WO1991015534A1 - Electrically conductive poly(aromatic vinylenes) and poly(heteroaromatic vinylenes) - Google Patents

Electrically conductive poly(aromatic vinylenes) and poly(heteroaromatic vinylenes) Download PDF

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Publication number
WO1991015534A1
WO1991015534A1 PCT/US1991/002096 US9102096W WO9115534A1 WO 1991015534 A1 WO1991015534 A1 WO 1991015534A1 US 9102096 W US9102096 W US 9102096W WO 9115534 A1 WO9115534 A1 WO 9115534A1
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carbon atoms
acid
alkyl
poly
homopolymer
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PCT/US1991/002096
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French (fr)
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Chien-Chung Han
Ronald L. Elsenbaumer
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Allied-Signal Inc.
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Publication of WO1991015534A1 publication Critical patent/WO1991015534A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule

Definitions

  • This invention relates to novel electrically
  • poly(heteroaromatic vinylenes) in the conductive form Another aspect of this invention relates to methods of using the solutions and blends of this invention to form conducting polymer articles, including films, fibers, and coatings and methods of using such solutions as conducting liquids. Yet another aspect of this invention relates to novel process for preparing the poly(heteroaromatic vinylenes) and the poly(aromatic vinylenes) of this invention.
  • US Patent Nos. 4,321,114 and 4,442,187 are directed to conjugated polymers having conjugation in all or a part of at least one backbone chain thereof, such as polyacetylene, polyphenylene and poly(phenylene sulfide). It has recently been discovered that these conjugated backbone polymers can be chemically doped in a controlled manner with electron acceptor and/or electron donor dopants to produce electrically conducting polymers.
  • Lewis Acid halides having a liquid phase under atmospheric pressure for at least one temperature between -150°C and +100°C, such as arsenic trifluoride, phosphorus trifluoride, phosphorous pentafluoride, phosphorus trichloride, boron trifluoride and the like.
  • a few conductive species of polyalkylthiophenes are known, having been primarily prepared by electrochemical polymerization. Illustrative of such species are
  • poly(3-methylthiophene) is environmentally stable.
  • a conductive oligomeric species of poly(thiophene vinylenes), i.e., 6 to 8 repeat units are described in G. Kossmehl et al., Makromol Chem., 131, 15-54, 1970, and G. Kossmehl, Ber. Bunsenges Phys. Chem., 83, 417-426, 1979.
  • These oligomeric species of poly(thiophene vinylenes) exhibit several undesirable properties, which limit their utility in potential applications such as EMI shielding, and as anti-static materials. For example, the
  • processability are infuseable which essentially precludes melt processability, and exhibit low conductivities on oxidative doping (10 -2 ohm -1 cm -1 ) which essentially
  • n, o and p are the same or different and are selected such that m, or the sum of n, o and p is greater than about 20, with the proviso that at least one of n or o is not zero;
  • q is the same or different at each occurrence and is an integer which can range from 0 to about 4;
  • D is a leaving group, with the proviso that at least about 1 mole % of D leaving groups based on the total moles of D leaving groups is selected from the group consisting of neutral moieties which on elimination form the anion of a strong non-oxidizing organic or inorganic protonic acid having a pKa equal to or less than about 4 or a species which can be converted into the anion of such an acid such as -OR 1 , -R 1 OCO 2 -, F, Cl, Br, I,
  • -OSiR 1 R 2 R 3 and the like, or zwitterionic moieties which on elimination form the anion of such a strong non-oxidizing organic or inorganic acid, protonic acid having a pKa equal to or less than about 4, or a species which can be converted into such an anion such as - + NR 1 R 2 R 3 Z-, -P + R 1 R 2 R 3 Z-,
  • R 3 are the same or different and include groups such as hydrogen alkyl, phenyl, phenylalkyl, or alkylphenyl which may be unsubstituted or substituted with halogen, sulfonic acid or the like such as
  • anionic species which may be bonded to the polymeric backbone of the homopolymer or copolymer by way of a divalent moiety such as an alkylene or alkenylene group such as -(CH 2 ) 3
  • R 10 , R 11 , R 12 , R 13 and R 14 are the same or
  • phosphoric acid alkylarylamino, arylthio, heteroaryl, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, esters, annhydrides and salts of said acids,
  • halogen nitro, cyano, sulfonic acid, or alkyl or phenyl substituted with one or more of sulfonic acid, phosphoric acid, carboxyiic acid, esters, annhydrides and salts of said acids, halo, amino, hydroxyl, nitro, cyano or epoxy moieties, or a moiety of the formula:
  • R 15 is a divalent alkylene moiety having from 1 to about 7 carbon atoms
  • R 16 is alkyl having from 1 to about 20 carbon
  • r is a natural number from 1 to about 50;
  • R 12 , or R 13 and R 14 substituents taken together are an alkylene, alkynylene or alkenylene 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 unsatuation and divalent heteroatoms of
  • X 1 and X 2 are the same or different and are S, O, Se, NR 17 , or PR 17 wherein R 17 is hydrogen,
  • alkylaryl arylalkyl, alkyl or aryl, or R 1 .
  • This invention also relates to solutions of the polymers of Formulas I to XI in protic or aprotic
  • R 14 , R 15 , R 16 and R 17 are as described above,
  • copolymers and homopolymer are simultaneously doped by the non-oxidizing protonic acid resulting from the elimination of D rendering the copolymer or homopolymer electrically conductive.
  • Another aspect of this invention relates to a solution which comprises:
  • Solutions of Formulas I to XI can be conveniently used to form conductive articles by optionally removing the solvent, then inducing elimination of "D” and "H", thereby producing doped electrically conductive polymers of Formulas XII to XXII.
  • the use of the solutions of this invention in the methods of this invention provides conductive article and composites of all shapes, as for example, films and fibers and coatings.
  • Another aspect of this invention relates to the processing of polymers of the Formulas I to XI and blends of these polymers and conventional thermoplastic and/or thermosetting polymers, i.e., polyolefins, polyesters, polyacrylates, halogenated polyolefins, polyvinyls, such as polyvinyl alcohol, and polyvinyl chloride,
  • polysiloxanes polycarbonates, polyamides, and the like to form conductive articles.
  • this invention provides a simplified thermally activated process for direct formation of conductive doped poly(heteroaromatic vinylenes) and poly(aromatic
  • long-chain alkyl or perfluoroalkyl carboxyiic or sulfonic acid type dopants can function as plasticizers and can serve to significantly modify the cohesive energy density of doped polymers.
  • acid dopant it should be possible to significantly improve the thermal stability, solution and melt processability, and
  • One aspect of this invention is a homopolymer or a copolymer comprising recurring monomeric units selected from the group consisting of those of the Formula I to XI, wherein o, q, p, n, m, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ,
  • R 15 , R 16 , R 17 , Z-, D, X 1 and X 2 are as
  • R 14 groups are hydrogen; cyano; nitro; halo; hydroxyl; amino; alkyl such as methyl, ethyl, butyl, pentyl, hexyl, octyl, nonyl, text-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1-propenyl,
  • diarylamino such as phenylamino, diphenylamino and the like; alkylsulfinyl, alkylsulfonyl, alkylthio,
  • arylsulfonyl such as butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl,
  • phenylsulfinyl propylthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, isopropylthio, phenylsulfonyl, methylsulfonyl, nonylthio, phenylthio, ethylthio,
  • alkoxycarbonyl such as methoxycarbonyl
  • alkyl amino and dialkylamino such as dimethylamino, methylamino, diethylamino, ethylamino, dibutylamino, butylamino and the like
  • cycloalkyl such as cyclohexyl, cyclopentyl
  • alkoxyalkyl such as methoxymethylene, methoxyethoxyethylene
  • methoxydiethoxyethylene methoxydiethoxyethylene, ethoxymethylene, butoxymethylene, propoxyethylene, pentoxybutylene and the like;
  • arylalkylamino such as methylphenylamino, ethylphenylamino and the like
  • aryloxyalkyl and aryloxyaryl such as
  • R 1 to R 14 groups are moieties of the formula:
  • Useful R 15 groups include divalent moieties of the
  • R 15 and R 16 are ethylene glycol
  • the nature of the D leaving group may vary widely with the proviso that at least about 1 mole percent of D leaving groups based on the total moles of D leaving groups is a moiety which upon elimination forms a non-oxidizing organic or inorganic protonic acid having a pKa equal to or less than about 4, or an acid which can be converted via complexation with Lewis Acids into such an acid.
  • at least about 2 mole % of D groups form such an acid
  • at least about 5 mole% of D groups form such an acid
  • at least about 10 mole % of D groups form such an acid.
  • the said D groups generate on elimination of said acids having the specified pKa, which may then simultaneously dope the polymer of Formula XII to XXII forming the electrically conductive polymer.
  • useful D groups fall into two general categories or classes of moieties, those which form the required inorganic or organic acid, and those which form species which can be converted into such acids.
  • Illustrative of D leaving groups which do not form the required acid but which can be converted into same pseudohalogens such as -OCN, -OR 1 , -SR 1 , -OCOR,
  • R 1 is hydrogen or an aliphatic or aromatic group such as alkyl
  • arylalkyl alkylaryl, alkoxyalkyl, arylalkoxy, and the like.
  • Another class of useful D leaving groups are neutral D groups which on elimination directly form the non-oxidizing inorganic or organic acid.
  • Illustrative of this class of D groups are species such as -OSO 2 R 1 ,
  • R 1 is as described above, as for example,
  • alkoxyalkyl such as methoxymethyl
  • alkyl such as methyl, ethyl, propyl, and butyl
  • aryl and alkylaryl such as phenyl, tolyl and the like
  • arylalkyl such as benzyl, phenethyl, 4-phenyl-butyl and the like
  • alkanoyl and aroyl such as acetyl, butanoyl, benzoyl, and the like
  • alkanesulfonyl and arylsulfonyl such as methenesulfonyl, ethanesulfonyl, butanesulfonyl, toluenesulfonyl, phenylsulfonyl, and the like
  • alkyl or aryl group substituted with carboxylic or sulfonic acid groups or salts thereof such as
  • butylsulfonic acid butylcarboxylic acid, pentyl sulfonic acid; pentyl carboxyiic acid, propane sodium sulfonate, pentane sodium sulfonate, and the like.
