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 a process for forming an electrically conductive solution comprising a solvent or solvent mixture and a solution phase of one or more electrically conductive conjugated backbone polymers doped with one or more dopants.
• This invention also relates to the electrically conductive solution
• This invention relates to an electrically
• conductive solution comprising a solvent and an electrically conductive conjugated backbone polymer doped with a dopant, wherein said dopant is selected such that solubility parameter of said doped conjugated backbone polymer is such that the doped conjugated backbone polymer is soluble in said solvent.
• This invention also relates to a process of forming an electrically conductive solution of conductive conjugated backbone polymer doped with a dopant in a solvent or solvent mixture by modifying the solubility characteristics of the conjugated backbone polymer through the dopant such that the solubility parameter of said solvent and said doped polymer are such that said polymer dissolves in said solvent to form said electrically conductive solution, and to a method of using the solution to form an article of manufacture by removing to solvent from the solution solidifying said electrically conductive conjugated backbone polymer in the desired configuration.
• the solution of this invention comprises two essential ingredients a solvent and an electrically conductive conjugated backbone polymer doped with a dopant so that the solubility parameters of the solvent and the doped electrically conductive conjugated are such that the desire amount of doped electrically conductive conjugated backbone polymer dissolves in the solvent to form the electrically conductive solution.
• a “solution” is a real solution or an ultrafine dispersion having an average particle size of less than about 100 nanometer. Solvents useful in the practice of this invention may vary widely. The only requirement is that the solvent is capable of dissolving the required quantity electrically
• Preferred solvents have dielectric constants measured at room temperature (i.e. 10-30°C) equal to or greater than 2.2.
• Illustrative of such useful solvents are water; dimethylsulfoxide; amides such as formamide, acetamide, N,N-dimethyl formamide, N,N-dimethyl acetamide,
• alcohols and glycols such as methanol, ethanol,
• amines such as methylamine, dimethylamine, dipropylamine,
• nitro compounds of aliphatic and aromatic hydrocarbons such as nitromethane, nitroethane, nitrobenzene, nitrotoluene, nitroaniline, tetranitromethane, and the like; halogenated aliphatic and aromatic hydrocarbons such as methylene chloride, chloroform, chloromethane, dibromoethylene, trichloroethane, chlorobenzene, o-difluorobenzene, bromotoluene and the like; esters such as methyl formate, ethyl acetate, ethyl
• acetoacetate methyl benzoate, benzyl acetate, ethyl oleate, butyl stearate, methyl salicylate, dimethyl phthalate, and the like; ethers such as methyl ether, ethyl ether, phenyl ether, tetrahydrofuran,
• phosphates such as
• tricresyl phosphate and the like; and silicates such as tetraethylsilicate, and the like; More preferred solvents are those having a relative dielectric
• dielectric constant equal to or greater than about 4.0, such as amides, acids, dimethyl sulfoxide, amines, and alcohols.
• the most preferred solvent is an amide, such as substituted or unsubstituted pyrrolidinone.
• conjugated backbone polymer is a polyunsaturated polymer containing conjugated unsaturation bond systems along the polymer backbone.
• conjugated backbone polymers are poly(unsaturated) polymers such as
• substituted or unsubstituted poly(heteroaromatics) such as polythiophenes, poly(furans) polypyrroles, polyquinolines, polyisothianaphthenes, polycarbazoles, poly(alkyl thiophenes) and the like; substituted or unsubstituted poly(aromatics) such as polyphenylene sulfides, polyanilines, polyphenylenes,
• poly(heteroaromatic vinylenes) such as poly(thienylene vinylene)
• Preferred conjugated backbone homopolymer or copolymers are substituted or unsubstituted
• polyanilines poly(heterocycles), and aromatic or heteroaromatic vinylenes.
• poly(heterocycles), and aromatic or heteroaromatic vinylenes are those
• n, o and p are the same or different and are integers at least about 20, with the proviso that at least one of n or o is greater than zero;
• q is an integer which can range from 0 to about 4;
• R' 12 , R' 13 and R' 14 are the same or different at each occurrence and are hydrogen or isotopes thereof, hydroxyl, alkyl, alkenyl, aryl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy,
• R, 16 is alkyl having from 1 to about 20 carbon atoms
• r is a natural number from 1 to about 50;
• R' 1 and R' 2 , or R' 3 and R' 4 , or R' 5 and R' 6 , or R' 7 and R' 8 , or R' 9 and R' 10 , or R' 11 and R' 12 or R' 13 and R' 14 substituents taken together may form an alkylene, alkenylene, or alkynylene group completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic or alicyclic carbon ring, which ring may optionally include one or more degrees of unsaturation or one or more heteroatoms of nitrogen, sulfur, phosphorus, selenium, sulfinyl, sulfonyl or oxygen; and
• X 1 and X 2 are the same or different and are S, O, Se, NR' 17 , or P R' 17 , wherein R' 17 is hydrogen,
• alkylaryl arylalkyl, alkyl or R 1 .
