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WO2009000049A1 - Polymeres a conduction intrinseque - Google Patents

Polymeres a conduction intrinseque Download PDF

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Publication number
WO2009000049A1
WO2009000049A1 PCT/AU2008/000952 AU2008000952W WO2009000049A1 WO 2009000049 A1 WO2009000049 A1 WO 2009000049A1 AU 2008000952 W AU2008000952 W AU 2008000952W WO 2009000049 A1 WO2009000049 A1 WO 2009000049A1
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WIPO (PCT)
Prior art keywords
dye
ionic dye
polymerisation
conducting polymer
substrate
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PCT/AU2008/000952
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English (en)
Inventor
Bjorn Winther-Jensen
Noel Clark
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CRC SMARTPRINT Pty Ltd
University of Wollongong
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CRC SMARTPRINT Pty Ltd
University of Wollongong
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Priority claimed from AU2007903493A external-priority patent/AU2007903493A0/en
Application filed by CRC SMARTPRINT Pty Ltd, University of Wollongong filed Critical CRC SMARTPRINT Pty Ltd
Publication of WO2009000049A1 publication Critical patent/WO2009000049A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Definitions

  • the present inventions relates generally to intrinsically conducting polymers.
  • the invention relates to a method of preparing an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, a method of forming the intrinsically conducting polymer on a surface of a substrate, a composition for preparing the intrinsically conducting polymer, and to a sensing device comprising the intrinsically conducting polymer.
  • polymers are electrical insulators and as such have been employed as insulation materials in numerous applications.
  • some polymers with an extended conjugated molecular structure have the potential to become conductive or in fact exhibit a degree of conductivity in their own right.
  • examples of such polymers include polypyrrole, polyaniline, polyphenylene, and polythiophene.
  • these types of polymers per se generally exhibit at best relatively low conductivity, their conductivity may be increased substantially through doping (i.e. the introduction of charge to the conjugated structure for example by (a) electron removal (oxidation or p-doping), (b) electron injection (reduction or n-doping), or (c) protonation (acid doping)).
  • ICPs intrinsically conducting polymers
  • Conjugated polymers amenable to p-doping may be prepared by a variety of techniques, including cationic, radical, coordination, step growth or electrochemical polymerisation. Although ICPs based on such polymers may be prepared by first forming the polymer and then doping it, this methodology has numerous limitations and in practice doping is typically conducted at the time when the polymer is formed.
  • ICPs can advantageously be employed in applications not previously suited to conventional metallic conductors.
  • ICPs In addition to being conductive, ICPs are also known to undergo chemical, physical and/or mechanical transitions when they are oxidised or reduced. This redox responsiveness has seen ICPs also find utility in applications associated with sensing, monitoring, actuation and controlled release technologies.
  • ICPs can be prepared with an ionic dye retained therein, and that the dye can be released upon the polymer being subjected to a redox process.
  • the ability of these polymers to release dye on demand presents a unique dye release mechanism having great potential for use in a diverse array of applications.
  • US 5,821,018 discloses an image forming member and an image forming process that makes use of such an ICP.
  • ICPs incorporating an ionic dye have been prepared by electrochemical polymerisation. Although this technique may be effective in that it enables such ICPs to be produced, it is relatively slow, expensive and difficult to implement in large scale industrial operations. Furthermore, the technique is limited to forming/depositing ICPs onto a conductive substrate.
  • the present invention therefore provides a method of preparing an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, the method comprising chemical oxidative polymerisation of monomers under acidic conditions in the presence of the ionic dye to form the intrinsically conducting polymer.
  • the invention also provides a method of forming on a surface of a substrate an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising applying to the surface of the substrate a mixture comprising a chemical oxidant and the ionic dye, and polymerising monomers under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the intrinsically conducting polymer, wherein the chemical oxidant promotes the polymerisation of monomers.
  • the invention further provides a method for forming on a surface of a substrate an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant and the ionic dye, and exposing the printed mixture to monomers in the vapour phase which polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the intrinsically conducting polymer, wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the invention also provides a method for forming on a surface of a substrate an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant, the ionic dye, monomer and a polymerisation retardant, wherein after printing the monomers polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the intrinsically conducting polymer, and wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the present invention also provides a composition comprising a chemical oxidant and an ionic dye, wherein said composition, upon being applied to a surface of a substrate and exposed to monomers in the vapour phase, will, under acidic conditions, promote the vapour phase polymerisation of the monomers to form an intrinsically conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • the present invention further provides a composition comprising a chemical oxidant, an ionic dye, monomer and a polymerisation retardant, wherein said composition, after being applied to a surface of a substrate will polymerise under acidic conditions to form an intrinsically conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • compositions in accordance with the invention can conveniently be provided within a print cartridge.
  • the print cartridges can be utilised with conventional printing equipment to form unique ICP patterned surfaces.
  • the invention further provides a sensing device comprising an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, wherein the intrinsically conducting polymer is formed by chemical oxidative polymerisation of monomers under acidic conditions in the presence of the ionic dye, and wherein the ionic dye is released from the polymeric matrix in response to a condition to be sensed.
  • ICPs having a polymeric matrix with an ionic dye retained therein may be prepared via chemical oxidative polymerisation.
  • chemical oxidative pathway instead of a conventional electrochemical oxidative pathway, the ICPs can advantageously be prepared rapidly and efficiently on a laboratory or industrial scale.
  • the methodology is particularly well suited to depositing/forming the ICPs on nonconductive substrates.
  • Figure 1 illustrates the release of phenol red dye from an ICP prepared in accordance with the invention using vapour phase polymerisation.
  • Figure 2 illustrates the absorbance of phenol red dye released from an ICP prepared in accordance with the invention after 20 minutes measured at 558nm as a function of pH.