  • D group Another class of useful D group are zwitteronic species in which the cationic portion can be eliminated as a neutral species, preferably a volatile one, and the anionic portion is an anion of a non-oxidizing organic or inorganic protonic acid or is anionic species which can be converted into such an anion.
  • zwitteronic species in which the cationic portion can be eliminated as a neutral species, preferably a volatile one, and the anionic portion is an anion of a non-oxidizing organic or inorganic protonic acid or is anionic species which can be converted into such an anion.
  • Illustrative of such D groups are species of the formulas: - + SR 1 R 2 Z-, pyridinium, Z-, -N + R 1 R 2 R 3 Z-, such as
  • R 1 , R 2 and R 3 are as described above, as for
  • alkyl such as methyl, ethyl, propyl, butyl and the like
  • alkylaryl, alkoxyaryl, and aryl such as phenyl, tolyl, anisyl, and the like
  • arylalkyl such as benzyl, phenethyl, 4-phenylbutyl, and the like
  • R 1 , R 2 , and R 3 together may form an alkenylene or alkylene chain such as -(CH 2 ) 4 -, -(CH 2 ) 3 -, -(CH 2 ) 7 -,
  • Z is the anion of a non-oxidizing protonic acid such as
  • Preferred for use in the practice of this invention are homopolymers, and random or block copolymers of the above Formulas I to XI in which:
  • n, o and p are the same or different and are selected such that m, or the sum of n, o and p is an integer at least about 40, with the proviso that at least one of n or o is greater than zero; preferably that the sum of n, o and p, or m is at least about 75;
  • q is an integer from 0 to about 4.
  • R 1 , R 2 , R 3 and R 4 are the same or different
  • phenylalkyl such as benzyl, phenethyl
  • alkoxy having from 1 to about 12 carbon atoms such as methoxy, ethoxy, and butoxy; alkanoyl having from 1 to 20 carbon atoms such as formyl, acetyl, and propenyl;
  • alkylthio having from 1 to 20 carbon atoms such as
  • alkoxyalkyl having from 1 to 20 carbon atoms such as methoxymethyl, ethoxyethyl, heptoxypropyl, methoxyethyl, alkenyl having from 1 to about 20 carbon atoms such as allyl, vinyl and 3-butenyl
  • alkynyl such as ethynyl, propynyl, butynyl; or phenyl and alkyl substituted with hydroxyl, epoxy, sulfonic acid, nitro, cyano, phosphoric acid, carboxylic acid esters, anhydrides, or halo
  • substituents such as trifluoromethyl, 3,4-epoxybutyl, cyanomethyl, 2-nitroethyl, 3-chloropropyl, 4-nitrophenyl, -CH 2 CH 2 CH 2 SO 3 H; -CH 2 CH 2 CH 2 P(O) (OH) 2 ; and
  • R 15 is alkyl 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, diethylene glycol monomethylether, triethylene glycol monomethylether, tetraethylene glycol monomethylether and the like; or any of R 1 and R 2 or R 3 and R 4 substituents taken
  • alkylene, alkynylene or alkenylene chain having from 2 to 20 carbon atoms completing a 4, 5,
  • 6, 7, 8, 9 or 10 membered ring system which may include one or more heteroatoms of oxygen, nitrogen or sulfur such as 1,4-butanediyl, 1,2-ethanediyl, -CH 2 SCH 2 -,
  • R 5 to R 14 are the same or different at each
  • alkyl having from 1 to about 12 carbon atoms substituted alkyl, phenyl, substituted phenyl, alkylthio having from 1 to about 12 carbon atoms or alkoxy having from 1 to about 12 carbon atoms; alkylamino having about 1 to about 12 carbon atoms or any of R 5 and R 6 , or R 7 and R 8 , or
  • substituents together may form an alkylene chain having 2 to about 20 carbon atoms completing a 4, 5 or 6 membered ring system which may include one or more heteroatoms of oxygen or sulfur such as 1,4-butendiyl, 1,2-ethanediyl, -CH 2 SCH 2 CH 2 OCH 2 -; -CH 2 -CH-CH-CH-, X, and X 2 are the same or different and are
  • D is the same or different at each occurrence and is moieties of the formula:
  • alkyl such as methyl, ethyl, propyl, butyl, hexyl, and octyl
  • alkanoyl, benzoyl or alkyl or alkoxy substituted benzoyl such as benzoyl, butanoyl, ethanoyl
  • phenoxy alkylphenyl and alkoxyphenyl such as tolyl, anisyl methlphenyl, dodecyl phenyl
  • alkoxyalkyl such as methoxyethyl
  • phenylalkyl such as benzyl or phenethyl
  • F, Cl, Br or I
  • R 1 and R 2 are the same or different at each
  • alkyl such as methyl, ethyl, or butyl
  • R 4 and R 2 together form an alkylene, alkynylene, or alkenylene chain containing one or more unsaturations such as 1,4-butanediyl, 1,3-propanediyl or 1,5-pentanediyl completing a saturated or unsaturated ring structure, or an aromatic or heteraromatic ring structure;
  • alkyl such as methyl, ethyl, propyl, and butyl
  • aryl arylalkyl such as benzyl and phenethyl
  • alkylaryl and alkoxyaryl such as tolyl and anisyl
  • alkoxyalkyl such as methoxymethyl
  • alkylene, alkynylene or alkenylene chain having one or more degrees of unsaturation completing a saturated ring structure such as piperidinium or an aromatic or
  • heterocyclic ring structure such as pyridinuim and substituted pyridinium
  • Z- is an anion such as
  • R 18 is alkyl, or aryl, which may be
  • q is an integer from 0 to 3;
  • n, o and p are at least about 100 and at least one of n or o is greater than zero.
  • R 1 , R 2 , R 3 and R 4 are the same or different
  • 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 having from 1 to about 12 carbon such as methoxy, nonyloxy, dodecanoxy, ethoxy and butoxy
  • alkylthio having from 1 to about 12 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio
  • alkoxyalkyl having from 1 to about 12 carbon atoms such as ethoxymethyl and butoxymethyl; or a moiety of the formula:
  • R 15 is alkylene of about 2 to 3 carbon atoms
  • R 16 is alkyl of from 1 to about 3 carbon atoms; and r is a natural number from 1 to about 10;
  • R 13 , and R 14 are the same or different at each
  • R 10 , R 11 and R 12 together may be propylene
  • R 18 is alkyl, phenyl, alkylphenyl or phenylalkyl which may be unsubstituted or substituted with one or more fluoro, chloro, Bromo or cyano groups;
  • X 1 and X 2 are the same or different and are
  • D is the same or different at each occurrence and is: a leaving group, with the proviso that at least about 2 mole % of D leaving groups based on the total moles of D leaving groups on an elimination forms an acid laving a pKa equal to or less than about 4, preferably less than or equal to about 3, more preferably equal to or less than about 2 and most preferably equal to or or less than about 1, or can be converted into such an acid and is selected from the group consisting of:
  • alkyl such as methyl, ethyl, butyl, and octyl
  • phenyl alkylphenyl and alkoxyphenyl such as tolyl and anisyl
  • phenylalkyl such as benzyl and phenethyl
  • alkanoyl and aryloyl such as acetyl and benzoyl
  • R 2 and R 3 are aryl such as phenyl; alkyl such as
  • alkoxyalkyl such as
  • R 1 , R 2 and R 3 together form an alkynylene, alkylene or alkenylene chain such as 1,4-butanediyl, 1,5- pentanediyl, and 1, 5-pent-1,3,5-trienediyl, completing a ring structure such as tetrahydrothiophenonium;
  • R 18 is alkyl having from 1 to about 20 carbon atoms, alkylphenyl having from 7 to about 20 carbon atoms or phenyl which may be unsubstituted or substituted one or more fluoro, chloro, alkyl, bromo, or cyano, alkoxy or sulfonic acid, carboxyiic acid, phosphoric acid or
  • q is an integer from 0 to about 2;
  • n, o and p are at least about 125 R 1 to R 4 are the same or different at each
  • R 15 is -(CH 2 ) 2 - or -CH 2 CH(CH 3 )-;
  • R 16 is -CH 3 or -CH 2 CH 3 ;
  • r is an integer from 0 to 10
  • D is the same or different at each occurrence and is: a leaving group, with the proviso that at least about 2 mole % of D leaving groups based on the total moles of D leaving groups on an elimination forms an acid having a pKa equal to or less than about 4.0, preferably less than or equal to about 3, more preferably equal to or less than about 2 and most preferably equal to or or less than about 1, or can be converted into such an acid and is selected from the group consisting of:
  • R 1 and R 2 are the same or different at each occurrence and are hydrogen; alkyl such as methyl, ethyl, propyl, and butyl; aryl such as phenyl; or R 1 and R 2 together may form an alkylene, alkynylene, or alkenylene chain and
  • R 1 , R 2 , R 3 are alkyl such as methyl; ethyl;
  • R 1 , R 2 and R 3 may form an alkylene
  • alkynylene, or alkenylene chain such as 1,4-butanediyl, 1,5-pentanediyl, and 1,5- ⁇ ent-1,3-dienediyl completing a saturated cyclic structure or an unsaturated aromatic or heteroaromatic structure such as pyridinium;
  • R 18 is alkyl having from 1 to
  • X 1 and X 2 are sulfur, or -NH- or -NR 17 -. Especially good results are provided in those embodiments of the invention where D is a moiety of the formula:
  • This invention also relates to solutions of the homopolymers and copolymers of Formula I to XI comprised of one or more of said copolymers and homopolymers and a protic and/or an aprotic solvent.
  • Useful solvents as can vary widely and include such solvents as water, ethanol, methanol, butanol, propanol, acetone, toluene, hexamethyl phosphoric triamide, dimethylformamide, dimethylacetamide, methylene chloride propylene carbonate, sulfolane and the like, or mixtures thereof.
