EP0916141B1 - Composition pour la fabrication d'un materiau composite conducteur contenant une polyaniline et materiau composite obtenu a partir de cette composition - Google Patents
Composition pour la fabrication d'un materiau composite conducteur contenant une polyaniline et materiau composite obtenu a partir de cette composition Download PDFInfo
- Publication number
- EP0916141B1 EP0916141B1 EP97935642A EP97935642A EP0916141B1 EP 0916141 B1 EP0916141 B1 EP 0916141B1 EP 97935642 A EP97935642 A EP 97935642A EP 97935642 A EP97935642 A EP 97935642A EP 0916141 B1 EP0916141 B1 EP 0916141B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyaniline
- composite material
- solvent
- composition according
- plasticiser
- 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.)
- Expired - Lifetime
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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
- the present invention relates to the manufacture of conductive composite materials electricity containing polyaniline.
- Films of this type can be used in particular in electrostatic shielding or deicing windows.
- This threshold depends strongly on the morphology of the conductive phase. So when the phase conductor consists of carbon black or metals, the percolation threshold is usually very high and very often above 0.5. However, we have recently made composite materials whose conductive phase is formed of carbon black, which have a very lower percolation threshold (0.4% by weight), as described by Gubbels et al. in Macromolecules, 28, 1995, pp. 1559-1566.
- phase conductor consists of a conductive polymer
- phase conductor can reach lower percolation thresholds in using manufacturing techniques from a solution or manufacturing techniques by hot pressing of a mixture of polymers in the state solid.
- US-A-5,232,631 discloses the manufacture of composite materials from a solution of the insulating polymer forming the host matrix and of a conductive polyaniline in a solvent.
- polyaniline is first reacted with a appropriate protonant that makes it possible to make it soluble in a suitable organic solvent.
- a suitable organic solvent we use then the solution to form a film by casting and evaporation of the solvent. We can reach with these very low percolation thresholds and high conductivities.
- EP-A-0 643 397 discloses the manufacture of conductive composite materials also comprising a polymer host matrix insulation in which is distributed a polymer conductor constituted by a polyaniline, which is obtained by hot compression molding of a mixture of the conductive polymer and the insulating polymer to which usually adds a plasticizer.
- polyaniline can be protonated by an agent organic protonant and compatibilizer can be constituted by an aromatic compound which, during the material manufacturing, dissolves polyaniline conductive and forms a strong molecular association with it, and on the other hand ensures compatibility between the polyaniline and the insulating polymer.
- the present invention specifically relates to compositions for the manufacture of a material conductive composite from solutions, which allow to obtain high conductivities with smaller amounts of conductive polymer.
- the presence of a plasticizer the insulating polymer allows so unexpectedly to lower the percolation threshold of the composite material and to obtain conductivities high.
- the plasticizer allows not only to give flexibility to the polymer insulation, but also to prevent training of polyaniline aggregates by weakening the forces adhesion between the polyaniline grains. This leads to better dispersion of polyaniline in the host matrix of insulating polymer and promotes the formation of a continuous network of polyaniline conductive in the composite. This allows, as we will see below, to lower the percolation threshold of the composite material by a factor of 10, this one being for example greater than 0.04 in the absence of plasticizer and becoming equal to about 0.004 with the plasticizer.
- the Insulating polymers used are polymers made generally in the plasticized state like polyvinyl chloride and polymers cellulose.
- cellulose derivative such as acetate of cellulose.
- the plasticizers used are chosen from the usual plasticizers for these types of polymers.
- plasticizer a mixture of dimethyl phthalate, phthalate diethyl and triphenyl phosphate.
- Conductive polyanilines used in the invention are of the emeraldine-salt form. They may be substituted or unsubstituted.
- Polyanilines can also be used substitutes such as those described in the EP-A-0643397 and US-A-0 532 631.
- a polyaniline is used protonated by a protonating agent capable of promoting the dissolution of the polyaniline in the solvent used.
- protonating agents of this type include a acid function and hydrocarbon chains their conferring a surfactant character and making them compatible with organic solvents generally used, thereby promoting the dissolution of polyaniline in the solvent.
- protonating agents include: monoesters and diesters aliphatic and / or aromatic phosphoric acid, for example the alkyl and / or aryl esters of phosphoric acid, arylsulphonic acids and arylphosphonic acids.