• R' 7 , R' 8 , R' 9 , R' 10 , R' 11 , R' 12 , R' 13 and R' 14 groups are hydrogen; hydroxyl; cyano; nitro; halo; alkyl such as methyl, ethyl, butyl, pentyl, octyl, nonyl,
• tert-butyl neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as l-propenyl, 4-butenyl, 1-pentenyl, 6-hexenyl, 1-heptenyl, 8-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy,
• alkanoyl such as butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the like
• arylamino and diarylamino such as phenylamino, diphenylamino and the like
• alkylsulfinyl, alkyIsulfonyl, alkylthio, arylsulfonyl, arylthio, and the like such as
• alkoxycarbonyl such as methoxycarbonyl
• alkyl amino and dialkylamino such as dimethylamino
• cycloalkyl such as cyclohexyl, cyclopentyl, cyclooctyl, cycloheptanyl and the like
• alkoxyalkyl such as methoxymethylene, ethoxymethylene, butoxymethylene, propoxyethylene, pentoxybutylene and the like
• arylalkylamino such as methylphenylamino, ethylphenylamino and the like
• aryloxyaryl such as phenoxyphenylene, phenoxymethylene and the like; and various substituted alkyl and aryl groups such as 1-hydroxybutyl, 1-aminobutyl,
• R' 1 to R' 14 groups are moieties of the formula:
• R' 15 groups include divalent moieties of the formulas -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 - and -(CH 2 CH(CH 3 ))-, and useful
• R' 16 , groups include -CH 3 , -CH 2 CH 3 and -(CH 2 ) 8 CH 3 .
• R' 15 and R' 16 are ethyleneglycol monomethylether, diethylene glycol monomethylether, triethylene glycol monomethylether, tetraethylene glycol, monomethylether, and the like.
• R' 17 groups are hydrogen, methyl, ethyl, propyl, hexyl, octyl, nonyl, phenyl, benzyl, vinyl, allyl, dodecylphenyl, phenethyl, phenylpropyl, 2,4-dimethylphenyl, 4-methylphenyl and the like.
• Polymers for use in the practice of this invention may vary widely, the only requirement is that they are comprised of conjugated backbone polymers. Polymers with oxidation potentials less than about 3.5V vs
• Li/Li + are more preferred for use in the practice of this invention.
• preferred for use in the practice of this invention are homopolymers, and random or block copolymers of the above Formulas I to XIV in which:
• n, o and p are natural numbers at least about 40, preferably at least about 50, with the proviso that at least one of n or o is not zero;
• q is an integer from 0 to about 4;
• R' 1 , R' 2 , R' 3 and R' 4 are the same or different at each occurrence and are hydrogen or hydroxyl or alkyl having from 1 to about 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; phenyl;
• alkylphenyl such as 2,4-dimethylphenyl, 4-methylphenyl, 4-ethylphenyl, and 4-butylphenyl; phenylalkyl such as benzyl, phenethyl; alkxoy having from 1 to about 12 carbon atoms such as methoxy, ethoxy, and propoxy;
• alkanoyl having from 1 to 20 carbon atoms such as formyl, acetyl, and propionyl
• alkylthio having from 1 to 20 carbon atoms such as methylthio, ethylthio, propylthio, dodecylthio and butylthio
• alkoxyalkyl having from 1 to 20 carbon atoms such methoxymethyl, ethoxyethyl and heptoxypropyl
• alkenyl having from 1 to about 20 carbon atoms such as allyl, vinyl and
• phosphonic acid and derivatives thereof cyano, nitro, epoxy, hydroxyl, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like; or halo substituents such as trifluoromethyl, 3,4-epoxybutyl, cyanomethyl,
• R' 15 is divalent alkylene having from 1 to about 4 carbon atoms
• R' 16 is alkyl having from 1 to about 10 carbon atoms
• r is a natural number from 1 to about 25 such as ethylene glycol monomethylether and the like; or any of R' 1 and R' 2 , or R' 3 and R' 4 , substituents taken together may form an alkylene, alkenylene or alkynylene chain having from 2 to 20 carbon atoms completing a 4, 5, 6, 7, 8, 9 or 10 membered ring system(s) which may include one or more degrees of unsaturation or one or more heteroatoms of oxygen, nitrogen or sulfur such as
• R' 5 to R' 14 are the same or different at each occurrence and are hydrogen, hydroxyl, alkyl having from 1 to about 12 carbon atoms, phenyl, alkylthio having from 1 to about 12 carbon atom or alkoxy having from 1 to about 12 carbon atoms; alkoxyalkyl having from 2 to about 12 carbon atoms; alkylamino having about 1 to about 12 carbon atoms alkyl; or phenyl substituted with hydroxyl, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts.
• acid functional groups such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts.
