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EP0563289A1 - Verfahren zur herstellung elektrisch leitfähiger polyaniline in lösungsmittelmischungen - Google Patents

Verfahren zur herstellung elektrisch leitfähiger polyaniline in lösungsmittelmischungen

Info

Publication number
EP0563289A1
EP0563289A1 EP92903538A EP92903538A EP0563289A1 EP 0563289 A1 EP0563289 A1 EP 0563289A1 EP 92903538 A EP92903538 A EP 92903538A EP 92903538 A EP92903538 A EP 92903538A EP 0563289 A1 EP0563289 A1 EP 0563289A1
Authority
EP
European Patent Office
Prior art keywords
acid
polyaniline
dopant
hydroxy
substituted
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.)
Withdrawn
Application number
EP92903538A
Other languages
English (en)
French (fr)
Inventor
Chien-Chung Han
Ronald L. Elsenbaumer
Lawrence W. Shacklette
Granville G. Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zipperling Kessler GmbH and Co
Original Assignee
AlliedSignal Inc
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
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of EP0563289A1 publication Critical patent/EP0563289A1/de
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof

Definitions

  • This invention relates to solutions of
  • Another aspect of this invention relates to a method of using such solutions to form polymer articles, such as films, printings, coatings and parts.
  • European Patent No. 0017717 is an apparent improvement in the compositions of U.S. Patent Nos. 3,963,498 and 4,025,463 and states that the polyaniline can be formed into a latex composite through use of acetone solutions of the oligomers of polyaniline and suitable binder polymers.
  • U.S. Patent No. 4,855,361 describes a conductive polymer blend which comprises mixing a polyamide with a base-type polymer containing carbon nitrogen linkages, such as polyaniline, having a polyamide-like group covalently linked to the nitrogen atoms of the
  • the conductive polymer blend is formed by first reacting a base-type non-conductive polymer containing carbon-nitrogen linkages, such as polyaniline, with a carbonyl anhydride, such as 3, 4, 3', 4'-benzophenone tetracarboxylic dianhydride to form a conductive polymer containing polyimide-like groups covalently linked to the nitrogen atoms of the
  • carbon-nitrogen linkages e.g. polyaniline
  • R + donor compound where R is an organic group, e.g.
  • carbon-nitrogen linkages e.g., polyaniline
  • a cation donor compound such as R 2 SO 4 , R'SO 2 Cl or
  • R, R' and R" are alkyl or aryl, such as dimethyl sulfate or tosyl chloride, and forming an electrically conductive polymer in which the R groups of R 2 SO 4 , the R'SO 2 groups of R'SO 2 Cl, or the R" 3 Si groups of R" 3 SiCl are covalently linked to the nitrogen atoms of the polymer.
  • U.S. Patent No. 4,822,638 describes a process for fabricating an electronic device on a non-conductive polymer substrate, particularly from the family of polyaniline, which comprises applying a covalent doping agent,such as an R+ donor compound, where R is an organic group, e.g., methyl iodide, to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, and converting such preselected portion of the polymer substrate to an electrically conductive polymer portion, by covalent linkage of the R groups of such donor compound, to the nitrogen atoms of the non-conductive polymer substrate.
  • a covalent doping agent such as an R+ donor compound, where R is an organic group, e.g., methyl iodide
  • carbon-nitrogen linkages e.g., polyaniline
  • an anhydride such as R-SO 2 -O-SO 2 -R' ,R-CO-O-CO-R' or R-CO-O-SO 2 R or mixtures thereof, where R and R' are alkyl or aryl, e.g., tosylic anhydride or benzophenone tetracarboxylic dianhydride, and forming an anhydride such as R-SO 2 -O-SO 2 -R' ,R-CO-O-CO-R' or R-CO-O-SO 2 R or mixtures thereof, where R and R' are alkyl or aryl, e.g., tosylic anhydride or benzophenone tetracarboxylic dianhydride, and forming an anhydride such as R-SO 2 -O-SO 2 -R' ,R-CO-O-CO-R' or R-CO-O-SO 2 R or mixtures thereof,
  • conductive polymers is the RSO 3 - or R'CO 2 - group.
  • carbon-nitrogen linkages e.g., polyaniline
  • R + donor compound where R is an organic group, e.g., methyl iodide, and forming an electrically conductive polymer in which the R groups are covalently linked to the nitrogen atoms of the polymer.
  • PCT WO89/01694 describes various electrically conductive polyanilines doped with certain sulfonated dopants. These materials are disclosed as thermally stable and capable of being melt blended t ⁇ 4 form blends with other types of polymers.
  • One aspect of this invention relates to a
  • plasticized composition comprising one or more
  • substituted or unsubstituted polyanilines one or more Lewis-base/dopant complexes, said Lewis base having pK a which is greater than that of said polyaniline and said dopant capable of doping said polyaniline to form electrically conductive polyaniline on release of said dopant from said complexes and one or more solvents capable of dissolving said complex and said polyaniline to some extent or capable of plasticizing said
  • solution is a real solution or an ultra-fine
  • uncharged backbone and "polyaniline base” is a particular form of undoped polyaniline which contains at least one quinoid diamine linkage in the backbone.
  • Another aspect of this invention relates to a method of forming a conductive article or forming a polymer coated substrate from the solution or
  • solution or plasticized composition comprising one or more substituted or unsubstituted polyanilines; one or more Lewis-base/dopant complexes, said Lewis base having pK a which is greater than that of said
  • said dopant capable of doping said polyaniline to form electrically conductive polyaniline on release of said dopant from said complexes and one or more solvents capable of dissolving said complexes and said polyanilines to some extent or capable of plasticizing said polyaniline or a combination thereof;
  • Yet another aspect of this invention relates to an article of manufacture formed through use of the solution and process of this invention.