- the protonating agent is chosen in the group consisting of camphorsulfonic acid, phenylphosphonic acid, dibutyl phosphate and dioctyl phosphate.
- the solvent organic can also be of different types but phenol solvents are generally preferred. such as cresols, and especially meta-cresol.
- compositions of the invention can be used for the manufacture of composite materials, especially in the form of conductive flexible films, highly transparent, by pouring the solution, followed by evaporation of the solvent.
- the composition is prepared in mixing a first solution of polyaniline protonated in the solvent to a second solution in the same solvent of the insulating polymer and the plasticizer.
- the invention also relates to an electrically conductive composite material obtained by this process, which comprises a cellulose acetate matrix in which are distributed a protonated conductive polyaniline and a plasticizer consisting of a mixture of dimethyl phthalate, phthalate and diethyl and triphenyl phosphate, the material having an electronic conductivity of 10 -6 to 10 S / cm.
- the polyaniline is protonated by phenylphosphonic acid.
- Figures 1 to 4 are graphs illustrating the conductivity of composite materials conductors, obtained by the process of the invention in depending on their polyaniline content; figures 1 at 4 correspond to the use of various agents protonants.
- a material is prepared composite according to the invention, using as cellulose acetate insulating polymer, as polyaniline of emeraldine protonated by phosphate dioctyl acid and as a plasticizer a mixture of dimethyl phthalate, diethyl phthalate and triphenyl phosphate.
- the protonation of this polyaniline is carried out by introducing 500 mg of polyemeraldine and 891 mg of di-isooctyl acid phosphate in 100 g of m-cresol. The protonation reaction is carried out for one week at room temperature with vigorous stirring.
- the conductivity of the films thus obtained measured using the standard four-point technique is 7 ⁇ 10 -2 S / cm.
- the conductivity of the film obtained under these conditions is less than 10 -10 S / cm.
- plasticizer significantly lowers the threshold of percolation.
- Example 2 The same procedure as in Example 1 is followed to prepare the solution of protonated polyaniline in m-cresol and the solution of cellulose acetate and plasticizer in m-cresol, but 2 g of the solution of cellulose acetate and plasticizer containing 304 mg of cellulose acetate and plasticizer with 0.6158 g of the polyaniline solution, or with 2.09 mg of emeraldine (estimated in unprotonated form).
- the films obtained from this composition have an emeraldine content of 0.7% by weight (estimate in unprotonated form).
- the conductivity of the film measured as before is 3.10 -3 S / cm.
- Example 2 The same procedure as in Example 2 is followed, except that the cellulose acetate solution does not contain plasticizer. A film having a conductivity of less than 10 -10 S / cm is thus obtained, which confirms the results obtained in Example 1 on the beneficial effect of the plasticizer.
- Figure 1 illustrates the results obtained, that is to say the conductivity of the composite material (log ⁇ ) depending on the polyaniline content (in% in weight).
- Example 2 We follow the same procedure as in Example 1, but it is used as protonating agent phenylphosphonic acid and mixing the solutions so as to have polyaniline contents in the material from 0.5% to 1.8% by weight.
- Figure 2 shows the conductivity of obtained material (log ⁇ ) according to its content in polyaniline (in% by weight).
- Example 3 we follow the same mode only in Example 1, but it is used as protonating agent di-n-butyl phosphate and one mix the two solutions to have levels in polyaniline ranging from 0.5 to 11% by weight.
- the conductivity of the material obtained (log ⁇ ) as a function of its content of polyaniline (% by weight) is given on the figure 3.
- Figure 4 illustrates the conductivity of material (log ⁇ ) according to its content in polyaniline.
- the percolation thresholds are ten times higher, for example f c> 0.04 in this das.
- Another very interesting property of the movies of composite material obtained in the examples above, is that they retain excellent flexibility plasticized cellulose acetate.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
- acétate de cellulose/m-crésol : de 5 à 12 % en poids, et
- plastifiant/acétate de cellulose : de 30 à 60 % en poids.
- polyaniline (calculée d'après la polyaniline de base) de 0,3 à 5 % en poids ;
- agent de protonation de 0,3 à 7 % en poids ;
- acétate de cellulose de 60 à 70 % en poids ;
- plastifiant de 15 à 40 %.