• esters, and the like cyano, nitro, epoxy, or halo substituents or any of R' 5 and R' 6 , or R' 7 and R' 8 , or R' 9 and R' 10 , or R' 11 and R' 12 or R' 13 and R' 14
• alkynylene or alkylene chain having 2 to about 20 carbon atoms completing a 4, 5, 6, 7, 8, 9 or 10 membered ring system(s) which may include one or more degrees of unsaturation or one or more heteroatoms of oxygen, sulfur, or nitrogen such as 1,4-butandiyl, 1,2-ethanediyl, -CH 2 SCH 2 - or -CH 2 OCH 2 -; and
• X 1 and X 2 are the same or different and are oxygen, sulfur or NR 17 wherein R' 17 is hydrogen or alkyl or aryl.
• q is an integer from 0 to about 3;
• n, o and p are at least about 100 with the proviso that at least one of n or o is not zero;
• R' 1 , R' 2 , R' 3 and R' 4 are the same or different at each occurrence and are hydrogen; hydroxyl; alkyl having from 1 to about 12 carbon atoms such as ethyl, methyl, propyl, n-butyl, sec-butyl, n-hexyl, n-octyl, and n-dodecyl; phenyl; alkoxy or alkylthio having from 1 to about 12 carbon atoms such as methylthio,
• R 15 is alkylene of about 2 to 3 carbon atoms
• R 16 is alkyl of from 1 to about 10 carbon atoms
• r is a natural number from 1 to about 10;
• R' 5 , R' 6 , R' 7 , R' 8 , R' 9 , R' 10 , R' 11 , R' 12 , R' 13 and R' 14 are the same or different at each occurrence and are hydrogen; hydroxyl; alkyl, such as methyl, ethyl or the like; substituted alkyl such as butylsulfonic acid, propylsulfonic acid, cyanomethyl, epoxybutyl,
• R' 10 , or R' 11 and R' 12 , or R' 13 and R' 14 together may be an alkenylene or alkylene chain forming an alicyclic, aromatic or heteroaromatic ring;
• X 1 and X 2 are the same or different and are oxygen, sulfur or -NR' 17 where R' 17 is hydrogen or alkyl having from 1 to about 10 carbon atoms.
• q is an integer from 0 to about 2;
• n, o and p are at least about 125 with the proviso that at least one of n or o is not zero;
• R' 1 to R' 4 are the same or different at each occurrence and are hydrogen, or alkyl, alkoxy or alkoxyalkyl having 1 to about 12 carbon atoms or a moiety of the formula:
• R' 15 is -(CH 2 ) 2 - or -(CH 2 CH(CH 3 ))-;
• R'16 is -CH 3 or -CH 2 CH 3 ;
• r is a natural number 1 to about 6;
• R' 14 are the same or different at each occurrence and are hydrogen, hydroxyl, alkyl, or any of R' 5 and R' 6 , R' 7 and R' 8 , R' 9 and R'10, or R' 11 and R' 12 , or R'13 and R'14 together may form a divalent alkylene or alkenylene chain forming an alicyclic, aromatic and/or heteroaromatic ring; and
• X 1 and X 2 are sulfur or NR'17 where R ' 17 is hydrogen or alkyl having from 1 to about 7 carbon atoms.
• Still other preferred electrically conductive polymers are polyanilines. As used herein,
• polyanilines are homopolymers or copolymers in which at least 50 mole % of the recurring backbone monomeric units in vary ratio are selected from the group
• neutral or undoped polyaniline is characterized by an uncharged backbone
• polyaniline base is a particular form of undoped polyaniline which contains at least one quinoid diimine linkage in the backbone and "electrically conductive or doped polyaniline” is characterized by a charged backbone which may be formed by a partial or complete protonation of the amine and/or imine nitrogen atoms.
• polyanilines for use in the invention are homopolymers and copolymers 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 and with the further proviso that at least one position on the aniline ring, preferably at the para position, is substituted with a substituent which will allow coupling of the aniline units, such halogen, hydrogen or other leaving group;
• R 1 is the same or different at each occurrence and is selected from the group consisting of alkyl
• alkylaryl arylalkyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, aryl,
• alkylsulfinyl aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, alkylsulfonyl, arylthio,
• alkylsulfonylalkyl arylsulfinyl, alkoxycarbonyl, arylsulfonyl, halo, hydroxy, cyano, acid functional groups, such as sulfonic acid, carboxylic acid,
• alkylsilane or any of the foregoing aryl, aliphatic or cycloaliphatic groups substituted with one or more acid functional groups, such as sulfonic acid,
• substituents are one or more acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like; halo, nitro, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, cyano or epoxy moieties ; or R 1 is an aliphatic moiety having repeat units of the formula:
• R 2 is selected from the group consisting of permissible R 1 substituents and hydrogen.
• R 1 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 amino; alkylamino, such as methylamino, ethylamino, butylamino and the like; dialkylamino, such as dimethylamino,
• arylamino such as phenylamino, p-methylphenylamino and the like;
• diarylamino such as diphenylamino
• alkylarylamino such as 2-phenyl-4-methylamino and the like; alkylsulfinyl, alkylsulfonyl, alkylthio,
• arylthio arylsulfinyl, and arylsulfonyl such as butylthio, neopentylthio, methylsulfinyl,
• alkoxycarbonyl such as methoxycarbonyl
• cycloalkyl such as cyclohexyl, cyclopentyl, cyclo-octyl,
• alkoxyalkyl such as
• sulfonic acid such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like: such as ethylsulfonic acid, propylsulfonic acid, 4-nitrobenzene sulfonic acid, butylsulfonic acid, phenylsulfonic acid, and the like.