  • Figure 3 illustrates the release of phenol red dye from an ICP prepared in accordance with the invention using bulk polymerisation.
  • ICP intrasically conducting polymer
  • the intrinsically conducting polymer has a polymeric matrix with an ionic dye retained therein.
  • the ionic dye being “retained” is meant that the dye is physically or chemically restrained within the polymeric matrix of the polymer, and for example cannot transfer by diffusion into a liquid within which the polymer is immersed.
  • the dye is released from the polymeric matrix of the intrinsically conducting polymer.
  • the ionic dye being "released” is meant that the dye is no longer physically or chemically restrained and can be expelled from the polymeric matrix, for example by way of diffusion into a liquid within which the polymer is immersed.
  • the ionic dye might therefore also be described as being releasably retained.
  • sufficient dye must be retained within the polymeric matrix such that upon its release, for example into a liquid in which the ICP is immersed, the dye can be detected by a means suitable for the intended application of the ICP. Suitable means for detection of the dye might include detection by the naked eye or detection using an electronic device such as a spectrophotometer. Generally the dye will be retained within the polymeric matrix at a concentration ranging from about 1 to 75% by weight, preferably from about 5 to about 75 % by weight.
  • an important feature of the invention is that in its retained state the dye maintains dye characteristics such that it can function as a dye upon being released from the polymeric matrix (i.e. the dye is not degraded upon being retained within or released from the polymeric matrix).
  • the ionic dye plays upon being retained within the polymeric matrix. Without wishing to be limited by theory, it is believed that the ionic dye may function as a dopant through association with the oxidised conjugated polymer backbone in the form of a counterion and/or simply reside as non-doping ionic species within the polymeric matrix. Where the ionic dye does not function as a dopant, the ICP will of course nonetheless comprise a dopant.
  • An advantageous feature of the present invention is that the ICP can be reduced, for example by electrochemical or chemical reduction, enabling the retained ionic dye to be released from the polymeric matrix.
  • the mechanism by which the ionic dye is released involves the reduction of the polymer backbone coupled with the influx of ions into the polymeric matrix from an ionic solution (i.e. electrolyte solution) within which the ICP is immersed.
  • reduction of the polymer neutralises any charge association the ionic dye may have with the polymer where it functions as a dopant.
  • solvent e.g. water
  • the retained dye does not function as a dopant
  • reduction of the polymer is believed to at least indirectly facilitate release of the dye through the aforementioned swelling of the polymeric matrix.
  • the ICPs are prepared by chemical oxidative polymerisation.
  • chemical oxidative polymerisation is meant that the monomer is oxidised by a chemical oxidant to form the polymer.
  • the chemical oxidative polymerisation is also conducted under acidic conditions.
  • acidic conditions is meant that the reaction medium in or interface at which the polymerisation occurs has a pH of less than 7.
  • the polymerisation is conducted at a pH of less than about 5, more preferably less than about 3.
  • the monomers are polymerised in the presence of the ionic dye.
  • the ionic dye is within a proximity to the monomers during polymerisation that enables the dye to be taken up and retained within the resulting polymeric matrix of the polymer.
  • the monomer may be intimately mixed with the dye or monomer may be contacted with or applied to a surface layer comprising the dye.
  • the term "ionic dye” is intended to mean an ionisable organic compound comprising a chromophore. Such compounds will typically be soluble in hydrophilic solvents such as water, alcohols or a combination thereof.
  • the ionic state of the dye may vary depending upon the type of dye used and whether the dye is retained within or has been released from the polymeric matrix.
  • the dye may be present as an anion or a zwitterion.
  • Dyes present as neutral moieties or cations are typically more difficult to retain within the polymer matrix (i.e. they are prone to diffusing into a surrounding liquid without the ICP being reduced).
  • ionic dye that may be used in accordance with the invention.
  • dyes present in the polymeric matrix as neutral moieties or cations are typically more prone to diffusing into a surrounding liquid without the ICP being reduced and are therefore unsuitable for use in accordance with the invention.
  • the dye will preferably be of a type capable of being ionised to form an anionic chromophore. Such dyes may be conveniently referred to as anionic dyes.
  • a preferred class of ionic dye for use in accordance with the invention are those selected from the family of triarylmethane dyes. Those skilled in the art will appreciate that this family of dyes is based on a substituted triarylmethane structure.
  • the triarylmethane dye is preferably substituted with a sulfonic, carboxylic, phosphonic, or phosphoric moity.
  • the triarylmethane dyes are substituted with at least one sulfonic moiety.
  • substituents may also be in the form of their corresponding salt, preferably their corresponding sodium salt.
  • a preferred class of triarylmethane dyes are the hydroxytriarylmethane dyes.
  • a preferred class of hydroxytriarylmethane dyes are the sulfonphthaleins.
  • suitable sulfonphthalein dyes include, but are not limited to, phenol red, xylene cyanol FF, thymol blue, m-cresol purple and cresol red.
  • Preferred dyes also include the ca ⁇ nine family.
  • An example of a suitable carmine dye includes, but is not limited to, indigo carmine.
  • ICPs prepared in accordance with the invention are formed through the chemical oxidative polymerisation of monomers.
  • Suitable monomers are those which undergo reaction with a chemical oxidant and polymerise in the presence of a dopant to form the ICP.
  • the monomer may be utilised in the form of a vapour phase (i.e. vapour phase polymerisation) or be present in a liquid reaction medium (i.e. bulk polymerisation).
  • the monomer When present in a liquid reaction medium, the monomer will generally be dissolved in a polar solvent such as water, alcohols (the latter optionally including chain lengths of up to 4 carbons and preferably primary alcohols with chain lengths of 2 or 4 carbons) or acetonitrile that have the capacity to dissolve other reaction components as well as the monomer.