  • solvents are selected from the group consisting of water, methanol, butanol, ethanol, propanol, sulfolane, dimethyl sulfoxide, methylene chloride, dimethylformamide, N-methyl pyrolidinone and mixtures thereof, and in the particularly preferred embodiments of the invention, the solvent is selected from the group consisting of water, sulfolane, methanol, butanol, and dimethyl formamide and mixtures thereof. Particularly preferred is water.
  • copolymers and homopolymers of Formulas I to XI can be conveniently prepared in a one or two step
  • this reaction is carried out in solution using the protic or aprotic solvents described above.
  • Bases for use in this reaction are not critical and the only
  • alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide
  • alkali metal carbonates and bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate
  • organic amine containing bases such as piperidine, pyridine, DABCO, ethylene diamine, tripropylamine, tributyl amine, and the like
  • alkali metal alkoxides such as potassium t-butoxide, lithium methoxide lithium ethoxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide
  • insoluble bases such as calcium oxide, Barium oxide, magnesium oxide and the like
  • polymeric bases such as poly(p-amino styrene), basic forms of ion exchange resins such as Amberlyst and amberlyte resins in OH- form or free base forms.
  • Preferred bases are sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide and sodium carbonate
  • particularly preferred bases are sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide.
  • most preferred are those embodiments of the invention in which the base is sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium methoxide.
  • solvents for use in this process are those in which the polymers of Formulas XXXIV - XLIV are soluble and can vary widely.
  • Preferred solvents are water, methanol, ethanol, butanol, dimethylsulfoxide, acetone, sulfolane, dimethylformamide, N-methylpyrrolidone and acetonitrile, and particularly preferred solvents are water, methanol, ethanol, dimethylformamide, and
  • N-methylpyrrolidone Amongst those particularly preferred solvents, most preferred solvents are methanol, ethanol, dimethylformamide and water.
  • Reaction temperatures are not critical and can vary widely. In general, the polymerization reaction is
  • reaction temperature of from about -15°C to about 200°C.
  • reaction temperature of from about -15°C to about 50°C and in the particularly preferred embodiments reaction temperatures are from about -5°C to about 25°C.
  • Reaction pressures are not critical and the reaction can be carried out at sub-atmospheric pressure
  • reaction is carried out at atmospheric or autogeneous pressure.
  • Reaction times can vary widely. In general, the reaction is carried out over a period of from about a few seconds to a few hours.
  • Useful agents may vary widely and depends on the nature of the D moiety.
  • Illustrative of useful agents are species of the formula:
  • R 1 is hydrogen or a metal ion and R 1 is as described above such as alkyl, aryl, arylalkyl, alkylaryl and the like.
  • suitable compounds are sodium toluene sulfonic acid, potassium methyl sulfonic acid, sodium trifluoroacetic acid, sodium acetate, potasium benzoate, and the like.
  • R 1 , R 2 , R 3 form an alkylene, alkenylene or alkynylene chain completing a monocyclic, bicyclic, alicyclic, aromatic or
  • NR 1 R 2 R 3 compounds are triethylamine, ethylamine,
  • 1,2-dihydroquinoline methylethylamine, benzyldimethylamino, N,N-dimethylaniline, trimethylamine, dimethylethylamine, piperidine, 5,6-benzoquinoline,
  • alkyl from 1 to about 20 carbons aryl alkylaryl, arylalkyl, alkoxy from 1 to about 20 carbons, aryloxy, alkylaryloxy or arylalkyloxy.
  • phosphine triphenyl phosphine, triethylphosphine, benzyl dimethyl phosphine, phenethoxy diethylphosphine,
  • triphenoxyphosphine tripentylphosphine
  • alkyl having from 1 to about 10 carbon atoms or aryl, alkylaryl, or arylalkyl having from about 6 to about 20 carbon atoms, or R 1 and R 2 together may form a cyclic structure.
  • alkyl having from 1 to about 10 carbon atoms or aryl, alkylaryl, or arylalkyl having from about 6 to about 20 carbon atoms, or R 1 and R 2 together may form a cyclic structure.
  • these materials are N,N-dimethyl hydroxyl amine, N,N-diethyl hydroxyl amine, N-phenyl-N-methyl hydroxyl amine,
  • R 1 is hydrogen, alkyl, aryl, alkoxyalkyl, alkylaryl, arylalkyl, and the like as
  • Particularly preferred agents are those of the formula:
  • R 1 is alkyl of 1 to about 20 carbons, fluorinated alkyl, alkylphenyl, alkoxyphenyl, phenyl, or benzyl;
  • alkylene, alkynylene or alkenylene chain which may form a monocyclic or bicyclic or alicyclic or aromatic ring structure of from about 6 to about 20 carbon atoms such as pyridine;
  • Most particularly preferred agents are pyridine, trimethylamine, triethylamine, tributylamine, quinoline, tributylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, 4-dimethylamino-pyridine and the like.
  • Z- moieties can be totally or partially changed through use of standard ion exchange techniques. Such techniques are well known to those of skill in the art and will not be discribed herein in any great detail. Such exchanges may be carried out for a number of
  • Another aspect of this invention relates to a process for preparing conductive polymers from conjugated backbone copolymers and homopolymers of the Formulas XII to XXII which are prepared from the corresponding polymers of the Formula I to XI.
  • these neutral conjugated backbone polymers are prepared by thermal treatment of the precursor polymers of Formulas I to XI, either as
  • useful temperatures may range from about -10°C to about 300°C.
  • the thermal treatment eliminates D in two ways, as DH or as D and HZ. Useful temperatures depend on the structure of the
  • a Lewis acid can be used to form a protonic acid doped conjugated polymer from a precursor non-conjugated polymer by a Lewis-acid- catalyzed elimination reaction.
  • Useful Lewis acids areAsX 3 , SbX 3 , PX 5 , PX 3 , BX 3 , AlX 3 (where X is
  • ethylene-1',2'-diyl which can be converted into protonic acid doped and conductive poly(2,5-dibutoxyphenylene vinylene) by treatment with BF 3 which induces
  • non-conducting host polymers by in-situ polymerization of the monomer in the presence of a conjugated polymer.
  • Illustrative of useful monomers are those which polymerize by ring opening reactions.
  • Such monomers include cyclic ethers, such as ethylene oxide, propylene oxide,
  • epichlorohydrin oxetanes, 3,3-bis(chloromethyl) oxetane, tetrahydrofuran, oxepane, or a mixture of tetrahydropyran and other cyclic ethers, and the like; cyclic ethers containing more than one oxygen, such as 1,3-dioxolanes, 1,3-dioxanes, 1,3-dioxepanes, 1,3-dioxocanes,
  • 1,3-dioxacyclotridecanes 1,3,5-trioxanes, 1,3,5- trioxepanes, 1,3,6-trioxocanes, 1,3,5,7-tetraoxanes, 1,3,6,9-tetraoxacycloundecanes, 1,3,6,11-tetraoxacyclotri- decanes, 1,3,6,9,12-pentaoxacyclotetradecanes,
  • cyclic sulfides such as thiacyclopropane
  • lactams such as
  • lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and the like.
  • lactones analogues such as glycolides, lactides, ethylene carbonate, 1,3-dioxepane-7-ones,
  • a conductive composite film comprised of protonic acid doped poly(3-methoxythienylene vinylene) and ⁇ oly(tetrahydrofuran) is obtained.
  • the conductive polymer solutions used can be either a true solution or a suspension.
  • the polymer can be either a conjugated polymer or a non-conjugated precursor polymer which is capable of acid-catalyzed transformation into its conjugated form.
  • the electrically conductive forms of the polymers of Formulas XII to XXII are formed by the elimination of D from polymers of Formulas I to XI.
  • conductivity is at least about 10 -8 ohm -1 cm -1 .
  • upper conductivity is not critical, and usually the highest conductivity which can be obtained is provided.
  • conductivity is equal to or greater than about
  • the conductivity is equal to or greater than about 10 -2 ohm -1 cm -1 . In the most preferred
  • the conductivity is equal to or greater than about 10 -1 ohm -1 cm -1 .
  • this invention also relates to
  • solvent type employed can vary widely, from polar to non-polar.
  • Useful solvents include water and various organic solvents.
  • solvents which can be used in the practice of this invention will have a dipole moment greater than zero and less than or equal to about 5, and a dielectric constant of less than about 190.
  • useful solvents are water, alcohols, such as methanol, ethanol, propanol, trifluoroethanol, benzyl alcohol, butanol and the like, amines such as
  • acids such as trifluoroacetic, acetic, formic, methane sulfonic, sulfuric and trifluoromethane sulfonic acids; anhydrides such as acetic anhydride, trifluoro acetic anhydride propionicanhydride and the like, sultones, such as propane sultone, butane sultone, pentane sultone and the like; alkyl alkanesulfonates such as methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate and the like;
  • linear and cyclic ethers such as 1,2-dimethoxyethane, dimethoxymethane, dioxane, glymes, diglymes,
  • nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile and the like
  • hydrocarbons such as cyclohexane, pentane, hexane and cyclopentane
  • halocarbons such as carbon tetrachloride, dichloromethane, dichloroethylene, and 1,2-dichloroethane, trichloroethylene
  • aromatic solvents such as benzene, toluene, xylene, nitrobenzene and the like
  • ketones such as 4-methyl-pentanone, methylethylketone, acetone, and the like
  • carbonates such as propylene carbonate, dimethyl carbonate, ethylene carbonate and the like
  • esters such as methyl formate, methyl acetate, Y-butyrolactone, ethyl acetate
  • organophosphorus compounds such as hexamethyl phosphorous triamide, diethylphosphate, triethylphosphate, trimethylphosphate and the like
  • organosulfur compounds such as
  • sulfolane methyl sulfolane, dimethyl sulfone, dimethyl sulfoxide, dimethyl sulfolane, glycol sulfite, tetraethylsulfamide and the like.
  • Mixtures of such solvents can also be used as for example mixtures of sulfolane and acetonitrile, or water and methanol.