• R 1 groups are divalent moieties derived from any two R 1 groups or a R 1 group with a R 2 group such as moieties having from about 2 to about 7 repeat units of the formula:
• R 3 groups are divalent alkenylene chains
• R 2 groups are hydrogen and the above-referenced representative R 1 groups described above such as alkyl as for example, methyl, ethyl, isopropyl, butyl, isobutyl, hexyl, octyl and the like; alkylsulfonyl such as methylsulfonyl, ethylsufonyl, propylsulfonyl and the like; arylsulfonyl such as phenylsulfonyl, p-methyl phenylsulfonyl,
• Preferred polyanilines for use in the practice of this invention are those of the type derived from aniline of the above Formulas XV or is a derivative of said polyaniline, wherein:
• 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 1 is aryl, alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halo, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like: amino, alkylamino,
• alkylarylamino or alkyl, aryl or alkoxy substituted with one or more acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like; dialkylamino, arylamino,
• diarylamino, alkylarylamino, hydroxy, alkoxy, alkyl, and R 2 is the same or different at each occurrence and is a R 1 substituent or hydrogen.
• Particularly preferred polyanilines for use in the practice of this invention are those of the type derived from head to tail polymerization of anilines of the above Formula XV or derivatives of said
• n is an integer from 0 to 1;
• n and m are integers from 4 to 5, with the proviso that the sum of n and m is equal to 5;
• R 1 is aryl, alkyl or alkoxy having from 1 to about 20 carbon atoms, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like, halo, amino, alkylamino,
• phosphonic acid phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, and halo substituents;
• R 2 is the same or different at each occurrence and is a R 1 substituent or hydrogen.
• polyaniline consists of repeat units of the Formulas XVI and/or XVII:
• n, m, R 1 and R 2 are as described above;
• x and y are integers equal to or greater than 0, with the proviso that the sum of x and y is greater than 0, preferably were x is an integer equal to or greater than 0 and/or that the ratio of x to y is greater than or equal to about 0, more preferably said ratio is equal to or greater than 0.5 and most
• said ratio is equal to or greater than about 1; and Preferred for use in the practice of this
• n is an integer from 0 to about 3;
• n and m are integers from 1 to 4, with the proviso that the sum of n and m is equal to 4;
• R 1 is alkyl, aryl or alkoxy having from 1 to about 30 carbon atoms, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like, amino, alkylamino, dialkylamino, arylamino, diarylamino, hydroxyamino, hydroxy,
• carboxylic acid phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like;
• R 2 is the same or different at each occurrence and are hydrogen, acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like;
• 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 XVIII to XXI in which:
• n is an integer from 0 to 2;
• n and m are integer from 2 to 4, with the proviso that the sum of n and m is equal to 4 ;
• R 1 is alkyl, alkoxy, amino, alkylamino,
• R 1 substituents include from 1 to about 30 carbon atoms and the aryl components of any R 1 substituent include from 6 to about 30 carbon atoms;
• R 2 is the same or different at each occurrence and are hydrogen, alkyl, carboxylic acid, amino,
• alkylamino dialkylamino, arylamino, diarylamino, hydroxyamino, hydroxy, alkylsulfonyl, arylsulfonyl, or alkyl substituted with one or more acid functional groups, such as sulfonic acid, carboxylic acid, phosphonic acid, phosphoric acid, phosphinic acid, boric acid, sulfinic acid and the derivatives thereof, such as salts, esters, and the like; wherein the aliphatic components of any R 2 substituent include from 1 to about 30 carbon atoms and the aryl components of any R 2 substituent include from 6 to 30 carbon atoms; 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 1; and z is an integer equal to or greater than about 10.
• 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 1 is alkyl of from 1 to about 20 carbon atoms, carboxylic acid, carboxylate, sulfonic acid, sulfonate, sulfinic acid, sulfinic acid salt, phosphinic acid, phosphinic acid salt, or alkyl of from 1 to about 20 carbon atoms substituted with one or more halo,
• carboxylic acid carboxylate, sulfonic acid, sulfonate, sulfinic acid, sulfinic acid salt, phosphinic acid or phosphinic acid salt, phosphonic acid, phosphonic acid salt, substituents;
• R 2 is carboxylic acid, methyl, ethyl, carboxylate, carboxylic acid, sulfonic acid, sulfonate, sulfinic acid, phosphinic acid, phosphinic acid salt, sulfinate, phosphonic acid, phosphonic acid salt, salt or
• x is an integer equal to or greater than 2; and y is an integer equal to or greater than 1, with the proviso that the ratio of x to y is greater than 1;
• n is 0;
• n 4;
• x is an integer equal to or greater than 2;
• y is an integer equal to or greater than 1 with the proviso that the ratio of x to y is greater than 1;
• the polyaniline is derived from aniline or
• N-alkylaniline either unsubstituted or substituted with at least one sulfonate, sulfonic acid, alkyl or alkoxy.