  • a polar solvent such as water, alcohols (the latter optionally including chain lengths of up to 4 carbons and preferably primary alcohols with chain lengths of 2 or 4 carbons) or acetonitrile that have the capacity to dissolve other reaction components as well as the monomer.
  • additional reaction components in the reaction medium may include surfactants and dispersants required to stabilise the reaction mixture against crystallisation or precipitation.
  • suitable materials for this purpose include, but are not limited to, polyurethane diol, polypropylene glycol and proprietary surfactant formulations such as Teric BL8 (C 12 ethoxylated fatty acid alcohol, Huntsman) and Glysolv (l-methoxy-2-propanol, Huntsman). These materials are used either neat or as a 5% solution in alcohol, the amount normally used being 10% of the dry mass of the oxidant.
  • Acids or bases may also be included in the reaction mixture and are used to optionally protonate the final conducting polymer for the purpose of increasing conductivity (mineral acids such as HCl or H 2 SO 4 ) or to retard polymerisation, suppress side reactions, mitigate printing equipment corrosion or for all three purposes at one and the same time (e.g. bases such as pyridine).
  • bases such as pyridine
  • the monomer When employed in the vapour phase, the monomer is used neat, with the optional application of heat or agitation to increase vapour concentration and hence the rate of reaction.
  • Examples of monomers that may be used in accordance with the invention include, but are not limited to, optionally substituted aromatic compounds.
  • Suitable optionally substituted aromatic compounds include, but are not limited to, optionally substituted aryl such as aniline, and optionally substituted aromatic heterocyclic compounds such as optionally substituted 5-membered aromatic heterocyclic compounds, hi the case of optionally substituted 5-membered aromatic heterocyclic compounds, it will be appreciated that only the ⁇ , ⁇ ' positions of the 5 membered rings can be substituted so as to allow for coupling of the monomers and subsequent formation of the polymer chain through the a, d positions.
  • Preferred optionally substituted aromatic compounds include, but are not limited to, optionally substituted pyrrole (including N-substituted pyrrole), optionally substituted thiophene, optionally substituted aniline, optionally substituted furan, optionally substituted pyridine, optionally substituted indole, optionally substituted carbazole.
  • Preferred optionally substituted 5-membered aromatic heterocyclic compounds include, but are not limited, those of general formula (I):
  • R 1 and R 2 are each independently selected from hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl or together form an optionally substituted cyclic substituent, and X is selected from O, S, and NR 3 , where R 3 is selected from hydrogen, optionally substituted alkyl, optionally substituted aryl, and optionally substituted arylalkyl.
  • R 1 and R 2 are each independently selected from hydrogen, optionally substituted C 1 -C 8 alkyl, optionally substituted C 6 -C 18 aryl, optionally substituted C 7 -C 18 arylalkyl or form together an optionally substituted C 2 -C 8 cyclic substituent.
  • R 3 is selected from hydrogen, optionally substituted C 1 -C 8 alkyl, optionally substituted C 6 -C 18 aryl, and optionally substituted C 7 -C 18 arylalkyl.
  • R 1 and R 2 forming together a "cyclic organic substituent” is meant that together with the ⁇ , jS'-carbon atoms of general formula (I) R 1 and R 2 form a ring or cyclic structure.
  • the resulting cyclic organic substituent or carbocyclyl group preferably is a C 2-20 (e.g. C 2-10 or C 2-6 ) cyclic organic substituent.
  • One or more of the carbon atoms in the cyclic organic substituent may be replaced by a heteroatom. Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms. Where one or more carbon atom of the cyclic organic substituent is replaced by a heteroatom, the substituent may be conveniently referred to as a heterocyclic organic substituent or a heterocylyl group.
  • Preferred compounds falling within the scope of formula (I) include, but are not limited to, optionally substituted pyrrole (including N-substituted pyrrole), and optionally substituted thiophene (e.g. 3,4-ethylenedioxythiophene).
  • one type of monomer may be used so as to form a homopolymer, or two or more types of monomers may be used so as to form a copolymer.
  • alkyl used either alone or in compound words denotes straight chain, branched or cyclic alkyl, preferably C 1-20 alkyl, e.g. C 1-10 or C 1-6 .
  • straight chain and branched alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, -fee- butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2- trimethylpropyl, heptyl, 5-methylhex
  • cyclic alkyl examples include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl” etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
  • aryl denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems.
  • aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl.
  • Preferred aryl include phenyl and naphthyl.
  • An aryl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkylthio alkenylthio
  • alkynylthio alkynylthio
  • arylthio alkyl, alkenyl, alkynyl, aryl groups as defined herein when linked by sulfur.
  • groups written as “[group A] [group B]” refer to group A when linked by a divalent form of group B.
  • [group A] [alkyl]” refers to a particular group A (such as hydroxy, amino, etc.) when linked by divalent alkyl, i.e. alkylene (e.g. hydroxyethyl is intended to denote HO-CH 2 -CH-).
  • arylalkyl is intended to mean an aryl group when linked by a divalent alkyl group.
  • an arylalkyl group includes a benzyl group (i.e. (C 6 H 5 )CH 2 -).
  • aromatic heterocyclic compound is intended to include any monocyclic, polycyclic or fused aromatic organic compound in which one or more carbon atoms are replaced by a heteroatom and which are capable of undergoing oxidative polymerisation to form a polymer backbone having an extended conjugated system.
  • Preferred aromatic heterocyclic compounds are five or six membered ring systems. Suitable heteroatoms include O, N, S, P, and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • Suitable examples of aromatic heterocyclic compounds include, but are not limited to, pyridine, pyrrole, thiophene, furan, indole, carbazole, 3,4- ethylenedioxythiophene.