Claims (13)
- Composition pour la fabrication d'un matériau composite conducteur, caractérisée en ce qu'elle est constituée par une solution dans un solvant des constituants suivants :a) une polyaniline conductrice protonée par un agent protonant apte à favoriser la dissolution de la polyaniline dans le solvant,b) un polymère isolant choisi parmi les polymères cellulosiques et les poly(chlorure de vinyle), etc) un plastifiant du polymère isolant.
- Composition selon la revendication 1, caractérisée en ce que le polymère isolant est l'acétate de cellulose.
- Composition selon l'une quelconque des revenidications 1 et 2, caractérisée en ce que le plastifiant est constitué par au moins un composé choisi parmi les phtalates d'alkyle et/ou d'aryle et les phosphates d'alkyle et/ou d'aryle.
- Composition selon la revendication 3, caractérisée en ce que le plastifiant est un mélange de phtalate de diméthyle, de phtalate de diéthyle et de phosphate de triphényle.
- Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce que l'agent protonant est choisi parmi les monoesters et diesters aliphatiques et/ou aromatiques de l'acide phosphorique, les acides arylsulfoniques et les acides arylphosphoniques.
- Composition selon la revendication 5, caractérisée en ce que l'agent protonant est choisi dans le groupe constitué par les acides camphosulfoniques, l'acide phénylphosphonique, le phosphate de dibutyle et le phosphate de dioctyle.
- Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le solvant est le m-crésol.
- Composition selon les revendications 2 et 7, caractérisée en ce que les rapports des concentrations pondérales du solvant, du polymère isolant et du plastifiant sont dans les gammes suivantes :acétate de cellulose/m-crésol : de 5 à 12 % en poids, etplastifiant/acétate de cellulose : de 30 à 60 % en poids.
- Procédé de fabrication d'un matériau composite conducteur contenant une polyaniline, caractérisé en ce qu'il comprend les étapes suivantes :1) préparer une composition selon l'une quelconque des revendications 1 à 8,2) former à partir de ladite composition le matériau composite conducteur par évaporation du solvant.
- Procédé selon la revendication 9, caractérisé en ce que l'on prépare la composition en mélangeant une première solution de la polyaniline protonée dans le solvant à une deuxième solution dans le même solvant du polymère isolant et du plastifiant.
- Matériau composite conducteur de l'électricité comprenant une matrice d'acétate de cellulose dans laquelle sont répartis une polyaniline conductrice protonée et un plastifiant constitué par un mélange de phtalate de diméthyle, de phtalate de diéthyle et de phosphate de triphényle, ayant une conductivité électronique de 10-6 à 10 S/cm.
- Matériau composite selon la revendication 11, caractérisé en ce que sa teneur en polyaniline est de 0,3 à 5 % en poids.
- Matériau composite selon l'une quelconque des revendications 11 et 12, caractérisé en ce que la polyaniline est protonée par l'acide phénylphosphonique.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9609521 | 1996-07-29 | ||
FR9609521A FR2751660B1 (fr) | 1996-07-29 | 1996-07-29 | Composition pour la fabrication d'un materiau composite conducteur contenant une polyaniline et materiau composite obtenu a partir de cette composition |
PCT/FR1997/001408 WO1998005040A1 (fr) | 1996-07-29 | 1997-07-28 | Composition pour la fabrication d'un materiau composite conducteur contenant une polyaniline et materiau composite obtenu a partir de cette composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0916141A1 EP0916141A1 (fr) | 1999-05-19 |
EP0916141B1 true EP0916141B1 (fr) | 2004-11-10 |
Family
ID=9494586
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97935642A Expired - Lifetime EP0916141B1 (fr) | 1996-07-29 | 1997-07-28 | Composition pour la fabrication d'un materiau composite conducteur contenant une polyaniline et materiau composite obtenu a partir de cette composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US6235220B1 (fr) |