• Polyaniline derived from unsubstituted aniline is the polyaniline of choice.
• the number of repeat units in the conjugated backbone homopolymer or copolymer is not critical and may vary widely. The greater the number of the greater the viscosity and molecular weight of the conjugated backbone homopolymer or copolymer. In those applications where a conjugated backbone
• the number of repeat units is at least about 10.
• the upper limit can vary widely depending on the desired molecular weight and viscosity and the required degree of processibility, such as melt processibility, solution processibility and the like.
• the number of repeat units is at least about 20, and in the particularly preferred embodiments, the number of repeat units is at least about 30.
• Conjugated backbone homopolymer and copolymers can be conveniently prepared through conventional
• preferred polyanilines can be prepared through use of chemical and electrochemical synthetic
• polyaniline can be prepared by treating aniline with ammonium
• 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 conjugated backbone homopolymer or copolymer is doped with a suitable dopant to render the polymer electrically conductive, i.e. an electrical
• the conjugated backbone homopolymer or copolymer is best doped by contacting the dopant with the polymer for a time sufficient to doped in the desired extent.
• the polymer can be contacted with the dopant in the gaseous state, in the liquid state, neat, or diluted by some suitable diluent such as a gas as for example air, or liquid such as water, or an organic liquid.
• the dopant can be contacted with the conjugated backbone
• the conjugated backbone homopolymer or copolymer may be doped in either by carrying out the polymerization in the presence of an acid having a pKa in the solution equal to or less than that of the homopolymer or copolymer. In general, the higher the pKa of the conjugated backbone homopolymer or
• the pKa of the acid is preferably equal to or less than about 5, more preferably equal to or less than about 4, and the most preferably equal to or less than about 3.
• the conjugated backbone copolymer or homopolymer can be doped after polymerization.
• the conjugated backbone copolymer or homopolymer can be doped after polymerization.
• conjugated backbone homopolymer or copolymer layer is doped by contact with a solution of the dopant in a suitable solvent such as water.
• Dopants for use in the practice of this invention can vary widely.
• a dopant is a compound or compound mixture which is capable of doping said conjugated backbone polymer to render said polymer electrically conductive.
• Useful dopants may vary widely.
• Useful dopants may vary widely, in general, such dopant solute is derived from a compound, which upon addition to the conjugated backbone polymer, creates charge carriers (holes or free electrons) on the conjugated backbone polymer and renders the polymer conductive.
• Useful dopants include "oxidizing dopants" and "reducing dopants". As used herein an "oxidizing dopant" is a dopant which renders the conjugated
• an "reducing dopant” is a dopant which renders the conjugated backbone polymer with desired conductivity via a reduction step.
• Oxidizing dopants and reducing dopants are well known in the conductive polymer art, and any of such known oxidizing dopants and reducing dopants can be used.
• 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 semi-conductive
• Useful reducing dopants are alkali metals, such as Li, Na, K, Rb, Cs, Fr, and the mixture thereof;
• alkaline-earth metals such as Be, Mg, Ca, Sr, Ba, Ra, and the mixture thereof; the complexes formed between such alkali or alkaline-earth metals and some highly conjugated compounds, such as benzene, naphthalene, phenanthrene, anthracene, and other polynuclear
• inventions are the complexes formed between alkali or alkaline metals and some highly conjugated compounds, such as naththalene.
• 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 , PCl 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 ions 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 -, ClO 4 -, OTs-, SO 3 -2 , C 6 H 5 CO 2 -, CH 3 SO 3 -, FSO 3 -, and FeCl 4 -.
• dopant ions 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 -, ClO 4 -
• Preferred oxidizing dopants for use in the practice of this invention are oxidizing dopants selected from the group consisting of MoOCl 4 , MoCl 5 , PCl 5 , POCl 3 , 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 consisting of MoOCl 4 , MoCl 5 , PCl 5 , POCl 3 , 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 , PCl 5 , POCl 3 , FeBr 3 and FeCl 3 .
• most preferred oxidizing dopants are those embodiments in which the oxidizing dopant is FeCl 3 .
• Such dopants include inorganic acid, hydrofluoric acid, hydroiodic acid, phosphoric acid, nitric acid, iodic acid, sulfuric acid and the like.
• R 4 and R 6 are the same or different at each
• M is a species having a positive charge equal to s, provided that at least one of M +s is a proton or a moiety which can be transformed by radiation, heat, chemicals and the like into a proton under use
• s is the same or different at each occurrence and is an integer equal to 1 to 8;
• 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.
• R 4 and R 6 group may vary widely and can be a substituted or unsubstituted aliphatic radical such as alkyl, nitroalkyl, haloalkyl and the like, or a substituted or unsubstituted aromatic radical such as phenyl, halophenyl, nitrophenyl, anthracyl, naphthyl, phenanthryl and the like.