  • the term "optionally substituted" [group] is intended to mean that the [group] may or may not be substituted with one, two, three or more of organic and inorganic groups, including those selected from: sulphonate, carboxylate, phosphonate, nitrate, alkoxy (such as a methoxy, and ring-forming alkoxy groups such as alkylene dioxy groups, such as ethylenedioxy groups), alkyl, alkenyl, alkynyl, aryl, arylalkyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocycly
  • alkenyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, preferably C 2-20 alkenyl (e.g. C 2-10 or C 2-6 ).
  • alkenyl examples include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3- decenyl, 1,3-butadienyl, 1 ,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4- hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5- cyclo
  • alkynyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined. Unless the number of carbon atoms is specified the term preferably refers to C 2-20 alkynyl (e.g. C 2-10 or C 2-6 ). Examples include ethynyl, 1-propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers. An alkynyl group may be optionally substituted by one or more optional substituents as herein defined.
  • halogen denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
  • Carbocyclyl includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-10 or C 3-8 ).
  • the rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds
  • carbocyclyl moieties are 5-6-membered or 9-10 membered ring systems. Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclop entenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
  • heterocyclyl when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-10 or C 3-8 ) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non-aromatic residue.
  • Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • the heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds. Particularly preferred heterocyclyl are 5-6 and 9-10 membered heterocyclyl.
  • heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathianyl, dithi
  • Preferred acyl includes C(O)-R, wherein R is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • R is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • examples of acyl include formyl, straight chain or branched alkanoyl (e.g.
  • C 1-20 such as, acetyl, propanoyl, butanoyl, 2- methylpropanoyl, pentanoyl, 2,2-dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; aralkan
  • phenylacetyl phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl
  • naphthylalkanoyl e.g. naphthylacetyl, naphthylpropanoyl and naphthylbutanoyl]
  • aralkenoyl such as phenylalkenoyl (e.g.
  • phenylpropenoyl e.g., phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g.
  • aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl
  • arylthiocarbamoyl such as phenylthiocarbamoyl
  • arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl
  • arylsulfonyl such as phenylsulfonyl and napthylsulfonyl
  • heterocycliccarbonyl heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl
  • sulfoxide refers to a group -S(O)R wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and arylalkyl. Examples of preferred R include C 1-20 alkyl, phenyl and benzyl.
  • sulfonyl refers to a group S(O) 2 -R, wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and arylalkyl. Examples of preferred R include C 1-20 alkyl, phenyl and benzyl.
  • sulfonamide refers to a group S(O)NRR wherein each R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and arylalkyl.
  • R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and arylalkyl.
  • preferred R include C 1-2 oalkyl, phenyl and benzyl.
  • at least one R is hydrogen.
  • both R are hydrogen.
  • amino is used here in its broadest sense as understood in the art and includes groups of the formula NR A R B wherein R A and R B may be any independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, arylalkyl, and acyl. R A and R B , together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3-10 membered ring, particularly, 5-6 and 9-10 membered systems. Examples of “amino” include NH 2 , NHalkyl (e.g.
  • C 1- 20 alkyl NHaryl (e.g. NHphenyl), NHaralkyl (e.g. NHbenzyl), NHacyl (e.g. NHC(O)C 1- 20 alkyl, NHC(O)phenyl), Nalkylalkyl (wherein each alkyl, for example C 1-20 , may be the same or different) and 5 or 6 membered rings, optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • NHaryl e.g. NHphenyl
  • NHaralkyl e.g. NHbenzyl
  • NHacyl e.g. NHC(O)C 1- 20 alkyl, NHC(O)phenyl
  • Nalkylalkyl wherein each alkyl, for example C 1-20 , may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and S
  • amido is used here in its broadest sense as understood in the art and includes groups having the formula C(O)NR A R B , wherein R A and R B are as defined as above.
  • amido include C(O)NH 2 , C(O)NHalkyl (e.g. C 1-20 alkyl), C(O)NHaryl (e.g. C(O)NHphenyl), C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.
  • carboxy ester is used here in its broadest sense as understood in the art and includes groups having the formula CO 2 R, wherein R may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, arylalkyl, and acyl.
  • R may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, arylalkyl, and acyl.
  • Examples of carboxy ester include CO 2 C 1-20 alkyl, CO 2 aryl (e.g. CO 2 ⁇ henyl), CO 2 aralkyl (e.g. CO 2 benzyl).
  • heteroatom refers to any atom other than a carbon atom which may be a member of a cyclic organic group.
  • heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
  • the monomers undergo chemical oxidative polymerisation to form the ICP.
  • Monomer therefore reacts with and is oxidised by a chemical oxidant (which is itself reduced) to yield a reactive species that propagates polymerisation and formation of polymer having cationic character.
  • the cationic character of the polymer is neutralised through association with a dopant (i.e. a suitable anionic species).
  • a dopant i.e. a suitable anionic species.
  • the dopant may be derived from the chemical oxidant (i.e. a self-doping chemical oxidant) or may be present as a separate distinct species.
  • Suitable chemical oxidants include, but are not limited to, metal salts with high oxidizing potential, including ferric salts such as ferric chloride and ferric p-toluene sulfonate, and corresponding copper(II) salts, vanadium(V) salts, cerium(IV) salts and auric(III) salts.
  • Other suitable oxidizing agents include, but are not limited to, persulfates such as ammonium and potassium persulfate, peroxides such as benzoyl peroxide and hydrogen peroxide, and gases such as fluorene, ozone and chlorine.
  • self-doping chemical oxidants include, but are not limited to, metal salts of sulfonates, sulfates, chlorides, perchlorates and phosphates.
  • the amount of chemical oxidant used in the preparation of the ICPs will vary with the nature of the monomer and chemical oxidant employed. For example, in vapour phase polymerisation the ratio of oxidant to monomer will progressively change as the oxidant is consumed, hi general, the oxidising agent will be initially applied in an amount ranging from about 0.5 to 4 calculated on a molar ratio basis relative to the monomer.
