 The Boeing Company Article having a hexavalent-chromium-free, corrosion-inhibiting organic conversion coating thereon, and its preparation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5515089B2 (ja) * 2008-06-05 2014-06-11 日産自動車株式会社 導電性高分子繊維およびその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262195A (en) * 1990-11-05 1993-11-16 Brewer Science Soluble conducting polymers and their use in manufacturing electronic devices
US5520852A (en) * 1994-06-08 1996-05-28 Neste Oy Processible electrically conducting polyaniline compositions
DE19653196A1 (de) * 1995-12-20 1997-06-26 Mando Machinary Co Leitfähiges mit Kampfersulfonsäure dotiertes Polyanilin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262195A (en) * 1990-11-05 1993-11-16 Brewer Science Soluble conducting polymers and their use in manufacturing electronic devices
US5520852A (en) * 1994-06-08 1996-05-28 Neste Oy Processible electrically conducting polyaniline compositions
DE19653196A1 (de) * 1995-12-20 1997-06-26 Mando Machinary Co Leitfähiges mit Kampfersulfonsäure dotiertes Polyanilin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAO YONG ET AL: "Effect of solvents and co-solvents on the processibility of polyaniline: I. solubility and conductivity studies", PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY OF SYNTHETIC METALS (ICSM'94). PART 1;SEOUL, SOUTH KOREA JUL 24-29 1994, vol. 69, no. 1-3 part 1, 24 July 1994 (1994-07-24), Synth Met;Synthetic Metals; Polymers Mar 1 1995 Elsevier Science S.A., Lausanne, Switzerland, pages 187 - 190, XP002091335 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0923083A1 (fr) * 1997-12-09 1999-06-16 Kemet Electronics Corporation Solution de polyaniline avec solvant à base de terpène bicyclique
JP2003504459A (ja) * 1999-07-13 2003-02-04 コミツサリア タ レネルジー アトミーク 導電性ポリアニリン膜のドーパントとしてのスルホン酸及びホスホン酸の用途及びポリアニリンをベースにした導電性複合材料
US6982514B1 (en) 2000-05-22 2006-01-03 Santa Fe Science And Technology, Inc. Electrochemical devices incorporating high-conductivity conjugated polymers
US6936955B1 (en) 2000-08-04 2005-08-30 Santa Fe Science And Technology, Inc. Conjugated polymer actuator responsive to electrical stimulation
KR100401349B1 (ko) * 2000-09-20 2003-10-17 스마트텍 주식회사 전도성 폴리아닐린 방사용액의 제조 방법
WO2003033747A1 (fr) * 2001-10-16 2003-04-24 University Of Wollongong Separation et recuperation de metaux precieux a l'aide de materiaux polymeres
WO2004042743A1 (fr) * 2002-10-30 2004-05-21 Santa Fe Science & Technology, Inc. Filage, dopage, dedopage et redopage d'une fibre de polyaniline
US7628944B2 (en) 2002-10-30 2009-12-08 Santa Fe Science And Technology, Inc. Spinning, doping, dedoping and redoping polyaniline fiber
US7897082B2 (en) 2002-10-30 2011-03-01 Santa Fe Science & Technology, Inc. Spinning, doping, dedoping and redoping polyaniline fiber
US8425822B2 (en) 2002-10-30 2013-04-23 Santa Fe Science And Technology, Inc. Spinning, doping, dedoping and redoping polyaniline fiber
WO2004051672A3 (fr) * 2002-12-02 2004-10-28 Santa Fe Science And Technolog Chauffage ohmique faisant appel a des fibres de polyaniline
US7132630B2 (en) 2002-12-02 2006-11-07 Sante Fe Science And Technology, Llc Resistive heating using polyaniline fiber
US7288871B1 (en) 2003-07-03 2007-10-30 Santa Fe Science And Technology, Inc. Solid-in-hollow polymer fiber electrochemical devices
WO2005011415A1 (fr) * 2003-08-01 2005-02-10 Santa Fe Science And Technology, Inc. Structures polymeres conductrices multifonctionnelles
US7463040B2 (en) 2003-08-01 2008-12-09 Santa Fe Science And Technology, Inc. Multifunctional conducting polymer structures
US7683643B2 (en) 2003-08-01 2010-03-23 Santa Fe Science And Technology, Inc. Multifunctional conducting polymer structures
US8481849B2 (en) 2004-03-31 2013-07-09 The Yokohama Rubber Co., Ltd. Electrolyte for photovoltaic device as well as photovoltaic device and dye-sensitized solar cell including that electrolyte
US8691028B2 (en) * 2006-05-10 2014-04-08 The Boeing Company Article having a hexavalent-chromium-free, corrosion-inhibiting organic conversion coating thereon, and its preparation

Also Published As

Publication number Publication date
JP2001522898A (ja) 2001-11-20
EP1029329A1 (fr) 2000-08-23
CA2309194A1 (fr) 1999-05-20
AU9637798A (en) 1999-05-31

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