  • the solvent or solvent mixture selected for use in any particular situation will depend primarily on the polarity of various R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ,
  • solvents chosen for use with polymers having relatively polar substituents will usually have a dipole moment of from about 0.3 to about 5.0, preferably from about 1.8 to about 5.0; and a dielectric constant of from about 10 to about 190, preferably from about 20 to about 100.
  • Illustrative of such solvents are alcohols, such as methanol, ethanol, isopropanol, and the like;
  • halocarbons such as
  • N,N-dimethylacetamide, N-methyl pyrrolidone and the like substituted aromatics, such as xylene, anisole, toluene and the like; nitriles, such as acetonitrile,
  • propionitrile, benzonitrile, butyronitrile, and the like sulfoxides and other sulfur containing solvents such as dimethylsulfoxide and the like; nitro substituted alkanes and aromatics such as nitromethane, nitropropane,
  • solvents chosen for use with polymers having relatively non-polar substituents will have a dipole moment of from about 0 to about 3.0, preferably from about 0 to about 2.5; and a dielectric constant of from about 2.0 to about 50, preferably from about 2.0 to about 35.
  • halocarbons such as dichloromethane, and the like
  • aromatic solvents such as toluene, xylene, benzene and the like
  • cyclic and linear ethers such as dimethoxyethane, tetrahydrofuran and the like
  • esters such as ethylacetate, methyl formate and the like
  • sulfoxides such as dimethylsulfoxide and the like
  • cyclic and linear amides such as dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide and the like
  • ketones such as acetone and the like and mixtures thereof.
  • 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 with doped or undoped polymers.
  • embodiments of the invention may be particularly useful for silkscreening, extruding fibers, and for applying thick film coatings on substrates.
  • embodiments of the invention may be particularly useful for silkscreening, extruding fibers, and for applying thick film coatings on substrates.
  • the solvent is present in sufficient amounts to lower the viscosity of the solution to less than about 2,000 centipoise, and more preferably from about 1 to about 1000 centipoise.
  • the solutions of this invention can include other optional ingredients and mixtures thereof 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 other conventional polymers such as polyacrylonitrile, polyvinylidene chloride, polyethylene oxide, polystyrene, nylon, polyvinylsulfonic acid,
  • nonsoluble components materials may be present which either fill or form a substrate for the conductive polymer cast from the solution.
  • non-soluble components include other polymers such as polyacetylene which may become conductive upon doping, graphite, carbons, metal conductors,
  • reinforcing fibers and inert fillers such as clays and glass.
  • the method of forming the solutions of this invention is not critical and can vary widely.
  • the solution of this invention can be prepared merely by dissolving the desired amount of the polymer in a solvent in which it is soluble such as water, toluene or
  • solutions can be formed by directly polymerizing the monomers and/or eliminating D from polymers in the solvent.
  • the solvent can be removed from the solution through use of any conventional solvent removal method but is removed preferably by evaporation.
  • the solvent can be removed by extraction with an extractant in which the solvent is substantially more soluble than the polymer.
  • removing a solvent from a solution enables one to prepare articles of a wide variety of shapes and sizes.
  • films and coatings of any desired thickness can be prepared.
  • fibers or films can be made.
  • shaped articles conforming in shape to the mold can be prepared.
  • shrinkage might occur between the solution in its last flowable state to the final article, but such shrinkage is conventionally accounted for in molding polymers from solution. It is also contemplated that, once a solution is formed, a partial or substantial removal of solvent will occur prior to placing the solution on a surface or in a mold, with the final venting of solvent occurring on the surface or in the mold. It is contemplated that, if additional soluble components are introduced into the solution, they will, unless also volatile, be present in the shaped article formed. If the fourth component is a non-volatile liquid, then the removal of volatile
  • additonal components may leave a new liquid or plasticized form of doped conducting polymer or neutral polymer. If the additonal components are volatile, then foamed or expanded cellular forms of the polymer may be formed.
  • the polymers of Formula I to XI or blends of such polymers and one or more thermoplastic polymers can also be melt processed into useful articles using conventional melt processing techniques. For example, if a blend is used, the various components are granulated, and the granulated components mixed dry in a tumbler, Banbury mixer or other suitable mixer. The components of the blend are usually mixed until the blend is uniform or as homogenous as possible. The blend is then heated above the melting point of at least one of the polymeric components preferably with mixing. Such treatment may cause elimination of D and formation of conductive polymers XII to XXII as a conductive blend with one or more thermoplastic polymers. For example, the blend may be conventionally melted by heating in a conventional extruder.
  • the ability of a polymer to be melt processed allows for the manufacture articles of a wide variety of shapes merely by placing the melt in a mold of the desired shape and cooling the melt below the melting point of at least one of the polymer components. For example, by spreading a melt on a surface and cooling, films of any desired thickness can be fabricated.
  • fibers and films can be made by extruding the melt through a suitable die, and shaped articles can be formed by placing a melt into a mold having the desired shape and cooling the melt below the melting point of one or more of the polymeric components.
  • polymers of Formulas I to XXII can be fabricated alone or as blends with one or more thermoplastics
  • Useful thermoplastic polymers may vary widely. Illustrative of useful polymers are those formed by
  • polypropylene polyethylene, poly(octadiene), polyiso- butylene, ⁇ oly(pentene), poly(styrene), poly(2-methyl styrene), poly(4-methylstyrene), poly(hexene), poly(methyl- hexene), poly(butylene), poly(methylpentene),
  • thermoplastic polymers poly(vinylidene fluoride), poly(vinyl alcohol), poly(acrylo- nitrile), poly(vinyl acetate), poly(vinylmethylether), poly(methylacrylate), ⁇ oly(methylmethacrylate), acrylo- nitrile-butadiene-styrene copolymer, polyacrylamide, and the like.
  • polyamides and polyesters such as the
  • nylon 7 7-aminoheptanoic acid
  • nylon 8 poly(8-aminooctanoic acid)
  • nylon 6 poly(6-aminohexanoic acid)
  • nylon 6 poly(hexamethylene adipamide)
  • poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7),
  • poly(decamethylene azelamide) (nylon 10,9), poly(deca- methylene sebacamide) (nylon 10,10), poly[bis(4-amino- cyclohexyl)methane-1,10-decanedicarboxamide], poly(m- xylylene adipamide), poly(p-xylylene sebacamide),
  • isophthalamide) Nomex
  • poly(p-phenylene terephthalamide) Kevlar
  • poly(11-amino-undecanoic acid) nylon 11
  • poly(12-aminododecanoic acid) nylon 12
  • poly(9-aminononanoic acid) nylon 9
  • polycaproamide poly(ethylene terephthalate), poly(cyclo- hexylenedimethylene, terephthalate), poly(ethylene
  • dodecate ⁇ oly(butylene terephthalate, ⁇ oly[ethylene(2,7- naphthalate)], ⁇ oly(methaphenylene isophthalate), poly- (glycolic acid), poly(ethylene succinate), poly(ethylene adipate), poly(ethylene sebacate), poly(decamethylene azelate), poly(decamethylene azipate), poly(decamethylene sebacate), ⁇ oly(dimethylpropiolactone), poly(para- hydroxybenzoate) (Ekonol), poly(ethylene oxybenzoate)
  • dimethylene terephthalate (trans), ⁇ oly(ethylene 1,5- naphthalate), poly(ethylene 2,6-naphthalate), poiy(1,4- cyclohexylidene dimethylene terephthalate) (Kodel) (cis), poly(1,4-cyclohexylidene dimethylene terephthalate)
  • the conductive polymers of this invention can be used in the fabrication of conductive articles such as housings for sensitive electronic equipment as for example microprocessors; infrared, radio wave, and microwave absorbing shields; flexible electrical conducting
  • liquid mercury is used in various devices.
  • examples of such devices include gravity switches, fluid level detecting devices and other electrical or electronic switches and sensors.
  • 1,4-Xylene bis(tetramethylene sulfonium chloride) (5g; 14.2 m mole) and 0.296 g of 2 , 5-dimethoxy-1,4- xylene bis (tetramethylene sulfonium chloride) (0.71 m mole) was dissolved in 37.5 ml of H 2 O). The solution (0.4 M) was filtered and then degassed by N 2 for 3h.
  • the resulting solution (about 200 ml) was dialyzed against deionized water from 3 to 5 days. About half of the dialyzed solution was cast into a precursor film, which was then thermally converted into the fully
  • the bissulfonium salt 2,5-dimethoxy-1,4-xylene bis (tetramethylene sulfonium chloride (1 g; 2.4 m mole), was dissolved in 6 ml of deionized water (0.4 M), and degassed by N 2 for about 4h. After cooling the solution for half an hour, a 0.4 M degassed NaOH aqueous solution (0.097 g in 6 ml H 2 O; 0.4 M) was added. A cloudy
  • the polymer solution was then placed into dialysis tubes having a molecular weight cutoff of 6000-8000.
  • This non-conductive, non-conjugated precursor polymer film was then placed at room temperature in a zip-lock bag and sealed. After sitting at room temperature for about 2 weeks, the film was found to have become non-transparent and conductive, with a green metallic luster.
  • the conductivity was measured to be 10 -2 Scm -1 , which is comparable to that of a fully eliminated

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Abstract

This invention relates to novel forms of electrically conductive poly(heteroaromatic vinylenes), and poly(aromatic vinylenes) and to solutions thereof and to processes and precursors for preparing same.

Description

ELECTRICALLY CONDUCTIVE POLY(AROMATIC
VINYLENES) AND POLY (HETEROAROMATIC VINYLENES)
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel electrically
conductive forms of poly(heteroaromatic vinylenes) and poly(aromatic vinylenes), to precursors for use in processes for formation of said poly(aromatic vinylenes) and ρoly(heteroaromatic vinylenes), and to solutions and blends comprising poly(aromatic vinylenes) or
poly(heteroaromatic vinylenes) in the conductive form. Another aspect of this invention relates to methods of using the solutions and blends of this invention to form conducting polymer articles, including films, fibers, and coatings and methods of using such solutions as conducting liquids. Yet another aspect of this invention relates to novel process for preparing the poly(heteroaromatic vinylenes) and the poly(aromatic vinylenes) of this invention.