  • Still another aspect of this invention relates to a process of dissolving a substituted polyaniline or an unsubstituted polyaniline doped with a dopant or a combination thereof to render it electrically
  • conductive which comprises the steps of mixing said polyaniline to a liquid or molten Lewis base having a basicity greater than the basicity of said polyaniline as determined by relative pk a 's, said Lewis base being capable of complexing with said dopant in said polymer to form a Lewis-base/dopant complex and undoped
  • polyaniline can be conveniently processed into useful conductive articles of all shapes such as fibers, coatings, films and the like using conventional solution or plasticized polymer techniques.
  • Figure 1 shows ultraviolet-visible-near-infrared spectra of sulfonated polyaniline complexed with triethylamine, tripropylamine and tributylamine in methanol.
  • Figure 2 shows ultraviolet-visible-near infrared spectra of sulfonated polyaniline complexed with tri-n-propyl amine in methanol and ethanol, and tri-n-butylamine in ethanol.
  • FIG. 3 shows an
  • Figure 4 shows a graph showing the Hansen
  • Figure 5 is a graph showing the Hansen Solubility Parameters relative to polyaniline base for solvents and non-solvents.
  • the non-electrically conductive solutions or plasticized compositions of this invention comprise three essential ingredients.
  • One essential ingredient is a substituted or unsubstituted polyaniline which is capable of being doped with a suitable dopant to become electrically conductive to at least about 10 -10 Scm -1 as measured by the co-linear four-probe method.
  • polyaniline can be conveniently used in the practice of this invention.
  • Illustrative of useful forms are those described in Green, A.G. and Woodhead, A.E., CXVII Aniline-black and Allied Compounds, Part I", J. Chem. Soc., 101, pp1117 (1912) and Kobayashi, et al.,
  • unsubstituted or substituted polyaniline useful forms of which are characterized by different ratios of phenylene amine and quinone amine backbone segments, include leucoemeraldine, protoemeraldine, emeraldine, nigraniline and pernigraniline.
  • polyanilines for use in the invention are homopolymers and ⁇ opolymers of the type derived from the
  • n is an integer from 0 to 5;
  • n and m are integers from 0 to 5, with the proviso that the sum of n and m is equal to 5;
  • R 2 is the same or different at each occurrence and is R 3 substituents or hydrogen;
  • R 3 is the same or different at each occurrence and is selected from the group consisting of boric acid, phosphinic acid, phosphoric acid, sulfinate, amido, carboxylic acid, hydroxyamino, phosphonic acid, halo, hydroxy, cyano, sulfinic acid, carboxylate, borate, phosphate, sulfonate, phosphinate, phosphonate, sulfonic acid, nitro, amino, cyano, deuterium or substituted or unsubstituted arylsulfinyl,
  • alkylsulfinylalkyl alkoxyalkyl, alkoxyaryl,
  • alkylsulfonyl arylthio, alkylsulfonylalkyl, or
  • alkylsilane or any two R 3 groups together or any R 3 group together with any R 2 group may form a substituted or unsubstituted alkylene, alkynylene, or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroaromatic, heteroalicyclic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl or oxygen atoms, wherein permissible
  • substituents are one or more amino, alkylamino,
  • R 3 is a divalent organic moiety bonded to the same or a different substituted or
  • R 3 is an aliphatic moiety having repeat units of the formula:
  • R 2 , and R 3 are as describe above;
  • n and m are the same or different at each occurrence and are integers from 0 to 4, with the proviso that the sum of n and m is 4;
  • y and x are the same or different at each occurrence and are integers equal to or greater than 0, with the proviso that the sum of x and y is greater than 0, preferably x is an integer equal to or greater than about 1 and/or the ratio of x to y is greater than or equal to about 0.5; and
  • z is an integer equal to or greater than 1.
  • R 2 groups are hydrogen, methyl, ethyl, isopropyl, butyl, isobutyl, hexyl, octyl, benzyl, and the like.
  • R 3 groups are hydrogen, alkyl such as methyl, ethyl, octyl, nonyl, tert-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonoxy, ethyoxy, octoxy, and the like; cycloalkenyl such as cyclohexenyl, cyclopentenyl and the like;
  • alkanoyl such as butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the like; alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfonyl, arylsulfonyl, and the like, such as butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl, phenylsulfinyl, propylthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, isopropylthio, phenylsulfonyl,
  • methylsulfonyl nonylthio, phenylthio, ethylthio. benzylthio, phenethylthio, sec-butylthio, naphthylthio and the like; alkoxycarbonyl such as methoxycarbonyl, ethoxyethyl, ethoxycarbonyl, butoxycarbonyl and the like; cycloalkyl such as cyclohexyl, cyclopentyl, cyclooctyl, cycloheptyl and the like; alkoxyalkyl such as methoxymethyl, ethoxymethyl, butoxymethyl,
  • acid groups such as sulfonic acid, carboxylic acid and the like; organic radicals substituted with acid groups and salts thereof such as alkoxy, alkoxyalkyl, alkylamino, arylamino, alkyl or aryl groups substituted with various acid groups such as phosphonic acid, phosphinic acid, sulfinate, sulfonic acid, sulfinic acid,
  • phosphoric acid, boric acid, or carboxylic acid groups such as ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, phenylsulfonic acid, and the corresponding phosphoric acid, boric acid, sulfonic acid, carboxylic acid, sulfinate, sulfinic acid, phosphonic acid, and phosphinic acid; and amino, alkylamino, dialkylamino, arylamino, diarylamino, or alkylarylamino groups such as amino, methylamino, ethylmethylamino, ethylamino, dimethylamino,
  • R 3 groups are divalent moieties derived from any two R 3 groups or a R 3 group with any R 2 group such as moieties of the formula: wherein a is an integer from about 3 to about 7, and b is an integer from 1 to 2 and R 3 is the same or
  • R 3 groups are divalent alkenylene chains
  • n is an integer from 0 to about 2;
  • n and m are integers from 2 to 4, with the proviso that the sum of n and m is equal to 4;
  • R 2 is the same or different at each occurrence and is a R 3 substituent or hydrogen
  • R 3 is aryl, alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halo, sulfonic acid, carboxylic acid, boric acid, borate, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid,
  • phosphinate sulfinic acid, sulfinate, carboxylate, sulfonate, amino, alkylamino, dialkylamino, arylamino, hydroxy, diarylamino, alkylarylamino, or alkyl, aryl or alkoxy substituted with phosphonic acid, phosphate, phosphoric acid, borate, sulfonate, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, hydroxy, alkoxy, phosphonate, boric acid, alkyl, phosphinic acid, phosphonate, phosphinate, carboxylic acid or sulfonic acid substituents;
  • x is an integer equal to or greater than 1;
  • y is equal to or greater than 0,
  • z is an integer equal to or greater than about 5.