EP (1) | EP0916141B1 (fr) |
JP (1) | JP4142106B2 (fr) |
DE (1) | DE69731536T2 (fr) |
FR (1) | FR2751660B1 (fr) |
WO (1) | WO1998005040A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2796379B1 (fr) * | 1999-07-13 | 2002-05-24 | Commissariat Energie Atomique | Acides sulfoniques et phosphoniques et leur utilisation comme dopants pour la fabrication de films conducteurs de polyaniline et pour la fabrication de materiaux composites conducteurs a base de polyaniline |
US6602741B1 (en) * | 1999-09-14 | 2003-08-05 | Matsushita Electric Industrial Co., Ltd. | Conductive composition precursor, conductive composition, solid electrolytic capacitor, and their manufacturing method |
FR2811466B1 (fr) * | 2000-07-05 | 2004-02-20 | Commissariat Energie Atomique | Preparation de materiaux composites conducteurs par depot d'un polymere conducteur dans un substrat poreux isolant et solution utile pour cette preparation |
FI119247B (fi) * | 2001-01-23 | 2008-09-15 | Panipol Oy | Sähköä johtava plastisaattorikoostumus ja menetelmä sen valmistamiseksi |
FR2830535B1 (fr) * | 2001-10-10 | 2003-12-19 | Commissariat Energie Atomique | Utilisation d'acides sulfoniques, phosphoniques comme dopants de la polyaniline et de materiaux composites conducteurs a base de polyaniline |
KR20040096630A (ko) | 2002-03-01 | 2004-11-16 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 첨가제를 함유하는 유기 전도성 중합체의 인쇄 |
US7211202B2 (en) | 2002-12-13 | 2007-05-01 | Atofina | Process to make a conductive composition of a fluorinated polymer which contains polyaniline |
ATE353090T1 (de) * | 2002-12-13 | 2007-02-15 | Arkema France | Verfahren zur herstellung einer leitfähigen zusammensetzung von fluoriertem polymer enthaltend polyanilin |
JP2006160770A (ja) * | 2004-12-02 | 2006-06-22 | Japan Science & Technology Agency | ファイバー状導電性ポリマーとその製造方法 |
KR100949399B1 (ko) * | 2008-07-11 | 2010-03-24 | 광 석 서 | 유기용제 분산성 전도성 고분자 및 이의 제조방법 |
MY173717A (en) * | 2011-07-29 | 2020-02-18 | Mimos Berhad | Composite electrode with in-situ polymerized polyaniline and preparation method thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4898921A (en) * | 1987-06-03 | 1990-02-06 | Montclair State College | Conducting polymer films, method of manufacture and applications therefor |
JPH01131288A (ja) * | 1987-11-16 | 1989-05-24 | Bridgestone Corp | 導電性塗料 |
US5232631A (en) | 1991-06-12 | 1993-08-03 | Uniax Corporation | Processible forms of electrically conductive polyaniline |
US5320780A (en) * | 1993-01-11 | 1994-06-14 | Tech Spray, Inc. | Composition and process for preventing electrostatic discharge |
CN1046750C (zh) | 1993-09-03 | 1999-11-24 | 耐斯特欧公司 | 导电组合物 |
JP3694038B2 (ja) * | 1993-09-09 | 2005-09-14 | 日東電工株式会社 | 固体電解コンデンサ |
FI102683B1 (fi) * | 1994-04-18 | 1999-01-29 | Neste Oy | Sähköä johtava kuivasekoite ja menetelmä sen valmistamiseksi |
IL110318A (en) * | 1994-05-23 | 1998-12-27 | Al Coat Ltd | Solutions containing polyaniline for making transparent electrodes for liquid crystal devices |
-
1996
- 1996-07-29 FR FR9609521A patent/FR2751660B1/fr not_active Expired - Fee Related
-
1997
- 1997-07-28 US US09/230,737 patent/US6235220B1/en not_active Expired - Fee Related
- 1997-07-28 WO PCT/FR1997/001408 patent/WO1998005040A1/fr active IP Right Grant
- 1997-07-28 JP JP50856698A patent/JP4142106B2/ja not_active Expired - Fee Related
- 1997-07-28 EP EP97935642A patent/EP0916141B1/fr not_active Expired - Lifetime
- 1997-07-28 DE DE69731536T patent/DE69731536T2/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO1998005040A1 (fr) | 1998-02-05 |
JP2001501017A (ja) | 2001-01-23 |
FR2751660B1 (fr) | 1998-08-28 |
US6235220B1 (en) | 2001-05-22 |
DE69731536T2 (de) | 2005-11-24 |
FR2751660A1 (fr) | 1998-01-30 |
DE69731536D1 (de) | 2004-12-16 |
JP4142106B2 (ja) | 2008-08-27 |
EP0916141A1 (fr) | 1999-05-19 |
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