  • suitable dopant anions include, but are not limited to, chloride, dodecylbenzenesulfonate, perchlorate, tetrafluoroborate, sulfate, sulfonate, oxalate, subsalicylate, or fluromethyl sulfonate. Where appropriate, a mixture of different oxidants and/or dopants may be used.
  • the monomers are polymerised under acidic conditions to form the ICP.
  • the acidic conditions may be provided by any suitable means.
  • the chemical oxidant or dopant may itself provide the acidic conditions or an additional acid such as a mineral acid or a carboxylic acid may be employed.
  • the chemical oxidative polymerisation of the monomers may be conducted in various ways to form the ICP.
  • a suitable ionic dye, chemical oxidant and monomer are selected such that an ICP having a polymeric matrix with the dye retained therein can be formed.
  • such reagents are selected by first having regard to the ICP required for use in the intended application. Having selected an ICP to suit the intended application, the other components of the reaction system may then be chosen.
  • Oxidants are typically chosen on the basis of their ability to polymerise the appropriate monomer, their potential for self-doping the ICP, and properties such as solubility and tendency towards crystallisation or precipitation on drying that can affect their ease of use.
  • Dyes are chosen on the basis of the suitability of their colour(s) across the intended pH range, their solubility in the intended reaction mixture and their compatibility with the chosen oxidant (e.g. azo dyes are reactive toward many oxidants and may therefore be unsuitable). In general, dyes that meet these criteria are suitable for use with a number of ICPs.
  • a mixture of the chemical oxidant and ionic dye may then be exposed to monomers that are in the vapour phase such that they undergo vapour phase polymerisation to form the polymer.
  • a mixture of the chemical oxidant, the anionic dye and the monomers may undergo bulk polymerisation to form the polymer.
  • the vapour phase and bulk polymerisation can conveniently be performed using conditions known to those skilled in the art.
  • the mixture comprising the chemical oxidant and the ionic dye may be applied to the surface of a substrate, and the coated substrate exposed to monomer in the vapour phase.
  • the mixture may be conveniently applied to the substrate by first forming a liquid mixture comprising the chemical oxidant and the ionic dye and applying this liquid mixture to the surface of the substrate.
  • the liquid mixture may be provided by combining the chemical oxidant and ionic dye in one or more suitable solvents. This might be achieved by dissolving the ionic dye in one or more solvents and dissolving the chemical oxidant in one or more solvents and combining these solutions to form the liquid mixture comprising the chemical oxidant and ionic dye.
  • the resulting liquid mixture may be applied to the surface of a substrate by any suitable means, for example using printing equipment/techniques such as inkjet printers, screen printing, flexographic printing, or simply by spraying.
  • any solvent present is preferably evaporated prior to performing the polymerisation.
  • the coated substrate may be subjected to elevated temperatures for sufficient time to remove solvent from the mixture.
  • the coated substrate can then be exposed to monomer vapour for sufficient time at a suitable temperature so as to form the ICP on the coated regions of the substrate.
  • the mixture comprising the chemical oxidant, the ionic dye and the monomers may be applied to the surface of a substrate to subsequently undergo polymerisation.
  • the mixture may be conveniently applied to the substrate by first forming a liquid mixture comprising the chemical oxidant, the ionic dye and the monomers, and applying this mixture to the surface of the substrate.
  • the liquid mixture may be provided by combining the chemical oxidant, the ionic dye and the monomer in one or more suitable solvents. This might be achieved by dissolving each of these components in one or more solvents and combining these solutions to form the liquid mixture.
  • the resulting liquid mixture may be applied to the surface of the substrate by any suitable means, such as the printing equipment/techniques mentioned above.
  • the mixture might further comprise a volatile polymerisation retardant such as a base that can complex with and render the chemical oxidant temporarily ineffective.
  • a suitable volatile base includes, but is not limited to, optionally substituted pyridine. Further details in relation to the use of an optionally substituted pyridine in this manner is described in WO 2005/103109.
  • the polymerisation retardant may also be in the form of a polyurethane resin.
  • the resin is believed to provide amine functionality that can also complex with and render the chemical oxidant temporarily ineffective.
  • reactivation of the chemical oxidant may be achieved simply by heating the applied mixture.
  • the invention also provides a method for forming on a surface of a substrate an intrinsically conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant, the ionic dye, monomer and a volatile polymerisation retardant, wherein upon evaporation of the volatile polymerisation retardant from the printed mixture the monomers polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the intrinsically conducting polymer, and wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the present invention further provides a composition comprising a chemical oxidant, an ionic dye, monomer and a volatile polymerisation retardant, wherein said composition, will, upon evaporation of the polymerisation retardant, polymerise under acidic conditions to form an intrinsically conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • a composition comprising a chemical oxidant, an ionic dye, monomer and a volatile polymerisation retardant, wherein said composition, will, upon evaporation of the polymerisation retardant, polymerise under acidic conditions to form an intrinsically conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • an optionally substituted pyridine as a volatile polymerisation retardant
  • the aforementioned mixtures used in performing the vapour phase or bulk polymerisation may include one or more other components.
  • a component may be required to suppress crystallisation or precipitation of the chosen oxidant on drying of the mixture.
  • Such a crystallisation or precipitation suppressant may include, but is not limited to, polyurethane diol, polypropylene glycol, proprietary surfactant formulations such as Teric BL8 (C12 ethoxylated fatty acid alcohol, Huntsman) and Glysolv (l-methoxy-2-propanol, Huntsman), or combinations thereof.
  • Additional components may also be required to improve film uniformity, film elasticity or hold out on porous substrates of the resulting ICP.
  • Such components may include, but are not limited to, polyurethane resins (which may also serve as a polymerisation retardant if required) of varying molecular structure and molecular weight, chosen to suit the requirements of the intended method of application.