  • Particularly preferred for use in the practice of this invention are polyanilines of the above Formulas in which:
  • n is an integer from 0 to 1;
  • n and m are integers from 3 to 4, with the proviso that the sum of n and m is equal to 4;
  • R 2 is the same or different at each occurrence and is a R 3 subsituent or hydrogen;
  • R 3 is aryl, alkyl or alkoxy having from 1 to about 20 carbon atoms, sulfonic acid, halo, carboxylic acid, amino, carboxylate, alkylamino, phosphonate,
  • x is an integer equal to or greater than 2;
  • y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 2; and z is an integer equal to or greater than about 5.
  • n is an integer from 0 to 1;
  • n and m are integers from 3 to 4, with the proviso that the sum of n and m is equal to 4;
  • R 2 is hydrogen
  • R 3 is aryl, alkyl or alkoxy from 1 to about 15 carbon atoms, amino, alkylamino, dialkylamino,
  • arylamino diarylamino, alkylarylamino, halo, sulfonic acid, sulfonate, carboxylic acid, carboxylate, or alkyl or aryl substituted with one or more sulfonic acid, carboxylate, amino, alkylamino, dialkylamino,
  • arylamino diarylamino, halo, alkylarylamino, sulfate, sulfonic acid, or carboxylic acid substituents;
  • x is an integer equal to or greater than 2;
  • y is equal to or greater than 1, with the proviso that the ratio of x to y is equal to or greater than about 2;
  • z is an integer equal to or greater than about 5.
  • the polyaniline is derived from
  • the number of aniline repeat units is not critical and may vary widely. The greater the number of aniline repeat units the greater the number of aniline repeat units
  • the number of aniline repeat units is preferably at least about 10.
  • the upper limit can vary widely depending on the desired viscosity and molecular weight. In the more preferred embodiments of the invention, the number of aniline repeat units is at least about 20, and in the particularly preferred embodiments, the number of repeat units is at least about 30.
  • polyanilines can be prepared through use of chemical and electrochemical synthetic procedures.
  • one form of polyaniline can be prepared by treating aniline with ammonium persulfate (NH 4 ) 2 S 2 O B in excess 1M HCl. This powdered form of polyaniline is blue green in color. After methanol washing and air drying this material exhibits a conductivity of 10 S/cm.
  • This conductive form of polyaniline can be treated with ammonium hydroxide in ethanol to form a non-conductive form of polyaniline which is dark blue in color and which has a conductivity equal to or greater than of about 10 -10 S/cm.
  • Useful forms of polyaniline can also be prepared electrochemically.
  • useful forms of polyaniline can be prepared by the electrochemical oxidation of aniline in aqueous fluoroboric acid electrolyte on a platinum foil anode.
  • the second essential ingredient of the solution or plasticized composition of this invention is a Lewis base/dopant complex.
  • the purpose of the dopant is a Lewis base/dopant complex.
  • component of the complex is to dope the polyaniline and render it electrically conductive on release of the dopant from the complex and/or removal of the solvent and/or Lewis base from the solution or composition.
  • dopant solute is derived from a compound, which upon addition to the polyaniline, ionizes the polymer via oxidative electron transfer or protonation with co-committent formation of a dopant solute species to form a charge transfer complex with polyaniline.
  • the complex has a conductivity equal to or greater than about 10 -10 ohm -1 cm -1 , preferably equal to or greater than about 10 -6 ohm -1 cm -1 , more preferably equal to or greater than about 10 -2 ohm -1 cm -1 and most preferably equal to or greater than about 10 -1 ohm -1 cm -1 .
  • Dopants for use in the practice of this invention can vary widely and can be such materials which are known in the art for use in doping conjugated backbone polymers to form conductive or semiconductive polymers, as for example, those described in detail in U.S.
  • Patent Nos. 4,442,187 and 4,321,114 which are hereby incorporated by reference.
  • Illustrative of useful dopant species are oxidizing dopants. Oxidizing dopants are well known in the conductive polymer art, and any of such known oxidizing dopants can be used.