• R 4 and R 6 groups may also be a polymeric radical such as a polymer having recurring pendant phenyl groups in the polymeric backbone substituted with sulfonic acid and derivatives thereof such as salts and esters, phosphoric acid and
• phosphonic acid and derivatives thereof such as salts and esters, sulfinic acid and derivatives thereof such as salts and esters, carboxylic acid and derivatives thereof such as salts and esters, boric acid and derivatives thereof such as salts and esters, or phosphonic acid and derivatives thereof such as salts and esters; moieties such as sulfonated or phosphonated polystyrene, poly(2-methylstyrene),
• R 4 and R 6 are aromatic radical and in the most preferred embodiments R 4 and R 6 are substituted or unsubstituted phenyl or naphthyl.
• the nature of the M +s group may vary widely.
• M+s may be be a non-metal cation such as Bu 4 N + , H + , NO + , NO 2 + , NH 4 + , +N(CH 3 ) 2 H 2 , + N(C 2 H 5 )H 3 , Ph 3 S + 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.
• M +s is a cationic species having a positive charge s
• s is an integer equal to or greater than 1, preferably from 1 to about 8;
• R 4 and R 6 are organic radicals or amino, and r is an integer equal to or greater than 1, preferably from 1 to about 8;
• M is H + , or other metal or non-metal cation with the proviso that at least one of M is H + or a moiety which can be thermally or chemically transformed into a proton under use conditions, such as + NH 4 , + N(CH 3 ) 2 H 2 , + N(C 2 H 5 )H 3 , Ph 3 S + and the like
• t 0, 1, 2, 3 or 4;
• h 0, 1, 2, 3 or 4;
• i 0, 1, 2, 3 or 4;
• c 0, 1, 2, 3 or 4;
• d 0, 1, 2, 3 or 4;
• f 0, 1, 2, 3 or 4;
• R 4 and R 5 are the same or different at each
• sulfonate salt perhaloalkyl, phenyl, alkoxy, halo, cyano, amino, haloalkyl, hydroxy, sulfonic acid, phosphoric acid, phosphate salt, boric acid, sulfinate salt, phosphinate salt, sulfinic acid, borate salt, phosphinic acid, phosphonate salt, phosphonic acid, carboxylic acid, nitro, carboxylate salt and the like, or any two R 6 , or any two R 5 , or R 4 and any R 6
• substituents together may form an alkenylene chain completing a fused-ring system which chain may be unsubstituted or substituted with one or more halo, phosphoric acid, hydroxy, boric acid, nitro, cyano, amino, sulfinate salt, phosphinic acid, alkylamino, dialkylamino, phosphinate salt, arylamino, diarylamino, alkylarylamino, sulfinic acid, phosphate salt,
• carboxylate salt phosphonic acid, phosphonate salt, sulfonate salt, borate salt, sulfonic acid or
• R 4 or R 5 is a moiety of the formula:
• q is a positive whole number from 1 to about 10;
• R 6 is alkyl, aryl, aryloxy or alkoxy.
• useful dopants are acids and/or acid
• c 0, 1, 2 or 3;
• d, t, f, g, h and i are the same or different at each occurrence and are with the proviso that at least one of c, d, t, f or g, i or h is other than 0;
• e 0, 1 or 2;
• R 4 and R 5 are the same or different are hydroxy, amino, alkylamino, dialkylamino, arylamino,
• R 6 is alkyl, alkoxy, aryloxy or aryl
• M is H + , or other metal or non-metal cation, with the proviso that at least one of M is H + or a moiety which can be thermally or chemically transformed into a proton under use conditions.
• useful dopants are acids and/or acid derivatives of the formula: R 4 (PO 2 (R 5 )M) g (PO 3 M 2 ) f (SO 3 M) c (CO 2 M) d
• c, d, e, f and g are the same or different and are 0, 1 or 2, with the proviso that at least one of c, d, f and g is not 0;
• R 4 and R 5 are the same or different at each
• alkyl phenyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or alkyl substituted with one or more fluoro, sulfonic acid, sulfonate salt, alkoxy, carboxylate salt,
• substituents together may form an alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthrene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, phosphinic acid, phosphinate salt, phosphonic acid, phosphonate salt, fluoroalkyl, sulfonic acid, s
• R 6 is aryl, aryloxy, alkyl or alkoxy
• M is H + or other metal or non-metal cation, with the proviso that at least one of M is H + or is a moiety which can be thermally transformed into a proton under use conditions.
• useful dopants are acids or acid derivatives of the formula: R 4 (SO 3 M) c (CO 2 M) d
• c is 1, 2 or 3;
• d is 1, 2 or 2 with the proviso that at least one of c, d is not 0
• e 0, 1 or 2;
• R 4 and R 5 are th same or different at each
• anthracene or phenanthrene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, fluoroalkyl, sulfonic acid, sulfonate salt, carboxylic acid, phosphinic acid, phosphinate salts, carboxylate salt, hydroxy, nitro, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or cyano groups;
• M is H + or other metal or non-metal cation or a moiety which can be thermally tranformed into a proton under conditions.