2. Erior Art
There has recently been an increased interest in the electrical conductivity of polymeric systems. For
example, US Patent Nos. 4,321,114 and 4,442,187 are directed to conjugated polymers having conjugation in all or a part of at least one backbone chain thereof, such as polyacetylene, polyphenylene and poly(phenylene sulfide). It has recently been discovered that these conjugated backbone polymers can be chemically doped in a controlled manner with electron acceptor and/or electron donor dopants to produce electrically conducting polymers.
Doping procedures and certain representative doped
polymers are described in US Patent Nos. 4,222,903 and 4,204,216.
In the general field of conducting polymers, it is believed very difficult to dope one of these conjugated backbone polymers to the extent that it becomes a good conductor (10-4-100 ohm-1cm-1) and thereafter
dissolve the polymer in any solvent-system. US Patent
4,452,727 and 4,599,194 disclose novel polymer solutions containing a doped sulfur-containing or oxygen-containing aromatic polymer. The solvent of this solution is
restricted to solvents containing Lewis Acid halides having a liquid phase under atmospheric pressure for at least one temperature between -150°C and +100°C, such as arsenic trifluoride, phosphorus trifluoride, phosphorous pentafluoride, phosphorus trichloride, boron trifluoride and the like. These solutions can be used to form
articles, as for example, by casting the solution onto a substrate, and removing the solvent. This solution and method represents a significant advancement over the art; however, it does suffer from certain economic and
practical disadvantages resulting from the cost and high environmental reactivity and toxicity of the specific solvents which must be used.
A few conductive species of polyalkylthiophenes are known, having been primarily prepared by electrochemical polymerization. Illustrative of such species are
poly(3-methylthiophene) and poly(3,4-dimethylthiophene). R.J. Waltman, J. Bargon and A.F. Diaz, J. Phys. Chem., 87, 1459-1463, 1983. G. Tourillon, D. Govrier, P. Gamier and D. Viven, J. Phys. Chem., 88, 1049-1051, 1984. S. Hotta, T. Hosaka and W. Shimotsuma, Syn. Metals., 6, 317-318, 1983. However, the polymers prepared electrochemically are not soluble in common organic solvents such as
acetonitrile,, propylene carbonate, tetrahydrofuran, dichloromethane, dimethyl formamide, nitrobenzene, nitropropane, toluene, and the like. In the absence of solutions, or plasticized forms, the ability to
economically fabricate articles out of the conducting forms of these poly(alkylthiophenes), especially
semi-conducting and conducting polymer films, fibers, and coatings, especially using conventional solvents or melt-forming techniques, is greatly restricted. In fact, the electrochemical methods are reported to give
homogeneous conductive polymer films only to film
thickness of about 2000 Å. Powdery deposits are obtained when attempts are made to grow films thicker than this. (G. Tourillon and F. Gamier, J. Polv. Polv. Phvs. Ed., 22, 33-39, 1984.)
The unsubstituted polythiophenes form highly
conductive complexes on doping which are not stable in normal environments (containing air or water vapor).
However, electrochemically prepared conductive
poly(3-methylthiophene) is environmentally stable.
(G. Tourillon and F. Gamier, J. Electrochem. Soc.,
Electrochem. Sci. Techn., 130, 2042-3, 1983.)
A conductive oligomeric species of poly(thiophene vinylenes), i.e., 6 to 8 repeat units are described in G. Kossmehl et al., Makromol Chem., 131, 15-54, 1970, and G. Kossmehl, Ber. Bunsenges Phys. Chem., 83, 417-426, 1979. These oligomeric species of poly(thiophene vinylenes) exhibit several undesirable properties, which limit their utility in potential applications such as EMI shielding, and as anti-static materials. For example, the
above-cited publications disclose that these oligomeric poly(thiophene vinylenes) are insoluble in common organic solvents which essentially precludes solution
processability, are infuseable which essentially precludes melt processability, and exhibit low conductivities on oxidative doping (10-2 ohm-1cm-1) which essentially
precludes use of such materials in EMI shielding and
circuitry applications.
Poly(aromatic vinylenes) and poly(heteroaromatic vinylenes) formed from various soluble precursor polymers are known. For example, US Patent No. 4,808,681 and its UK counterpart 8429111 describes various conductive
poly(2,5-furanylene vinylenes) and poly(2,5-thienylene vinylenes) which are prepared by heat treatment of
sulfonium salt containing precursor polymers resulting in elimination of the sulfide to form the vinylene group.
Similarly, Kwan-Yue Jen et al. "Poly(2,5-Thienylene, Vinylene) Prepared Via a Soluble Precursor Polymer", J. Chem. Soc., Chem. Commun., p.309, (1987) describes the preparation of poly(2,5-thienylene vinylenes) from various water soluble polyelectrolytes precursor polymers
containing pendant sulfonium groups. The elimination of these groups results in the formation of conjugated unsaturation in the polymeric backbone.
SUMMARY OF THE INVENTION
One embodiment of this invention relates to
homopolymers and copolymers which are useful in the formation of poly(heterocyclic vinylenes), said
homopolymers and copolymers comprising recurring units selected from the group consisting of those of the
Formulas I to XI:
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
wherein :
m, n, o and p are the same or different and are selected such that m, or the sum of n, o and p is greater than about 20, with the proviso that at least one of n or o is not zero;
q is the same or different at each occurrence and is an integer which can range from 0 to about 4;
D is a leaving group, with the proviso that at least about 1 mole % of D leaving groups based on the total moles of D leaving groups is selected from the group consisting of neutral moieties which on elimination form the anion of a strong non-oxidizing organic or inorganic protonic acid having a pKa equal to or less than about 4 or a species which can be converted into the anion of such an acid such as -OR1, -R1OCO2-, F, Cl, Br, I,
-OSO2R1, -OSO3R1, -CO2R1, -OPO(OR1) (OR2),
-OSiR1R2R3, and the like, or zwitterionic moieties which on elimination form the anion of such a strong non-oxidizing organic or inorganic acid, protonic acid having a pKa equal to or less than about 4, or a species which can be converted into such an anion such as -+NR1R2R3Z-, -P+R1R2R3 Z-,
-+SOR1R2 Z-, -+SR1R2 Z-,
-+NOR1R2Z- and the like where Z- is an anion of
a non-oxidizing inorganic or organic protonic acid having a pKa equal to or less than about 4 or an anionic species which can be converted into such an anion such as
4
Figure imgf000009_0001
and R3 are the same or different and include groups such as hydrogen alkyl, phenyl, phenylalkyl, or alkylphenyl which may be unsubstituted or substituted with halogen, sulfonic acid or the like such as
Figure imgf000009_0002
, is said anion
Figure imgf000009_0003
on said anionic species which may be bonded to the polymeric backbone of the homopolymer or copolymer by way of a divalent moiety such as an alkylene or alkenylene group such as -(CH2)3
Figure imgf000009_0004
R1, R2, R3, R4, R5, R6, R7, R8, R9,
R10 , R11, R12, R13 and R14 are the same or
different at each occurrence and are hydrogen or isotopes thereof, hydroxy, amino, alkyl, alkenyl, aryl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkynyl, alkylaryl, arylalkyl, amido, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl,
arylamino, diarylamino, alkylamino, dialkylamino,
phosphoric acid, alkylarylamino, arylthio, heteroaryl, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, esters, annhydrides and salts of said acids,
halogen, nitro, cyano, sulfonic acid, or alkyl or phenyl substituted with one or more of sulfonic acid, phosphoric acid, carboxyiic acid, esters, annhydrides and salts of said acids, halo, amino, hydroxyl, nitro, cyano or epoxy moieties, or a moiety of the formula:
-(OR15)rOR16 or -R15-(OR15)rOR16 wherein:
R15 is a divalent alkylene moiety having from 1 to about 7 carbon atoms;
R16 is alkyl having from 1 to about 20 carbon
atoms; and
r is a natural number from 1 to about 50; or
and R1 and R2, or R3 and R4, or R5 and
R6, or R7 and R8, or R9 and R10, or R11 and
R12, or R13 and R14 substituents taken together are an alkylene, alkynylene or alkenylene 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 unsatuation and divalent heteroatoms of
nitrogen, sulfur, sulfinyl, phosphorus, selenium, sulfonyl or oxygen; and
X1 and X2 are the same or different and are S, O, Se, NR17, or PR17 wherein R17 is hydrogen,
alkylaryl, arylalkyl, alkyl or aryl, or R1.
This invention also relates to solutions of the polymers of Formulas I to XI in protic or aprotic
solvents. These solutions thereof can be used to form articles such as films of the polymers of Formula I to XI, which upon subsequent treatment such as heat treatment, or treatment with chemical agents, eliminates "D" to form doped electrically conductive conjugated copolymers and homopolymers having regular or random recurring conjugated units of the following Formulas XII to XXII:
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
wherein m, n, o, p, q, X1, X2, R1 , R2 , R3, R4,
R5, R6, R7, R8, R9, R10, R11 , R 12, R13,
R14, R15, R16 and R17 are as described above,
which copolymers and homopolymer are simultaneously doped by the non-oxidizing protonic acid resulting from the elimination of D rendering the copolymer or homopolymer electrically conductive.
Another aspect of this invention relates to a solution which comprises:
a) an aqueous or organic solvent; and
b) one or more forms of the copolymers and
homopolymers of Formulas I to XI.
Solutions of Formulas I to XI can be conveniently used to form conductive articles by optionally removing the solvent, then inducing elimination of "D" and "H", thereby producing doped electrically conductive polymers of Formulas XII to XXII. The use of the solutions of this invention in the methods of this invention provides conductive article and composites of all shapes, as for example, films and fibers and coatings.
Another aspect of this invention relates to the processing of polymers of the Formulas I to XI and blends of these polymers and conventional thermoplastic and/or thermosetting polymers, i.e., polyolefins, polyesters, polyacrylates, halogenated polyolefins, polyvinyls, such as polyvinyl alcohol, and polyvinyl chloride,
polyvinylidene dichloride, polyalkylene oxides,
polysiloxanes, polycarbonates, polyamides, and the like to form conductive articles.