  • Illustrative of useful oxidizing dopants are AsF 5 , MoOCl 4 , MoCl 5 , PCI 5 , POCl 3 , PCl 3 , AlCl 3 , NO + and NO 2 + salts (such as NOBF 4 , NOPF 6 , NOSbF 6 , NOAsF 6 , NOCH 3 CO 2 , NO 2 BF 4 , NO 2 PF 6 , NO 2 AsF 6 , NO 2 SbF 6 , and NO 2 CF 3 SO 2 ) , HClO 4 , HNO 3 , H 2 SO 4 , benzoylperoxide, SO 3 , Br 2 , (FSO 3 ) 2 , ZnCl 2 , FSO 3 H, and Fe(III) salts (such as Fe(BF 4 ) 3 , FeBr 3 ,
  • Fe(CH 3 SO 3 ) 3 , Fe(ClO 4 ) 3 , FeCl 3 , Fe(OTs) 3 , and Fe(CF 3 SO 3 ) 3 which give rise to doped polymers containing dopant solutes such as NO 3 -, CH 3 SO 3 -, AlCl 4 -,BF 4 -, ZnCl 4 -, PCl 4 -, PF 6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 -, CIO 4 -, OTs-, SO 3 -, C 6 H 5 CO 2 -, CH 3 SO 3 -, FSO 3 -, and FeCl 4 -.
  • dopant solutes such as NO 3 -, CH 3 SO 3 -, AlCl 4 -,BF 4 -, ZnCl 4 -, PCl 4 -, PF 6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 -, CIO 4
  • oxidizing dopants include electrolyte salts such as LiClO 4 ,LiBF 4 , LiAsF 6 , NaPF 6 , Bu 4 NClO 4 , Bu 4 NOTs, Bu 4 NCF 3 SO 3 , LiCF 3 SO 3 , AgOTs, and the like.
  • Preferred oxidizing dopants for use in the practice of this invention are oxidizing dopants selected from the group consisting of MoOCl 4 , MoCl 5 , and Fe (III) salts such as Fe(ClO 4 ) 3 , FeCl 3 ,
  • FeBr 3 , and Fe(CF 3 SO 3 ) 3 and particularly preferred oxidizing dopants for use in the practice of this invention are dopants selected from the group
  • oxidizing dopants consisting of MoOCl 4 , MoCl 5 , and FeCl 3 .
  • most preferred oxidizing dopants are those embodiments in which the oxidizing dopant is FeCl 3 .
  • Such dopants include inorganic acids, such as hydrofluoric acid hydriodic acid, hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and the like.
  • R 1 is the same or different at each occurrence and is an organic radical or an amino group
  • s is a positive integer equal to or greater than 1, preferably from 1 to about 8;
  • M is a species having a positive charge equal to s
  • r is the same or different at each occurrence and is 0 or a positive integer equal to or greater than 1, with the proviso that at least one of r is other than 0.
  • the R 1 group may vary widely and can be amino, a substituted or unsubstituted aliphatic radical such as alkyl, alkylamino, dialkylamino, nitroalkyl, haloalkyl and the like, or a substituted or unsubstituted
  • aromatic radical such as phenyl, halophenyl,
  • R 1 may also be a polymeric or oligomeric radical such as a polymer having recurring pendant phenyl groups in the polymeric backbone substituted with sulfonic acid and derivatives thereof; such as salts; phosphoric acid and derivatives thereof; such as salts; phosphonic acid and derivatives thereof; such as salts; sulfinic acid and derivatives thereof; such as salts; carboxylic acid and derivatives thereof; such as salts; boric acid and derivatives thereof; such as salts; or phosphonic acid and
  • R 1 is an aromatic radical and in the most preferred embodiments R 1 is substituted or unsubstituted phenyl or naphthyl.
  • M +s may vary widely.
  • M +s may be be a non-metal cation such as Bu 4 N + , H + , NO + , NO 2 + , NH 4 + and the like, or may be a metal cation such as Na + , Li + , Ag + , Ba +2 , Co +3 , Al +3 , Fe +3 and the like.
  • organic acid dopants more preferably protonized forms of those having anionic portions of the formulas:
  • R 1 (P0 3 -) r (PO 2 -R 1 ) r (PO 3 H-) r (BO- 2 ) r (SO 3 ) r (CO 2 -) r (BO 2 H-) r where R 1 and r are as described above.