  • polyurethane resins which may also serve as a polymerisation retardant if required
  • a short chain polyurethane resin may be required to suit the viscosity and elastomeric requirements of inkjet printing
  • a long chain resin maybe required to increase the viscosity for screen printing.
  • the aforementioned polymerisation techniques can advantageously be applied in performing a method according to the invention of forming on a surface of a substrate a conducting polymer having a polymeric matrix with an ionic dye retained therein.
  • a mixture comprising a chemical oxidant and the ionic dye
  • the mixture may be exposed to the monomers that are in the vapour phase to form the ICP by vapour phase polymerisation.
  • the mixture applied to the substrate may further comprise the monomer, and the ICP may be formed by bulk polymerisation.
  • the mixture applied to the substrate may comprise a polymerisation retardant and/or one or more other components, and the mixture may be applied to the substrate using the aforementioned printing equipment/techniques.
  • ICPs prepared in accordance with the invention may be prepared, for example, in a mold and formed into a shaped article or applied to the surface of a conducting or non-conducting substrate.
  • the method of the present invention is particularly suited to forming the ICP on the surface of a non-conductive substrate such as paper by applying the relevant mixture to the substrate using conventional printing equipment/techniques.
  • vapour phase polymerisation a mixture comprising the chemical oxidant and ionic dye may be applied to the surface of a substrate using conventional printing techniques/equipment, and the resulting printed substrate exposed to monomer in the vapour phase to form the ICP only on the printed regions of the substrate.
  • a mixture comprising the chemical oxidant, ionic dye, monomer and typically a polymerisation retardant may be applied to the surface of a substrate using conventional printing equipment/techniques where the ICP will form only on the printed regions of the substrate.
  • the morphology of the ICP formed on a given substrate may vary depending upon the mode of polymerisation used. For example, vapour phase polymerisation techniques may give rise to ICP's having a more porous morphology compared with the same class of polymer being formed using bulk polymerisation techniques.
  • the invention therefore enables ICP patterned substrates to be prepared with ease.
  • suitable substrates upon which the ICPs may be formed include, but are not limited to, non-conductive substrates such as paper, plastic, wood, glass, ceramic, textiles and fabrics, and conductive substrates such as metals (e.g. silicon, zinc, iron, aluminium, copper, lead, tin, magnesium and alloys thereof), conducting metal oxides such as tin oxide and indium tin oxide, and conducting polymers (e.g. polypyrrole, polyaniline, polythiophene, poly(3,4-ethylenedioxythiophene), polyfuran, polyphenylene and derivatives thereof).
  • non-conductive substrates such as paper, plastic, wood, glass, ceramic, textiles and fabrics
  • conductive substrates such as metals (e.g. silicon, zinc, iron, aluminium, copper, lead, tin, magnesium and alloys thereof), conducting metal oxides such as tin oxide and indium tin oxide, and conducting polymers (e.g. polypyrrole, polyaniline, polythiophene, poly(3,
  • the manner in which the ICP deposits on the substrate may vary depending on the type of substrate employed.
  • a porous paper substrate may enable the ICP to penetrate into the substrate
  • a relatively non-porous plastic substrate e.g. polyethylene terephthalate (PET) film
  • PET polyethylene terephthalate
  • the reagents required to perform the method of the invention can conveniently be provided in the form of a unique composition.
  • the present invention further provides a composition comprising a chemical oxidant, an ionic dye, monomer and a polymerisation retardant, wherein said composition, after being applied to a surface of a substrate will polymerise under acidic conditions to form an intrinsically conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • the present invention further provides a composition comprising a chemical oxidant, an ionic dye, monomer and a volatile polymerisation retardant, wherein said composition, upon being applied to a substrate, will, upon evaporation of the volatile polymerisation retardant, polymerise under acidic conditions to form a conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • the present invention also provides a composition comprising a chemical oxidant and an ionic dye, wherein said composition, upon being applied to a substrate and exposed to monomers in the vapour phase, will, under acidic conditions, promote the vapour phase polymerisation of the monomers to form a conducting polymer having a polymeric matrix with the ionic dye retained therein.
  • the compositions according to the invention may be conveniently provided within a cartridge or dispenser for use in printing equipment or techniques.
  • the compositions according to the invention may be provided within a print cartridge that can be used in conventional printing equipment to print the composition onto the surface of a substrate.
  • the ICP may be formed directly from the printed composition, or the printed composition may need to be exposed to monomer in the vapour phase that will polymerise to form the ICP.
  • the compositions may be desirable that they are filtered to remove any undesirable particulate material.
  • the compositions may be passed through a 0.45 micron filter.
  • print cartridge is intended to mean a container which is designed to contain and dispense as required onto a nominated surface a composition according to the invention.
  • These cartridges can include, but are not limited to, cartridges for piezoelectric or thermal inkjet printers, provided such printers have print heads capable of satisfactory resistance to the oxidants, acids and solvents employed in the reaction mixture.
  • the method for forming on a surface of a substrate an ICP having a polymeric matrix with an ionic dye retained therein is particularly suited for use in printing applications.
  • the invention also provides a method for forming on a surface of a substrate a conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant and the ionic dye, and exposing the printed mixture to monomers in the vapour phase which polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the conducting polymer, and wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the invention further provides a method for forming on a surface of a substrate a conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant, the ionic dye, monomer and a polymerisation retardant, wherein after printing the monomers polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the intrinsically conducting polymer, and wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the invention also provides a method for forming on a surface of a substrate a conducting polymer having a polymeric matrix with an ionic dye retained therein, said method comprising printing onto the surface of the substrate a mixture comprising a chemical oxidant, the ionic dye, monomer and a volatile polymerisation retardant, wherein upon evaporation of the volatile polymerisation retardant from the mixture the monomers polymerise under acidic conditions in the presence of the chemical oxidant and the ionic dye to form the conducting polymer, and wherein the chemical oxidant promotes the polymerisation of the monomers.