• the dopant is a sulfonic acid or sulfonic acid derivative of the formula:
• c is 1, 2 or 3;
• e 0, 1 or 2;
• R 5 is alkyl or alkyl substituted with one or more fluoro groups, or any two R 5 groups together may form an alkenylene chain completing a naphthalene fused ring system which may be substituted with one or more sulfonic acid, sulfonic salt group or a combination thereof;
• M is a proton, or other metal or non-metal cation, with the proviso that at least one of M is proton.
• the dopant or dopant mixture should have a desired set of averaged solubility parameters which will modify, after coupling to said polymer via doping interaction, the solubility parameters of said doped conducting polymer to establish a relationship to the solubility parameters of said solvent or solvent mixture to render said conductive polymer soluble in said solvent or solvent mixture to the desired extent.
• the resultant solubility parameter of the doped conjugated backbone is equal to the volume fractional sum of the solubility parameters of the individual components (i. e. the neutral conjugated backbone polymer and the dopant or dopants), as expressed in the
• X i is the molar fraction of the i-th component
• V i is the molar volume of i-th component.
• the molar volume of the i-th component is equal to the ratio of the molecular weight of the i-th component to the density of the i-th component.
• solubilty parameters of the i-th component can also be calculated from the heat of vaporization of component i according to following equation:
• D i is the density of the i-th component
• M i is the molecular weight of the i-th component
• ⁇ H v i is the heat of vaporization of the i-th component which may be found in "Handbook of Physics and Chemistry";
• T is the temperature (in Kelvin) at which the measurement was conducted.
• R is ideal gas constant
• ⁇ E V i is the energy of vaporization of the i-th component
• V i is the molar volume of the i-th component
• ⁇ e j is the energy of evaporation contributed from the sub-group type j of the i-th component which can be found in the "Handbook of Solubility Parameters and Other Cohesion Parameters" (A.F.M. Barton, CRC Press, 1983);
• the solubility parameter of useful solvents can be determined by any suitable means. For example,
• solubility parameters can be obtained from suitable handbooks as for example the three handbooks mentioned hereinabove.
• the solubility parameter can also be determined through use of conventional methods as for example group contribution methods.
• the amount of dopant used in the practice of this invention can vary widely. Any amount of dopant can be used as long as the used amount renders a desired amount of conjugated backbone polymers soluble in the desired solvent or solvent mixture for conveniently performing the desired process.
• an amount of dopant is used to render from about 0.001 wt% to about 100 wt% of said conjugated backbone polymer soluble in said solvent or solvent mixture; more preferred from about 0.1 wt% to about 100 wt% of said conjugated polymer; particularly preferred from about 1 wt% to about 100 wt%; most preferred from about 10 wt% to about 100 wt %.
• concentration of the dissolved electrically conductive conjugated polymer in the desired solvent or solvent mixture is not critical. Any concentration can be used which is suitable for any processing techniques either known in the art or will developed in the future. In the preferred embodiments of this
• the concentration of said conjugated polymer in the solution is at least about 0.001 wt % based on the weight of said solution; more preferred is at least 0.01 wt%; particularly preferred is at least 0.1 wt %, and most preferred is at least 1 wt%.
• the solution of this invention can be formed through use of any suitable procedure, as for example by direct dissolution of the doped electrically
• the neutral conjugated backbone polymer can be dissolved (if soluble) or dispersed (if insoluble) in the desired solvent and then mix with the desired dopants or dopant solution of the same or different solvent or solvent mixture.
• the conjugated polymer can also be dissolved in a solvent other than the desired solvent and then mix with a solution of said desired dopant in the desired solvent.
• the conjugated polymer and the desired dopant can be first dissolved separately in a slovent different from the desired solvent and then mix to each other in the desired solvent.
• the conjugated polymer and the desired dopant can be dispersed
• Another aspect of this invention relates to a method of using the conductive solution for making conductive articles, such as films, fibers, foams, parts, paints, and inks.
• Methods for forming such conductive articles can vary widely. Any method known in the art may be used. For example, solution spinning and gel spinning techniques can be used for forming conductive fibers from the conductive solution of this invention. Spin coating, cast coating, doctor blades, transfer coating, graphic printing can be used for forming conductive films either free standing or on a substrate and coatings from the conductive solution of this invention.
• Conductive composites or blends can be prepared from the conductive solution of this invention by adding desired organic or inorganic fillers or binders into said conductive solution. This formed conductive blends or composite can then be processed further, using any processing method known in the art, into various conductive articles, such as conductive films, fibers, foams, parts, paints and inks.
• Useful fillers, binders or substrates may be formed of organic materials, inorganic materials, or a combination of such materials. Illustrative of useful inorganic fillers, binders or substrates are materials such as carbon black, graphite, mica, clay, glass, ceramics, SiO 2 , and the like. Useful organic fillers, binders and substrates include polymeric materials such as thermoset and thermoplastic polymers. Thermoset polymers for use in the practice of this invention may vary widely.