  • M is a metal or hydrogen or other non-metal cation
  • c 0, 1, 2, 3 or 4;
  • d 0, 1 or 2;
  • e 0, 1 or 2;
  • f 0, 1 or 2;
  • g is 0, 1 or 2 with the proviso that at least one of c, d, f and g is other than 0;
  • R 6 is nitro, phosphonate, phosphonic acid
  • sulfinate sulfinic acid, sulfate, quaternary ammonium, cyano, hydroxy, halo, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, alkoxy or substituted or unsubstituted aryl or alkyl having from 1 to about 30 carbon atoms wherein permissible
  • substituents include perhaloalkyl, phenyl, alkoxy, halo, cyano, amino, phosphate, alkylamino,
  • R 6 is a moiety of the formula:
  • q is a positive whole number from 1 to about 10;
  • useful dopants are acid or acid derivatives of the formula:
  • M is the same or different at each occurrence and is a metal or hydrogen or other non-metal cation
  • c 0, 1, 2 or 3;
  • d is 0 or 1
  • e is 0 or 1;
  • f is 0 or l
  • g is 0 or 1, with the proviso that at least one of c, d, f or g is other than 0;
  • Re is halo, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, hydroxy, phenyl, haloalkyl, perhaloalkyl, cyano, nitro, alkoxy, phosphonate, phosphonic acid, sulfinic acid or
  • sulfinate substituted or unsubstituted phenyl or alkyl wherein permissible substituents are selected from the group consisting of alkyl, halo, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, hydroxy, phenyl, haloalkyl, perhaloalkyl, cyano, nitro, alkoxy, boric acid, borate, phosphonate, phosphonic acid, carboxylate, sulfonate, phosphate, sulfonic acid, carboxylic acid, phosphoric acid, sulfinic acid or sulfinate or Re may form an unsubstituted or
  • substituted alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused ring system wherein permissible substituents are one or more halo, amino, alkylamino, dialkylamino, arylamino, alkyl, diarylamino, alkylaryl, amino, hydroxy, phenyl, haloalkyl, perhaloalkyl, cyano, nitro, alkoxy, boric acid, borate, hydroxy, phosphonate, phosphonic acid, carboxylate, sulfonate, alkoxy, phosphate, sulfonic acid, carboxylic acid, phosphoric acid, sulfinic acid or sulfinate substituted or unsubstituted phenyl; and
  • M is a cation such as NO + , NO 2 + , Fe(III), H + ,
  • useful dopants are acids or acid derivatives of the formula:
  • c is 1, 2 or 3;
  • d and e are the same or different and are 0 or 1;
  • R 6 is alkyl, phenyl, biphenyl, fluoro, amino, alkylamino, phosphate, phosphoric acid, borate, boric acid, dialkylamino, arylamino, diarylamino,
  • alkylarylamino alkyl substituted with one or more fluoro, sulfonic acid, phosphate, phosphoric acid, borate, boric acid, sulfonate, alkoxy, carboxylate, hydroxy, nitro, cyano, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or carboxylic acid groups, or phenyl or biphenyl substituted with one or more alkyl, fluoro, alkoxy, fluoroalkyl,
  • alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate, phosphate, phosphoric acid, borate, boric acid,hydroxy, nitro, cyano, or carboxylic groups or Re may form an unsubstituted or substituted alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, fluoroalkyl, phosphate, phosphoric acid, borate, boric acid, sulfonic acid,
  • TsOH toluenesulfonic Acid
  • the amount of dopant is not critical and may vary widely. In general, sufficient dopant is included in the complex such that on release of the dopant from the complex and removal of the Lewis base and/or solvent from the composition or solution, the polyaniline is doped to a conductivity of at least about 10 -10
  • the upper level of conductivity is not critical and will usually depend on the type of aniline polymer employed. In general, the highest level of conductivity obtained is provided without unduly adversely affecting the environmental stability of the polymer. In the preferred embodiments of the
  • the amount of dopant employed is sufficient to provide a conductivity of at least about 10 -6 ohm -1 cm -1 and in the particularly preferred embodiments is sufficient to provide a conductivity of from about 10-4ohm -1 cm -1 to about 10 +2 ohm -1 cm -1 .
  • the second component of the Lewis base/dopant complex is a Lewis base.
  • the Lewis base has several essential characteristics.
  • the base has a pK a greater than that of the polyaniline in the solution or the composition; and is capable of complexing with the dopant for the electrically conductive polyaniline to form a dopant/Lewis base complex which is soluble in the solvent to some extent.
  • the pK a of the Lewis base is greater than the pK a of the neutral (undoped) form of the polyaniline.
  • the pK a of the conjugate acid of the Lewis base component of the solution is then
  • the Lewis base may be a solid or a liquid but is such that it can be removed from the complex releasing the dopant to dope the polyaniline, and preferably is removable from the solution or the composition.
  • Lewis base can be removed from the complex by any suitable means as for example chemical reaction, extraction, evaporation and the like.
  • the Lewis base is preferably relatively volatile which enhances the quality of conductive polyaniline articles formed from the solution or plasticized composition.
  • volatile means that the Lewis base can be volatilized from the composition or solution when subjected to heat and has a
  • volatilization temperature such as a boiling point, a sublimation point and the like equal to or less than about 300°C under use conditions, preferably at
  • the lower limit to the volatilization temperature is not critical as long as the base can be easily handled under use conditions.
  • the volatilization temperature of the Lewis base may vary and is preferably less than about 250oC, more preferably from about 30 to about 150° and most
  • the Lewis base is a liquid under use conditions. This aids in a removal of the Lewis base from the composition or solution when they are used to form the article or coatings.
  • Lewis bases are primary, secondary and tertiary aromatic and aliphatic amines, phosphine compounds, amides, phosphoroamides and polymers containing amine or phosphine functional groups such as morpholine, 4-amino morpholine,
  • ethylamine 4-picoline, pyrrolidone, 2-oxazolidone, 2-imidazolidone, triphenylamine, benzylamine. diethylmethylamine, allylmethylamine, aniline,
  • dibutylamine triethylamine, dibenzylethylamine, piperazine, diethylamine, diisopropylamine,
  • N,N'-dimethyl-ethylenediamine tetrahydrofurfurylamine, 1,2,3,4-tetrahydroisoquinoline, trimethylphosphine triethylphosphine and the like.
  • the Lewis base of choice is selected from the group consisting of:
  • Lewis bases consisting of amines, amides, and phosphoramides. More preferred Lewis bases are primary, secondary and tertiary aliphatic amines, diamines, pyridine and amides. Such liquid Lewis bases as amides, diamines, amines and pyridine are preferred because they are strong enough bases to complex with the dopant; and because they are liquid at room temperature and are relatively volatile (boiling point of from about 30° to about 200°) and can be easily and completely removed on casting of the solution or composition in the desired form to form the desired solid electrically conductive articles or coated substrates. Most preferred amines, diamines, pyridine, and amides include piperdine, pyrrolidine, 2-picoline, benzylamine,
  • tetrahydrofurfurylamine trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylamine. diethylamine, dipropylamine,. dibutylamine, methylamine, ethylamine, propylamine, butylamine, amylamine,
  • the amount of Lewis base may vary widely but is usually at least an amount which is sufficient to complex with all or a portion of the dopant in the electrically conductive polyaniline.