Several advantages flow from this invention. For example, this invention provides a simplified thermally activated process for direct formation of conductive doped poly(heteroaromatic vinylenes) and poly(aromatic
vinylenes) from non-conjugated precursor polymers without the need for a distinct doping step.
The discovery that non-oxidizing protonic acids dopants render conjugated polymers highly conductive now provides a wide range of new p-type dopants with attributes previously not available. These new protonic acid dopants offer a significant advantage over the previous art (redox dopants) because no. by-products are produced by the doping process. In contrast, redox dopants such as FeCl3, NOBF4, SbF5, MoCl5 and the
like, produce a neutral by-product from the doping process (i.e. FeCl2, NO, AsF3, SbF3, MoOCl). Additionally, these new dopants can impart additional desirable
properties to doped polymers. In particular, long-chain alkyl or perfluoroalkyl carboxyiic or sulfonic acid type dopants can function as plasticizers and can serve to significantly modify the cohesive energy density of doped polymers. With the proper choice of acid dopant, it should be possible to significantly improve the thermal stability, solution and melt processability, and
environmental stability of presently known highly
conductive polymers.
DETAILED DESCRIPTION OF THE INVENTION
One aspect of this invention is a homopolymer or a copolymer comprising recurring monomeric units selected from the group consisting of those of the Formula I to XI, wherein o, q, p, n, m, R1, R2, R3, R4, R5, R6,
R7, R8, R9, R10, R11, R12, R13, R14,
R15, R16, R17, Z-, D, X1 and X2, are as
described above.
Illustrative of useful R1, R2, R3, R4, R5,
R6, R7, R8, R9, R10, R11, R12, R13 and
R14 groups are hydrogen; cyano; nitro; halo; hydroxyl; amino; alkyl such as methyl, ethyl, butyl, pentyl, hexyl, octyl, nonyl, text-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1-propenyl,
4-butenyl, 1-pentenyl, 6-hexenyl, 1-heptenyl, 8-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonyloxy, ethoxy, octyloxy, and the like; cycloalkenyl such as cyclohexenyl, cyclopentenyl and the like; alkanoyl such as butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the like; arylamino and
diarylamino such as phenylamino, diphenylamino and the like; alkylsulfinyl, alkylsulfonyl, alkylthio,
arylsulfonyl, arylthio, 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,
ethoxycarbonyl, butoxycarbonyl and the like; alkyl amino and dialkylamino such as dimethylamino, methylamino, diethylamino, ethylamino, dibutylamino, butylamino and the like; cycloalkyl such as cyclohexyl, cyclopentyl,
cyclooctyl, cycloheptyl and the like; alkoxyalkyl such as methoxymethylene, methoxyethoxyethylene,
methoxydiethoxyethylene, ethoxymethylene, butoxymethylene, propoxyethylene, pentoxybutylene and the like;
arylalkylamino such as methylphenylamino, ethylphenylamino and the like; aryloxyalkyl and aryloxyaryl such as
phenoxyphenylene, phenoxymethylene and the like; and various substituted alkyl and aryl groups such as
1-hydroxybutyl, 1-aminobutyl, 1-hydroxylpropyl,
1-hydroxypentyl, 1-hydroxyoctyl, 1-hydroxyethyl,
2-nitroethyl, trifluoromethyl, 3,4-epoxybutyl,
cyanomethyl, 3-chloropropyl, 4-nitrophenyl,3-cycanophenyl, 1-hydroxy-methyl, and the like; sulfonic acid terminated alkyl and aryl groups, and salts thereof; carboxyiic acid and derivatives thereof such as esters, anhydrides and salts thereof, and phosphoric acid terminated alkyl and aryl groups, and derivatives thereof such as esters, and salts thereof; such as ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid and sodium salts, phenylsulfonic acid, and the corresponding carboxyiic acids, esters and anhydrides and salts thereof. Exemplary of other useful R1 to R14 groups are moieties of the formula:
-(OR15)r-OR16 or -R15-(OR15)-OR16 where r, -R15- and -R16 are as described above.
Useful R15 groups include divalent moieties of the
formulas -(CH2)2-, -(CH2)3- and
(CH2C(CH3)2)-, and useful R16 groups include
-CH3, and -CH2CH3. Illustrative of substituents
having such R15 and R16 are ethylene glycol
monomethylether, diethylene glycol monomethylether, triethylene glycol monomethylether, tetraethylene glycol monomethylether, and the like.
The nature of the D leaving group may vary widely with the proviso that at least about 1 mole percent of D leaving groups based on the total moles of D leaving groups is a moiety which upon elimination forms a non-oxidizing organic or inorganic protonic acid having a pKa equal to or less than about 4, or an acid which can be converted via complexation with Lewis Acids into such an acid. In the preferred embodiments of the invention, at least about 2 mole % of D groups form such an acid, in the more preferred embodiments of the invention, at least about 5 mole% of D groups form such an acid, and in the most preferred embodiments of the invention, at least about 10 mole % of D groups form such an acid. The said D groups generate on elimination of said acids having the specified pKa, which may then simultaneously dope the polymer of Formula XII to XXII forming the electrically conductive polymer. Generally, useful D groups fall into two general categories or classes of moieties, those which form the required inorganic or organic acid, and those which form species which can be converted into such acids. Illustrative of D leaving groups which do not form the required acid but which can be converted into same pseudohalogens such as -OCN, -OR1, -SR1, -OCOR,
-SeR1, -P(OR1)2, and the like where R1 is hydrogen or an aliphatic or aromatic group such as alkyl,
arylalkyl, alkylaryl, alkoxyalkyl, arylalkoxy, and the like. Another class of useful D leaving groups are neutral D groups which on elimination directly form the non-oxidizing inorganic or organic acid. Illustrative of this class of D groups are species such as -OSO2R1,
-CO2R1, -OSO3R1 -OPO(OR1) (OR2), and halogen
where R1 is as described above, as for example,
hydrogen; alkoxyalkyl, such as methoxymethyl,
ethoxymethyl, and the like; alkyl such as methyl, ethyl, propyl, and butyl; aryl and alkylaryl such as phenyl, tolyl and the like; arylalkyl such as benzyl, phenethyl, 4-phenyl-butyl and the like; alkanoyl and aroyl such as acetyl, butanoyl, benzoyl, and the like; alkanesulfonyl and arylsulfonyl such as methenesulfonyl, ethanesulfonyl, butanesulfonyl, toluenesulfonyl, phenylsulfonyl, and the like; and alkyl or aryl group substituted with carboxylic or sulfonic acid groups or salts thereof such as
butylsulfonic acid, butylcarboxylic acid, pentyl sulfonic acid; pentyl carboxyiic acid, propane sodium sulfonate, pentane sodium sulfonate, and the like.
Another class of useful D group are zwitteronic species in which the cationic portion can be eliminated as a neutral species, preferably a volatile one, and the anionic portion is an anion of a non-oxidizing organic or inorganic protonic acid or is anionic species which can be converted into such an anion. Illustrative of such D groups are species of the formulas: - +SR1R2 Z-, pyridinium, Z-, -N+R1R2R3 Z-, such as
-+P(O)R1R2 Z-,-P+R1R2R3 Z-,
-+N(O)R1R2 Z- and S(O)R1R2 Z, wherein
R1, R2 and R3 are as described above, as for
example, alkyl, such as methyl, ethyl, propyl, butyl and the like; alkylaryl, alkoxyaryl, and aryl such as phenyl, tolyl, anisyl, and the like; arylalkyl such as benzyl, phenethyl, 4-phenylbutyl, and the like; or R1, R2, and R3 together may form an alkenylene or alkylene chain such as -(CH2)4-, -(CH2)3-, -(CH2)7-,
-(CH2)5-, -(CH2)6-, -CH-CH-CH2-, -CH-CH-CH-CH-,
-CH2SCH2-, and -CH2-O-CH2-, -CH2NH-CH2-,
-CH2-CH2-CH2-NH-, and the like or an alkenylene or alkynylene chain having one or more unsaturated moieties completing an alicyclic ring or an aromatic or heterarommatic ring structure;
Z is the anion of a non-oxidizing protonic acid such as
",
Figure imgf000018_0001
3 2 3 g
perfluorooctanoic acid, CH3C6H4
Figure imgf000018_0002
3 3 and the like.
Figure imgf000018_0003
Preferred for use in the practice of this invention are homopolymers, and random or block copolymers of the above Formulas I to XI in which:
m, n, o and p are the same or different and are selected such that m, or the sum of n, o and p is an integer at least about 40, with the proviso that at least one of n or o is greater than zero; preferably that the sum of n, o and p, or m is at least about 75;
q is an integer from 0 to about 4;
R1, R2, R3 and R4 are the same or different
at each occurrence and are hydrogen, hydroxyl, halo, amino, cyano, or alkyl having from 1 to about 20 carbon atoms, such as 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-di-methylphenyl, 4-methylphenyl, 4-ethylphenyl, and 4-butylphenyl; phenylalkyl such as benzyl, phenethyl;
alkoxy having from 1 to about 12 carbon atoms such as methoxy, ethoxy, and butoxy; alkanoyl having from 1 to 20 carbon atoms such as formyl, acetyl, and propenyl;
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 as methoxymethyl, ethoxyethyl, heptoxypropyl, methoxyethyl, alkenyl having from 1 to about 20 carbon atoms such as allyl, vinyl and 3-butenyl; alkynyl such as ethynyl, propynyl, butynyl; or phenyl and alkyl substituted with hydroxyl, epoxy, sulfonic acid, nitro, cyano, phosphoric acid, carboxylic acid esters, anhydrides, or halo
substituents such as trifluoromethyl, 3,4-epoxybutyl, cyanomethyl, 2-nitroethyl, 3-chloropropyl, 4-nitrophenyl, -CH2CH2CH2SO3H; -CH2CH2CH2P(O) (OH)2; and
-CH2CH2CH2CO2H; moiety of the formula:
-(OR15)r-OR16 or -R15-(OR15)r-OR16 wherein
R15 is alkyl having from 1 to about 4 carbon atoms;
R16 is alkyl having from 1 to about 10 carbon atoms; and
r is a natural number from 1 to about 25 such as ethylene glycol monomethylether, diethylene glycol monomethylether, triethylene glycol monomethylether, tetraethylene glycol monomethylether and the like; or any of R1 and R2 or R3 and R4 substituents taken
together may form an alkylene, alkynylene or alkenylene chain having from 2 to 20 carbon atoms completing a 4, 5,
6, 7, 8, 9 or 10 membered ring system which may include one or more heteroatoms of oxygen, nitrogen or sulfur such as 1,4-butanediyl, 1,2-ethanediyl, -CH2SCH2-,
-N-CH-CH-CH-, -CH-CH-CH-CH-, -CH2OCH2-,
-CH2CH2-NH-CH2-, or -CH2CH2-NH-.