  • the amount (e.g. layer thickness) of ICP dye host that is to be formed on the surface of the substrate there is no particular limitation on the amount (e.g. layer thickness) of ICP dye host that is to be formed on the surface of the substrate, and this will generally be dictated by the intended application of the resulting coated substrate.
  • the ICP dye host may be formed on the surface of the substrate so as to have a layer thickness ranging from about 0.2 to about 10 microns. In some embodiments, the layer thickness may range from about 0.5 to about 1.5 microns.
  • the invention further provides a sensing device comprising an ICP formed in accordance with the invention, wherein the ionic dye is released from the polymeric matrix in response to a condition to be sensed.
  • the ionic dye can be released from the ICP as a result of the ICP being reduced.
  • the ICP may be reduced by electrochemical and/or chemical means. Those skilled in the art will appreciate that such a reduction reaction will generally be conducted in an electrolyte solution.
  • the rate of dye release will generally vary depending on the nature of the dye, polymeric matrix and conditions by which release has been promoted. For example, under similar reduction conditions, a given dye may be released more rapidly from a polypyrrole polymeric matrix than a poly(3,4-ethylenedioxythiophene) polymeric matrix.
  • the ICP will form part of an electrochemical cell, with the ICP necessarily forming all or part of the cathode.
  • Both galvanic or voltaic and electrolytic cells may be used to promote the electrochemical reduction of the ICP.
  • galvanic or voltaic and electrolytic cells may be used to promote the electrochemical reduction of the ICP.
  • to promote substantially uniform and complete reduction of the ICP it may be desirable for it to be applied or coated onto a substrate that will remain conductive throughout the reduction reaction.
  • reduction of the ICP will be limited unless a reducing potential can be carried to the remainder of the ICP, for example by an underlying conducting substrate.
  • a conducting material such as an ICP as the underlying substrate of the cathode (i.e. as a separate layer to the ICP dye host) in order to (a) promote substantially uniform reduction of the ICP dye host, and (b) produce a device whose components can all conveniently be printed in a reel-to-reel production process.
  • the ICP should have a reduction potential compatible with the ICP dye host.
  • polypyrrole could be employed as the ICP dye host, since the difference between the reduction potentials of the ICPs (polypyrrole: -0.56V; poly(3,4-ethylenedioxythiophene): -0.82V) is great enough to allow the release of the dye from the polypyrrole.
  • Other underlying conducting substrates such as metals or metal oxides may not suffer this limitation and may be used for all ICP dye hosts.
  • ICP dye host is intended to mean an ICP prepared in accordance with the invention.
  • the anode of the cell may be any suitable conducting material.
  • the anode may be a metal, including but not limited to, aluminium, magnesium or zinc. Anodes constructed of these metals must provide sufficient galvanic potential to cause the reduction of the ICP cathode, with consequent release of retained dye.
  • Suitable electrolyte solutions include, but are not limited to, aqueous solutions of ionic salts at low concentration, for example 0.1M sodium chloride, or ionic liquids, for example l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI).
  • EMI-TFSI l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • the sensing device in accordance with the invention will typically comprise at least a first electrode comprising the ICP, a second electrode, and an electrolyte. Where the reduction is performed in an electrolytic cell, the device may further comprise a source of electrical charge such as a battery.
  • the reduction can be promoted by exposing the ICP to alkaline conditions (i.e. a pH greater than 7.0).
  • alkaline conditions i.e. a pH greater than 7.0
  • a solution in which the ICP is immersed may be rendered alkaline by the absorption of alkaline particles, solutions or vapours.
  • the degree of alkalinity required for the dye to be released and the rate at which it is released will vary depending on the type of dye and ICP employed. Generally, most ICPs will become sufficiently reduced to release the dye at a pH ranging from about 9 to about 12, preferably from about 10 to about 12.
  • the dye is released into a surrounding alkaline electrolyte solution, preferably a weak ionic electrolyte, including but not limited to aqueous solutions of ionic salts at low concentration, for example 0.1M sodium chloride, or ionic liquids, for example EMI- TFSA.
  • a sensing device in accordance with the invention need only comprise the ICP and an appropriate electrolyte solution.
  • the ionic dye is released from the polymeric matrix in response to a condition to be sensed.
  • reduction of the ICP promotes release of the ionic dye into a solution within which the ICP is immersed, it will be appreciated that the reduction per se may or may not be the condition to be sensed, hi other words, the device according to the invention may be designed to sense one or more conditions that directly or indirectly give rise to an environment that enables the reduction reaction to occur.
  • the sensing device may be designed to sense temperature change whereby a first electrode comprising the ICP dye host and a second electrode in electrical contact with the first electrode through a source of electrical charge (e.g. a battery) are immersed in an electrolyte solution having a specific freezing point. Provided the electrolyte solution is maintained at a temperature below its freezing point, charge will be prevented from flowing in the resulting electrolytic cell. However, if the temperature of the electrolyte solution is increased above its freezing point, charge can begin to flow and the ICP will be reduced with the ionic dye being released into the electrolyte solution.
  • a source of electrical charge e.g. a battery
  • such a device can be used as a temperature sensor, whereby the device signals that a temperature above the freezing point of the electrolyte solution has been reached by release of a highly coloured dye into the otherwise clear electrolyte solution.
  • Such devices might find use in monitoring the temperature history of frozen food products.
  • a similar self-powered device might also be devised in the form of a galvanic cell.
  • Other conditions that might be sensed include, but are not limited to, humidity, where the device might comprise a first electrode comprising the ICP dye host, a second electrode in electrical contact with the first electrode through a source of electrical charge (e.g. a battery) and a hydroscopic electrolyte that is non conductive in the dry state. On absorption of a predetermined amount of moisture, the electrolyte would become conductive allowing charge to flow to reduce the ICP and release the dye, signalling an increase in humidity above the designed threshold level.