  • the amount of Lewis base used may vary widely and depends to a significant extent on the amount of dopant and
  • the amount of Lewis base is at least about 25 mole percent based on total moles of polymer repeat units.
  • the amount of Lewis base is at least about 50 mole percent based on the total moles of polymer repeat units, and in the more preferred embodiments of the invention, the amount of Lewis base is more than 100 mole percent based on the total moles of polymer repeat units.
  • the upper limit to the amount of Lewis base is not critical but excess Lewis base will function in part as a solvent or plasticizer for the Lewis-base/dopant complex and the polyaniline, and the solubility parameters of the excess base must be taken in combination with those of any additional solvents.
  • the third component of the solution of this invention is a polar organic or inorganic solvent which is capable of dissolving neutral polyaniline and the Lewis-base/acid-dopant complex to form the solution of this invention.
  • a polar organic or inorganic solvent is a solvent which has a relative dielectric constant of equal to or greater than about 5, and a dipole moment equal to or greater than about 3.5 ⁇ 10 -30 Cm.
  • Preferred solvents are those solvents with dielectric constants equal to or greater than about 6 and dipole moments equal to or greater than about 5 ⁇ 10 -30 Cm.
  • Preferred solvents have a relatively strong hydrogen bonding capability.
  • the degree of hydrogen bonding capability can be assessed by a variety of techniques.
  • One method which we find to be most predictive of suitable solvents for the present invention is that Craver, J. Appl. Polvm Sci. 14. 1755 (1970). This method is based upon the relative sound velocity (g w ) in paper wetted by the solvent, where water is arbitrarily assigned a value of 100.
  • suitable solvents are those which have a hydrogen bonding capability greater than about 50, and more preferably greater than about 60.
  • Suitable solvents are the solubility parameter of the liquid, also referred to as the Hildebrand Parameter (d) .
  • Preferred solvents have a Hildebrand Parameter which lies in the range of from about 17 to about 29, more preferably in the range of from about 18 to about 26, and most preferably in the range of from about 19 to about 25.
  • r [4(17.4-d d ) 2 + (8.5-d p ) 2 + (10.4 -d h ) 2 ]
  • d d , d p and d h are the Hansen Parameters for a prospective solvent for polyaniline base, then suitable solvents are those for which r is less than about 7, more preferably less than about 6, and most preferably less than about 5 MPa.
  • Solvents for use in the practice of this invention are volatile.
  • a "volatile" solvent is a liquid which has a boiling point of equal to or less than about 300oC under use condition, preferably at atmospheric or autogenous pressure.
  • the lower limit to the boiling point is not critical provided that the solvent is in the liquid state under use conditions.
  • the boiling point of the solvent is less than about 250°C.
  • Particularly preferred solvents have boiling points of less than about 200°C. More preferred solvents have boiling points of less than about 150°C and most preferred solvents have boiling points of from about 40°C to about 100oC.
  • alkanesulfonates such as methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate; nitriles such as acetonitrile,
  • propionitrile, butyronitrile, benzonitrile, and the like aromatic solvents such as nitrobenzene, benzene, toluene and the like; carbonates such as propylene carbonate, dimethyl carbonate, ethylene carbonate and the like; nitroalkanes such as nitromethane,
  • amides such as dimethyl formamide, dimethyl thioformamide, diethyl formamide, N,N-dimethylacetamide,
  • organophosphorus compounds such as hexamethyl phosphoramide, diethylphosphate, triethylphosphite, trimethyphosphate and the like; glycols such as
  • amines such as pyrrolidine, piperidine, morpholine, ethylamine, benzylamine, butylamine, propylamine, ethylenediamine, propylene diamine, piperazine, pyridine, indoline, picoline, toluidine, quinoline, aniline and the like; and other organonitrogen compounds such as
  • Mixtures of such organic solvents can also be used as for example mixtures of N-methyl pyrrolidinone and pyrrolidine or tetrahydrofuran and
  • 2- (ethylamino) ethanol When employing mixtures of organic solvents or an excess of the Lewis base, an average set of Hansen Parameters can be calculated using the techniques of matrix algebra. Suitable solvent mixtures are then preferably those whose average values of d d , d p , and d h lead to a value of r which is less than about 7 MPa.
  • the solutions of this invention can include other optional ingredients which either dissolve or do not dissolve in the solution.
  • optional ingredients can vary widely, and include those materials which are known to those of skill in the art for inclusion in polymer articles.
  • materials may be present which alter the physical or mechanical properties of either the solution or the articles eventually cast from the solution.
  • examples of such materials include salts such as, for example, LiCl, LiBr, LiCF 3 SO 3 , KCF 3 (CF 2 ) 2 SO 3 , and the like which may be included to provide dopant counterions for the polyaniline or which may improve the solubility of the polyaniline or other additional conventional polymers.
  • These other conventional polymers which may be present include, for example, polycarbonate, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride,
  • polyethylene oxide polystyrene, nylon, cellulose poly(1,4-cyclohexylidene dimethylene terephthalate), poly(phenylene sulfide), poly(ethylene terephthalate), poly(4-aminobutyric acid), poly(hexamethylene
  • nonsoluble fourth components materials may be present which either fill or form a substrate for the
  • conductive polymer cast from the solution include other conductive polymers, such as conjugated backbone polymers as for example poly(phenylene sulfide), polyacetylene, polyphenylene, polythiophene and the like which may become conductive upon doping, graphite, carbon blacks, metal conductors, reinforcing fibers and inert fillers (such as clays and glass).