R5 to R14 are the same or different at each
occurrence and are hydrogen, hydroxyl, halo, amino, cyano, alkyl having from 1 to about 12 carbon atoms, substituted alkyl, phenyl, substituted phenyl, alkylthio having from 1 to about 12 carbon atoms or alkoxy having from 1 to about 12 carbon atoms; alkylamino having about 1 to about 12 carbon atoms or any of R5 and R6, or R7 and R8, or
R9 and R10, or R11 and R12, or R13 and R14
substituents together may form an alkylene chain having 2 to about 20 carbon atoms completing a 4, 5 or 6 membered ring system which may include one or more heteroatoms of oxygen or sulfur such as 1,4-butendiyl, 1,2-ethanediyl, -CH2SCH2 CH2OCH2-; -CH2-CH-CH-CH-, X, and X2 are the same or different and are
oxygen, sulfur or -NR17 wherein R17 is hydrogen or
alkyl, or R1;
D is the same or different at each occurrence and is moieties of the formula:
(a) -OSO3R1, -OSO2R1, -OPO(OR1)(OR2)
-NR1R1, -OCOR1, -OSOR1, -OSO2NR1R2,
-OSONR1R2, or -OSiR1R2R2; wherein R1 and R2 and R3 are the same or different
at each occurrence hydrogen; alkyl, such as methyl, ethyl, propyl, butyl, hexyl, and octyl; alkanoyl, benzoyl or alkyl or alkoxy substituted benzoyl, such as benzoyl, butanoyl, ethanoyl; phenoxy; alkylphenyl and alkoxyphenyl such as tolyl, anisyl methlphenyl, dodecyl phenyl; and ; alkoxyalkyl such as methoxyethyl; phenylalkyl such as benzyl or phenethyl; (b) F, Cl, Br or I;
(c) -+S(O)R1R2 Z-, and -S+R1R2 Z- and
-+N(O)R1R2 Z-, where R1 and R2 are the same or different at each
occurrence and are alkyl such as methyl, ethyl, or butyl, or R4 and R2 together form an alkylene, alkynylene, or alkenylene chain containing one or more unsaturations such as 1,4-butanediyl, 1,3-propanediyl or 1,5-pentanediyl completing a saturated or unsaturated ring structure, or an aromatic or heteraromatic ring structure; and
(d) -N+R1R2R3Z-, and -P+R1R2R3Z-, where R1, R2, R3 are the same or different at each
occurrence and are hydrogen, alkyl such as methyl, ethyl, propyl, and butyl; aryl; arylalkyl such as benzyl and phenethyl; alkylaryl and alkoxyaryl such as tolyl and anisyl; and alkoxyalkyl such as methoxymethyl; or two or three of R1, R2 and R3 together may form an
alkylene, alkynylene or alkenylene chain having one or more degrees of unsaturation completing a saturated ring structure, such as piperidinium or an aromatic or
heterocyclic ring structure such as pyridinuim and substituted pyridinium; and
Z- is an anion such as
Figure imgf000021_0001
Figure imgf000021_0003
AsXb- where X is halogen, or a moiety of the
formula
Figure imgf000021_0002
wherein R18 is alkyl, or aryl, which may be
unsubstituted or substituted with one or more halo, alkyl, alkoxy or aryl groups.
Particularly preferred for use in the practice of this invention are homopolymers or random copolymers of the above-referenced Formula I to XI wherein:
q is an integer from 0 to 3;
m, and the sum of n, o and p are at least about 100 and at least one of n or o is greater than zero.
R1, R2, R3 and R4 are the same or different
at each occurrence and are hydrogen; hydroxy; halo; cyano; amino; 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 having from 1 to about 12 carbon such as methoxy, nonyloxy, dodecanoxy, ethoxy and butoxy; alkylthio having from 1 to about 12 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio; alkoxyalkyl having from 1 to about 12 carbon atoms such as ethoxymethyl and butoxymethyl; or a moiety of the formula:
-(OR15)r-OR16 or -R15(OR15)r-OR16 wherein :
R15 is alkylene of about 2 to 3 carbon atoms;
R16 is alkyl of from 1 to about 3 carbon atoms; and r is a natural number from 1 to about 10;
R5, R6, R7, R8, R9, R10, R11 , R12 ,
R13, and R14 are the same or different at each
occurrence and are hydrogen; hydroxy; halo; amino; cyano; alkyl, such as methyl, ethyl or the like; substituted alkyl such as butylsulfonic acid, propylsulfonic acid, cyanomethyl, epoxybutyl, hydroxy butyl, methyl propyl carboxylate, pentafluoroethyl, nitropropyl, and
butylcarboxylic acid; alkoxy such as methylthio, ethylthio and the like; or any of R5 and R6, R7 and R8, R9
and R10, R11 and R12 together may be propylene,
butylene or a like divalent alkylene group forming a ring structure ;
Z- is
Figure imgf000022_0001
where X is halogen, or l I
Figure imgf000022_0002
wherein R18 is alkyl, phenyl, alkylphenyl or phenylalkyl which may be unsubstituted or substituted with one or more fluoro, chloro, Bromo or cyano groups;
X1 and X2 are the same or different and are
oxygen, sulfur, or NR17 and
D is the same or different at each occurrence and is: a leaving group, with the proviso that at least about 2 mole % of D leaving groups based on the total moles of D leaving groups on an elimination forms an acid laving a pKa equal to or less than about 4, preferably less than or equal to about 3, more preferably equal to or less than about 2 and most preferably equal to or or less than about 1, or can be converted into such an acid and is selected from the group consisting of:
(a) -OSO2R1 and -R1CO2- where R1 is
hydrogen; alkyl such as methyl, ethyl, butyl, and octyl; phenyl; alkylphenyl and alkoxyphenyl such as tolyl and anisyl; phenylalkyl such as benzyl and phenethyl; and alkanoyl and aryloyl such as acetyl and benzoyl; or (b) -N+R1R2R3 Z-, -S+(O)R1R2 Z-,
-+N(O)R1R2 Z- or -S+R1R2 Z-, wherein R1,
R2 and R3 are aryl such as phenyl; alkyl such as
methyl, ethyl, and butyl; alkoxyalkyl such as
methoxymethyl; arylalkyl such as benzyl and phenethyl; and alkylphenyl and alkoxyphenyl such as tolyl and anisyl; or R1, R2 and R3 together form an alkynylene, alkylene or alkenylene chain such as 1,4-butanediyl, 1,5- pentanediyl, and 1, 5-pent-1,3,5-trienediyl, completing a ring structure such as tetrahydrothiophenonium;
pyridinium; and piperidinium; and
Figure imgf000023_0001
g
where X is halogen, or
Figure imgf000023_0002
wherein R18 is alkyl having from 1 to about 20 carbon atoms, alkylphenyl having from 7 to about 20 carbon atoms or phenyl which may be unsubstituted or substituted one or more fluoro, chloro, alkyl, bromo, or cyano, alkoxy or sulfonic acid, carboxyiic acid, phosphoric acid or
derivatives thereof (e.g. salts, esters and the like) .
Amongst these particularly preferred embodiments, most preferred are random copolymers and homopolymers of Formula I to XI in which:
q is an integer from 0 to about 2;
m, or the sum of n, o and p is at least about 125 R1 to R4 are the same or different at each
occurrence and are hydrogen, hydroxyl, cyano, halogen, alkyl having 1 to about 12 carbon atoms, alkoxy having 1 to about 12 carbon atoms, or alkoxyalkyl having 2 to about 12 carbon atoms or a moiety of the formula:
-(OR15)rOR16 and -R15(OR15)r-OR16 wherein:
R15 is -(CH2)2- or -CH2CH(CH3)-;
R16 is -CH3 or -CH2CH3; and
r is an integer from 0 to 10,
R5, R6, R7, R8, R9, R10, R11 and R12
are the same or different at each occurrence and are hydrogen, hydroxy, cyano, amino, alkyl, or any of R5 and R6, R7 and R8, R9 and R10, R11 and R12
together may form a divalent alkylene, alkynylene or alkenylene group having from 2 to about 6 carbon atoms forming an aromatic or saturated ring;
D is the same or different at each occurrence and is: a leaving group, with the proviso that at least about 2 mole % of D leaving groups based on the total moles of D leaving groups on an elimination forms an acid having a pKa equal to or less than about 4.0, preferably less than or equal to about 3, more preferably equal to or less than about 2 and most preferably equal to or or less than about 1, or can be converted into such an acid and is selected from the group consisting of:
(a)
Figure imgf000024_0004
+R1R2 Z- or -S+R1R2 Z- wherein
R1 and R2 are the same or different at each occurrence and are hydrogen; alkyl such as methyl, ethyl, propyl, and butyl; aryl such as phenyl; or R1 and R2 together may form an alkylene, alkynylene, or alkenylene chain and
(b) -N+R1R2R3 Z-, or
Figure imgf000024_0003
wherein R1, R2, R3 are alkyl such as methyl; ethyl;
and butyl; benzyl; phenyl; phenethyl; or two or more of R1, R2 and R3 together may form an alkylene,
alkynylene, or alkenylene chain such as 1,4-butanediyl, 1,5-pentanediyl, and 1,5-ρent-1,3-dienediyl completing a saturated cyclic structure or an unsaturated aromatic or heteroaromatic structure such as pyridinium; and
(c) Z- is of the formula or
Figure imgf000024_0001
wherein R18 is alkyl having from 1 to
Figure imgf000024_0002
about 20 carbon atoms which may be substituted with one or more halogen groups or, alkylphenyl having from 7 to about 20 carbon atoms; and
(d) X1 and X2 are sulfur, or -NH- or -NR17-. Especially good results are provided in those embodiments of the invention where D is a moiety of the formula:
+
-N+R1R2R3 Z- or -SR1R2 Z- wherein R1, R2, R3 and Z- are as described above.