  • a source of electrical charge e.g. a battery
  • a hydroscopic electrolyte that is non conductive in the dry state.
  • the electrolyte would become conductive allowing charge to flow to reduce the ICP and release the dye, signalling an increase in humidity above the designed threshold level.
  • Such devices might find use in monitoring the storage conditions of sensitive electronic components or perishable foodstuffs.
  • tissue paper was first coated with a conducting polymer, poly(3,4- ethylenedioxythiophene), hereafter abbreviated as PEDOT.
  • PEDOT poly(3,4- ethylenedioxythiophene), hereafter abbreviated as PEDOT.
  • PEDOT poly(3,4- ethylenedioxythiophene)
  • the latter step was carried out in a glass vessel with a small amount of the liquid monomer in the bottom which was maintained in equilibrium with the atmosphere in the vessel by magnetically stirring.
  • the paper substrate was fully coated with PEDOT and it was withdrawn from the treatment chamber and any unreacted monomer evaporated.
  • the PEDOT-coated paper was then washed in water and air dried.
  • the coated tissue paper sample was used as the cathode in a galvanic cell, with a strip of zinc metal as the anode.
  • the electrolyte used was 1OmL of 0.1 M NaCl. Upon completion of the galvanic circuit, phenol red dye molecules were released into the electrolyte solution as illustrated in Figure 1.
  • polypyrrole and phenol red were applied directly to filter paper and released as a result of reduction of the polymer at high pH.
  • the sodium salt of phenol red 50 mg was dissolved in a 50:50 mixture (w/w) of water:ethanol (2 mL). This solution was then added to 0.15 mL of pyridine and 3.25 mL of 40% iron(III)/?-toluenesulfonate in butan-1-ol solution.
  • the dye-oxidant mixture was applied to filter paper and dried on a hotplate at 7O 0 C for 5 min.
  • the coated substrate was exposed to pyrrole vapour in a glass vessel with a small amount of the liquid monomer in the bottom which was maintained in equilibrium with the atmosphere in the vessel by magnetically stirring.
  • Example 3 After 20 minutes at room temperature, the paper substrate was fully coated and it was withdrawn from the treatment chamber to evaporate any unreacted monomer. The coated paper was washed three times in deionised water (3 x 100 mL at pH 6.5) for 10 min in order to remove reaction products and excess chemicals. The coated filter paper was subdivided into samples and immersed in 10 mL aliquots of 0.1M NaCl with varying amounts of NaOH solution added to adjust pH in the range from 8 to 13. The amount of dye released after 20 minutes exposure to the alkali-adjusted electrolyte was monitored with a UV-vis spectrophotometer at a wavelength of 558 nm. The absorbance of phenol red released from polypyrrole after 20 minutes measured at 558 nm as a function of pH is graphically illustrated in Figure 2. The amount of dye released increased to a maximum at pH 12 and remained relatively constant thereafter. Example 3
  • phenol red dye was held and released from within poly(3,4- ethylenedioxythiophene), hereafter abbreviated as PEDOT, the polymer being produced by bulk chemical polymerization rather than vapour phase polymerization.
  • PEDOT poly(3,4- ethylenedioxythiophene)
  • a monomer formulation was first prepared for mixing with other components, comprising 3.38 g of 3,4-ethylenedioxythiophene, 2.31 g pyridine, 1.69 g polyurethanediol and 2.62 g butan-1- ol.
  • This stock mixture (0.5 g) was mixed with 0.05 g phenol red, 0.12 g pyridine, 1.38 g ethanol and 5 g of the oxidant, which was 40% iron(III)p-toluenesulfonate in butan-1-ol.
  • a conductive substrate (ITO coated glass) was coated with the formulation and heated for 20 min on a hotplate at 70°C to evaporate the pyridine and initiate polymerisation of the PEDOT. After polymerisation the substrate was washed in water to remove reaction products and excess chemicals.
  • the coated glass was used as the cathode of an electrochemical cell, with a PEDOT-coated PET film used as the anode.
  • the electrolyte was 0.1M NaCl and a potential of 1.5 VDC was applied from an external power supply. Upon completion of the electrolytic circuit, phenol red dye molecules were released into the electrolyte solution as illustrated in Figure 3.
  • Example 6 the procedure employed as described in Example 1 above was repeated; with the exception that Phenol red dye was replaced by Thymol Blue. Again release of the dye was successfully achieved by application of a galvanic potential from a strip of zinc metal immersed in 10 mL of 0.1 M NaCl electrolyte.

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Abstract

L'invention concerne un procédé de préparation d'un polymère à conduction intrinsèque comprenant une matrice polymère contenant un colorant ionique. Ce procédé consiste à effectuer une polymérisation par oxydation chimique de monomères dans des conditions acides, en présence du colorant ionique, de sorte à former ledit polymère à conduction intrinsèque. L'invention concerne également un procédé de formation de ce polymère à conduction intrinsèque sur la surface d'un substrat, une composition servant à préparer ledit polymère, ainsi qu'un dispositif de détection comprenant le polymère à conduction intrinsèque.
PCT/AU2008/000952 2007-06-28 2008-06-27 Polymeres a conduction intrinseque Ceased WO2009000049A1 (fr)

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CN109860598A (zh) * 2019-01-29 2019-06-07 上海交通大学 3d打印一次成型水系锌离子电池及其实现方法
CN113173570A (zh) * 2021-04-21 2021-07-27 国网黑龙江省电力有限公司电力科学研究院 一种类石墨烯片状氮掺杂多孔碳材料的制备方法及应用

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CN109860598B (zh) * 2019-01-29 2021-06-18 上海交通大学 3d打印一次成型水系锌离子电池及其实现方法
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