  • conjugated backbone polymers such as poly(phenylene sulfide), polyacetylene, polyphenylene, polythiophene and the like which may become conductive upon doping, graphite, carbon blacks, metal conductors, reinforcing fibers and inert fillers (such as clays and glass).
  • the proportion of polymer and solvent in the solution or plasticized composition of this invention containing the substituted or unsubstituted polyaniline homopolymer or copolymer, the Lewis base/dopant complex and the organic solvent are not critical and can vary widely, such that the composition varies from a
  • the amount of solvent as a proportion of the amount of solution is not believed to be critical, since any amount as a liquid will form at least a viscous gel or a plasticized composition with the polymer.
  • the solvent is present in
  • the method of forming the solutions or plasticized compositions of this invention is not critical and can vary widely.
  • one preferred method of forming the present composition or solution containing the substituted or unsubstituted polyaniline is to add the polyaniline doped with a suitable dopant such as toluene sulfonic acid and a suitable Lewis base such as piperdine or pyrrolidine to a suitable solvent such as N-methyl pyrrolidone in a mixing vessel. All or a portion of the Lewis base complexes with the acid dopant of the conductive polyaniline forming the Lewis base/acid complex and neutral undoped polyaniline base. The complex and the neutral polyaniline then dissolve in the liquid.
  • a suitable dopant such as toluene sulfonic acid and a suitable Lewis base such as piperdine or pyrrolidine
  • a suitable solvent such as N-methyl pyrrolidone
  • to complex means to form an association or ionic bond such as a conjugate acid base pair between the Lewis base and the dopant for the electrically conductive polyaniline.
  • the solution or plasticized composition can be placed in the desired configuration. As the liquid and the Lewis base are removed, the complex decomposes
  • Another preferred method is to react,
  • a acid dopant such as toluene sulfonic acid, dodecyl benzene sulfonic acid or naphthalene disulfonic acid as a solid into a mixing vessel
  • undoped polyaniline in the leuco form of Formula IV can be added to a suitable mixing vessel with a suitable solvent such as N-methylpyrrolidone, a suitable Lewis base such as pyrrolidine or piperidine and a suitable oxidizing dopant such as NOSbF 6 , FeCl 3 or mixture of an acid and oxygen and an oxidizing agent such as toluenesulfonic acid and oxygen to form the solution or composition of this invention from which the conductive polyaniline can be cast.
  • a suitable solvent such as N-methylpyrrolidone
  • a suitable Lewis base such as pyrrolidine or piperidine
  • a suitable oxidizing dopant such as NOSbF 6 , FeCl 3 or mixture of an acid and oxygen and an oxidizing agent such as toluenesulfonic acid and oxygen
  • An alternate technique of preparing the solution of this invention containing the doped polymer is to mix first the polyaniline, the Lewis base and the solvent, thereafter add the dopant to the solution, if the dopant is soluble in the solvent, or to form a two phase system if the dopant is insoluble.
  • a soluble solvent such as N-methylpyrrolidone and a Lewis base such as propylamine, morpholine or pyrrolidine
  • a suitable dopant to this suspension such as toluene sulfonic acid, causes the Lewis base and the dopant to complex. Even if the dopant is insoluble in the solvent, it will still go into the solution, provided that the complexed dopant and base is soluble in the solvent.
  • the Lewis base and the solvent can be removed from the solution through use of any conventional solvent removal method but is removed preferably by evaporation to form a conductive polyaniline.
  • the Lewis base solvent can be removed by extraction with an extractant in which the Lewis base and the solvent are substantially more soluble than the doped polymer.
  • films of any desired thickness can be prepared. Extremely thin films can be prepared which are substantially
  • the doped polymer will form around, or be filled with, the insoluble material. If, for example, the additional components are glass fibers, depending on the relative amounts of fibers and doped polymer, the removal of the solvent will cause either the
  • polymer to be fiber-filled, or the fibers to be polymer coated or impregnated, or some intermediate composite of fibers and doped polymer to be formed In the case of systems wherein the amount of non-soluble component greatly exceeds the doped polymer remaining, individual particles or shapes of non-soluble components coated or impregnated with doped polymer will be formed.
  • Examples of articles formed from non-soluble components and the present polymer solutions include conductive polymer coated-housings for sensitive electronic equipment (microprocessors), infrared and microwave absorbing shields, flexible electrical conducting connectors, conductive bearings, brushes and semiconducting photoconductor junctions, antistatic materials for packaging electronic components, carpet fibers, tiles, or waxes for floors in computer rooms and antistatic spray finishers for plastics, and thin, optically transparent antistatic finishes for CRT screens, aircraft, auto windows and the like.
  • sensitive electronic equipment microprocessors
  • infrared and microwave absorbing shields flexible electrical conducting connectors
  • conductive bearings brushes and semiconducting photoconductor junctions
  • antistatic materials for packaging electronic components, carpet fibers, tiles, or waxes for floors in computer rooms and antistatic spray finishers for plastics, and thin, optically transparent antistatic finishes for CRT screens, aircraft, auto windows and the like.
  • a third application for the present polymer solutions is in the doping of other materials, and especially other conjugated backbone polymers which could also be doped by the electron-acceptor dopant alone. Such doping may occur as a part of the process of casting the polymer solution onto the second polymer article, but may also be accomplished without,
  • the conductivity of the dried and pressed pellet formed from this material was 1 Scm -1 as measured by the co-linear four-probe method.
  • the conductivity of the moisture-saturated pellet was 20 Scm -1 .