• thermoset polymers are alkyds derived from the esterification of a polybasic acid such as phthalic acid and a polyhydric alcohol such as glycol; allylics such as those produced by polymerization of dialkyl phthalate, dialkyl
• cycloaliphatic epoxies such as resins derived from reaction of substituted and unsubstituted phenols such as cresol and phenol with an aldehyde such as formaldehyde and acetaldehyde; polyesters;
• silicones and urethanes formed by reaction of a polyisocyanate such as 2,6-tolylene diisocyanate,
• 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate with a polyol such as polyether polyol (trimethylol propane, 1,2,6-hexanetriol, 2-methyl glycoside,
• polyester polyols such as those prepared by esterification of adipic acid, phthalic acid and like carboxylic acids with an excess of
• difunctional alcohols such as ethylene glycol
• diethylene glycol propanediols and butanediols.
• Thermoplastic polymers for use in the formulation of the composition of this invention may vary widely.
• Illustrative of such polymers are polyesters such as poly(pivaloyl lactone), poly(para-hydroxybenzoate), poly(ethylene oxybenzoate), poly(ethylene
• isophthalate poly(ethylene terephthalate)
• polyamides such as poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6), poly(11-aminoundecanoic acid) (nylon 11),
• poly(hexamethylene adipamide) nylon 6,6
• poly(p-phenylene terephthalamide) (Kevlar), and the like; polycarbonates such as poly[methane
• ⁇ , ⁇ -unsaturated monomers such as polyethylene
• polypropylene poly (4-methyl-1-pentene),
• polyisobutylene poly (isoprene)
• 1,2-poly(1,3-butadiene) polystyrene, poly(vinyl chloride), poly(vinylidene fluoride), poly(vinylidene chloride), poly(tetrafluoroethylene) (Teflon),
• polydienes such as poly(1,3-butadiene) and the like; polyoxides such as poly
• the non-conductive homopolymer or copolymer is a
• thermoplastic homopolymer or copolymer Preferred thermoplastic polymers are polyamides, polyesters, poly(carbonates), poly( ⁇ -olefins), poly(vinyl halides), polysulfones and acrylonitrile/butadiene/styrene terpolymer. More preferred thermoplastic homopolymer or copolymers are polyamides, polycarbonates, polyesters and poly( ⁇ -olefins), and most preferred thermoplastic polymers are poly(ethylene terephthalate), nylon-6, nylon-6,6, nylon-12, polyethylene, polypropylene and polystyrene.
• the electrically conductive solution of the invention, and the article of this invention formed from the solution can be used for any purpose for which conductive solutions and articles are useful.
• articles include conductive polymer housings for EMI Shielding of sensitive electronic equipment such as microprocessors; infrared, radio frequency and
• microwave absorbing shields flexible electrical conducting connectors; conductive bearings and brushes; semiconducting photoconductor junctions; electrodes; capacitors; optically transparent or non-transparent corrosion-preventing coatings for corrodible materials such as steel; antistatic materials and optically transparent or non-transparent coatings for packaging electronic components; carpet fibers; waxes for floors in computer rooms; antistatic finishes for CRT screens, aircraft, and auto windows; and the like.
• conducting coatings produced by the present process and solution such as in conducting plastic gas tanks; solar window coatings; transparent electrical elements for heated windows and heated liquid crystal displays;
• electrochromic displays electrical contacts for
• Specially useful coating of conducting polymers are those which are transparent in the visible spectral region.
• transparent in the visible region it is meant that at least 30% of the solar energy spectrum in the visible region is transmitted by the coating.
• aniline (0.54 mole) and 172g tosylic acid (0.90 mole) was added dropwise at 15°C a solution of ammonium persulfate (153.4g in 336.5 mL H 2 O) over a period of 40 minutes. The reaction was then allowed to continue at 15°C for 0.5 hour.
• the conductivity of the dried and pressed pellet was 1 Scm -1 as measured by the four in line probe method.
• moisture-saturated pellet was 20 Scm -1 by the four-in-line probe method.
• the yield was 78g.
• the intrinsic viscosity (in H 2 SO 4 at 25°C was 0. 66 dL/g.
• the elemental analysis were:
• Poly(anilinium tosylate) (50g) obtained in Example I was suspended in 500 mL H 2 O and stirred with 30g of sodium carbonate at ambient temperature for 20 hrs. The resulting solid was collected by filtration and rinsed with 2 L of deionized water. The filter cake was dispersed in 1.5 L of deionized water and stirred for 4 h to remove sodium carbonate residue. The solid was then re-collected by filtration and rinsed with 2 L of deionized water. The resulting filter cake was air-dried at 25°C for 20 h and then vacuum-dried at 80°C for 3 h.
• backbone polymer such as polyaniline
• a solvent such as N-methyl pyrrolidinone
• Example II Into a 2 dram vial was placed 0.1 g of the neutral polyaniline obtained in Example II. To the vial 2 mL of N-methyl pyrrolidinone was added. The neutral polyaniline dissolved to form a blue solution. Into this blue solution about 0.2 g of a selected acid dopant was added to doped the polyaniline in the solution. The doped polyaniline either remained dissolved in the solvent to form an electrically conductive solution, or precipitated out of the solvent, depending the acid dopant used. The results are summarized in the following Table I.

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