  • Poly(anilinium tosylate) (13g) obtained from Example 1 was suspended in 270ml of fuming sulfuric acid and stirred for 10 hrs. The resultant solution was then added dropwise to 2700 ml of methanol to precipitate the sulfonated polyaniline. The resultant sulfonated-polyaniline was collected by filtration, washed with 4 L of methanol, and then dried under dynamic vacuum for 15 hrs. The yield was 11g. The conductivity of a pellet formed from this material was measured (by a co-linear four-probe method) and was 0.05-0.1 Scm -1 . Elemental analysis gave:
  • polyaniline/amine complexes is greatly affected by the amines used for complexation.
  • the sulfonated-polyaniline is
  • FIG. 1 shows ultraviolet-visible-near infrared (UV-VIS-NIR) spectra of three different amine-complexed sulfonated-polyanilines (triethylamine, tripropylamine, tributylamine). Although these three samples have different dissolution characteristics (see Tables 1 and 2), they showed no differences in their UV-VIS-NIR absorption characteristics in methanol. Figure 2 shows that solvents also had little effect on the spectra.
  • UV-VIS-NIR ultraviolet-visible-near infrared
  • Example 3 The solutions prepared in Example 3 can be used to prepare sulfonated polyaniline coatings on plastic films.
  • the initially coated film was originally blue and non-conductive and was made conductive by
  • the color of the coated film turned more and more green, with a continued
  • UV-VIS-NIR spectroscopy was found to be a very useful analytical tool for characterization of the sulfonated-polyaniline coating prepared from the tripropylamine-complexed form and evaporated at room temperature. The spectrum is recorded in Figure 3.
  • Poly(anilinium tosylate) prepared in Example 1 was suspended in N-methylpyrrolidone (NMP) as an insoluble green powder.
  • NMP N-methylpyrrolidone
  • An equivalent amount of tripropylamine was then added as a complexation agent for the dopant (i.e. toluene sulfonic acid) .
  • the green solid turned blue as soon as the amine was added, and then became soluble, giving a deep blue particle-free solution.
  • the intrinsic viscosity of the polyaniline in the solution was 0.53 dl/g which was comparable to that obtained for this polymer in a concentrated sulfuric acid solution (0.55 dl/g). This result indicated that the above poly(anilinium tosylate) solution was a true solution.
  • Poly(anilinium tosylate) (2g) obtained in Example 1 was dissolved in 150 ml of N-methylpyrrolidone (NMP) containing 2 ml of tripropylamine (NPr 3 ).
  • NMP N-methylpyrrolidone
  • NPr 3 tripropylamine
  • the conductivity of this film can be further increased by either heating or re-doping to accelerate the removal of the complexed amine.
  • the conductivity was 0.56 Scm -1 after re-doping for 2 days with a 20 wt% toluene sulfonic acid aqueous solution.
  • NMP N-methyl pyrrolidone
  • NPr 3 tri-n-propyl amine
  • Poly(anilinium methanesulfonate), poly(anilinium benzene disulfonate), poly(anilinium polystyrene sulfonate) were prepared from poly(anilinium tosylate) by anion exchange with aqueous solutions of methane sulfonic acid, poly(styrene sulfonic acid) and
  • NMP NMP/NPr 3 poly(anilinium tosylate) I VS poly(anilinium dihydrogen phosphate) I S poly(anilinium-trifluoromethanesulfonate I S poly(anilinium methanesulfonate) I VS poly(anilinium benzenedisulfonate) I VS poly(anilinium polystyrenesulfonate) I S poly(anilinium chloride) I S
  • tosylate can be prepared by dissolving 3.75 g of poly(anilinium tosylate) obtained in Example 1 in a solvent mixture containing 35 ml of N-methylpyrrolidone and 3.3 ml of tripropylamine. The resultant blue solution is then heated at 100°C for half an hour. A viscous gel was formed after the solution was cooled to room temperature. By drawing this conducting polymer gel, a green, conductive, polymer fiber was obtained after the amine was removed by evaporation.
  • This conducting polymer gel will also be useful for making other conducting polymer articles such as, conductive molded articles, compression molded sheets, and the like.
  • polyaniline will be those whose own solubility
  • Example 1 and then undoped (neutralized) by treatment with an aqueous solution of sodium carbonate. Solvents which were demonstrated to dissolve undoped polyaniline are shown in Table 4 below and in Figure 4.
  • the polymer is characterized as having a "solubility sphere" in a three dimensional space defined by the coordinates d d , d p , d h .
  • the center point of the solubility sphere is (d , d ,d' p ,d , h ) and the radius of the sphere is R.
  • the polymer should be soluble in a given solvent when r ⁇ R.
  • Hansen Method with Polyaniline and Various Solvents (1) The following values of the Hansen Parameters (all in units of MPa ) were determined for polyaniline by sampling Hansen Space (i.e., the range of possible values for d d , d p and d h ) with the series of solvents in Table 5.
  • Table 5 sets forth the Hansen Parameters of various liquids which have been shown to be solvents for unsubstituted and undoped polyaniline base.
  • N-methylpyrrolidone 16.5 10.4 13.5 4.1
  • NMP N-methylpyrrolidone
  • N-methylpyrrolidone is predicted and was found to be a solvent.
  • Example 10 in Figure 5.
  • the majority of non-solvents in Table 6 have as expected, r>R (R_6 from Example 10); however, there are also a few exceptions.
  • Example 1 The experiments were conducted by mixing 2 mg of poly(anilinium tosylate) with 1 ml of amine. The results are set forth in the following Table 7.
  • Example 1 and dissolved as in Example 12.

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