This invention also relates to solutions of the homopolymers and copolymers of Formula I to XI comprised of one or more of said copolymers and homopolymers and a protic and/or an aprotic solvent. Useful solvents as can vary widely and include such solvents as water, ethanol, methanol, butanol, propanol, acetone, toluene, hexamethyl phosphoric triamide, dimethylformamide, dimethylacetamide, methylene chloride propylene carbonate, sulfolane and the like, or mixtures thereof.
The solvent chosen for use in any particular
situation will usually depend on the nature of the various substituents. For example, the more polar the particular substituents, the more polar the solvent; and conversely, the less polar the substituent the less polar the
solvent. In the preferred embodiments of this invention, solvents are selected from the group consisting of water, methanol, butanol, ethanol, propanol, sulfolane, dimethyl sulfoxide, methylene chloride, dimethylformamide, N-methyl pyrolidinone and mixtures thereof, and in the particularly preferred embodiments of the invention, the solvent is selected from the group consisting of water, sulfolane, methanol, butanol, and dimethyl formamide and mixtures thereof. Particularly preferred is water.
The copolymers and homopolymers of Formulas I to XI can be conveniently prepared in a one or two step
procedure. In the first step, polymers of the Formula I to XI in which D is -+SR1R2 Z- are formed. In
this step, a compound or group of compounds, whichever is applicable, of the following Formulas XXIII to XXXIII:
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
is treated with one mole equivalent of base to form polymers of the Formula XXXIV to XLIV:
J i
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000030_0001
In general, this reaction is carried out in solution using the protic or aprotic solvents described above. Bases for use in this reaction are not critical and the only
requirement being that the base is active in the solvent in which the reaction is being conducted. Illustrative of useful bases are alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal carbonates and bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; organic amine containing bases such as piperidine, pyridine, DABCO, ethylene diamine, tripropylamine, tributyl amine, and the like; alkali metal alkoxides such as potassium t-butoxide, lithium methoxide lithium ethoxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide; water
insoluble bases such as calcium oxide, Barium oxide, magnesium oxide and the like; and polymeric bases such as poly(p-amino styrene), basic forms of ion exchange resins such as Amberlyst and amberlyte resins in OH- form or free base forms. Preferred bases are sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide and sodium carbonate, and particularly preferred bases are sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. Amongst these particularly preferred embodiments, most preferred are those embodiments of the invention in which the base is sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium methoxide.
As noted above, solvents for use in this process are those in which the polymers of Formulas XXXIV - XLIV are soluble and can vary widely. Preferred solvents are water, methanol, ethanol, butanol, dimethylsulfoxide, acetone, sulfolane, dimethylformamide, N-methylpyrrolidone and acetonitrile, and particularly preferred solvents are water, methanol, ethanol, dimethylformamide, and
N-methylpyrrolidone, Amongst those particularly preferred solvents, most preferred solvents are methanol, ethanol, dimethylformamide and water.
Reaction temperatures are not critical and can vary widely. In general, the polymerization reaction is
carried out at a temperature of from about -15°C to about 200°C. In the preferred embodiments, reaction temperature of from about -15°C to about 50°C and in the particularly preferred embodiments reaction temperatures are from about -5°C to about 25°C.
Reaction pressures are not critical and the reaction can be carried out at sub-atmospheric pressure,
atmospheric pressure and super-atmospheric pressure. For convenience, the reaction is carried out at atmospheric or autogeneous pressure.
Reaction times can vary widely. In general, the reaction is carried out over a period of from about a few seconds to a few hours.
In the second step of the process, those polymers of the Formulas I to XII in which D is other than
-+ SR1R2 Z-, or those in which D is a mixture of
- +SR1R2 Z- with various other permissible D
groups are formed from polymers of the Formulas XXXIV to XLIV. In this step, solutions of polymers of the Formulas XXXIV to XLIV are treated with various agents or mixtures thereof to convert all or a portion of the -+SR1R2
Z- groups into other permissible D groups or mixtures of -+SR1R2 Z- and other permissible D groups.
Useful agents may vary widely and depends on the nature of the D moiety. Illustrative of useful agents are species of the formula:
(a) MOSO2R1, MCO2R1 and MOSO3R1 where M
is hydrogen or a metal ion and R1 is as described above such as alkyl, aryl, arylalkyl, alkylaryl and the like. Illustrative of suitable compounds are sodium toluene sulfonic acid, potassium methyl sulfonic acid, sodium trifluoroacetic acid, sodium acetate, potasium benzoate, and the like.
(b) NR1R2R3 where R1, R2 and R3 are the
same or different at each occurrence and are as described above such as hydrogen, alkyl from 1 to about 20 carbons aryl, alkylaryl or arylalkyl, or R1, R2, R3 form an alkylene, alkenylene or alkynylene chain completing a monocyclic, bicyclic, alicyclic, aromatic or
heteroaromatic ring system. Illustrative of suitable NR1R2R3 compounds are triethylamine, ethylamine,
diethylamine, cyclohexylamine, benzylamine,
1-phenylethylamine, tri-propylamine, methylaniline, diphenylamine, pyrazole, imidazole, oxazole, thiazole, or heterocyclic compounds such as pyridine,
1,2-dihydroquinoline, methylethylamine, benzyldimethylamino, N,N-dimethylaniline, trimethylamine, dimethylethylamine, piperidine, 5,6-benzoquinoline,
N-methyl piperdine, pyrrolidine, picoline, quinoline, isoquinoline, pyrrole, carbazole, purine, purimidine, morpholine, and the like.
(c) PR1R2R3, wherein R1, R2 and R3 are
the same or different at each occurrence and are as described above such as alkyl from 1 to about 20 carbons, aryl alkylaryl, arylalkyl, alkoxy from 1 to about 20 carbons, aryloxy, alkylaryloxy or arylalkyloxy.
Illustrative of such compounds are diphenylethyl
phosphine, triphenyl phosphine, triethylphosphine, benzyl dimethyl phosphine, phenethoxy diethylphosphine,
triphenoxyphosphine, tripentylphosphine,
tri-(3-tolyl)phosρhine, tri-(4-tolyl) phosphine, and the like.
(d) MX wherein M is a metal ion and X is OH-,
OR1, Cl-, F-, Br- and I-. Illustrative of these
materials are sodium iodide, sodium chloride, lithium fluoride, sodium bromide, sodium hydroxide, sodium
ethoxide and the the like.
OH
(e) R1NR2 wherein R1 and R2 are the same or
different and are alkyl having from 1 to about 10 carbon atoms, or aryl, alkylaryl, or arylalkyl having from about 6 to about 20 carbon atoms, or R1 and R2 together may form a cyclic structure. Illustrative of these materials are N,N-dimethyl hydroxyl amine, N,N-diethyl hydroxyl amine, N-phenyl-N-methyl hydroxyl amine,
l-hydroxypiperdine and the like.
(f) R1OH wherein R1 is hydrogen, alkyl, aryl, alkoxyalkyl, alkylaryl, arylalkyl, and the like as
described above.
Although we do not wish to be bound by any theory, we believe that these agents function in certain cases as nucleophiles to displace the labile sulfonium groups in polymers of Formulas I to XI which contain the other D groups. By judicious choice of agent or agents, reaction solvent and reaction time, the properties of polymers of Formulas I to XI can be tailored to meet desired
processing conditions, film forming properties, and morphology of the desired conjugated polymers of Formulas XII to XXII.
Particularly preferred agents are those of the formula:
MOSO2R1, MOSO3R1 and R1CO2M wherein M is
hydrogen or a metal ion, and R1 is alkyl of 1 to about 20 carbons, fluorinated alkyl, alkylphenyl, alkoxyphenyl, phenyl, or benzyl;
NR1R2R3, wherein R1, R2 and R3 are the
same or different at each occurrence and are hydrogen, alkyl of 1 to about 20 carbons, phenyl or alkylphenyl, alkoxyphenyl or phenylalkyl having from about 6 to about 20 carbon atoms or R1, R2, R3 taken together may
form an alkylene, alkynylene or alkenylene chain which may form a monocyclic or bicyclic or alicyclic or aromatic ring structure of from about 6 to about 20 carbon atoms such as pyridine; and
PR1R2R3, wherein R1, R2 and R3 are
alkoxy, aryloxy, alkylaryloxy, arylalkyloxy or alkyl.
Most particularly preferred agents are pyridine, trimethylamine, triethylamine, tributylamine, quinoline, tributylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, 4-dimethylamino-pyridine and the like.
In those embodiments of this invention where D is zwitterionic, Z- moieties can be totally or partially changed through use of standard ion exchange techniques. Such techniques are well known to those of skill in the art and will not be discribed herein in any great detail. Such exchanges may be carried out for a number of
purposes, for example, to modify the solubility
characteristics of a polymer, to modify the conductivity characteristics of the conjugated backbone polymer
resulting from elimination of the D group. Another aspect of this invention relates to a process for preparing conductive polymers from conjugated backbone copolymers and homopolymers of the Formulas XII to XXII which are prepared from the corresponding polymers of the Formula I to XI. In general, these neutral conjugated backbone polymers are prepared by thermal treatment of the precursor polymers of Formulas I to XI, either as
solutions or in the solid state as precast or
prefabricated articles. Generally, useful temperatures may range from about -10°C to about 300°C. The thermal treatment eliminates D in two ways, as DH or as D and HZ. Useful temperatures depend on the structure of the
polymer, the nature of D and the nature of Z-, if
present, and may vary widely. Temperatures which are generally useful can be determined by routine
experimentation. The elimination of D forms one of two acidic species of DH and HZ, D and Z have been selected such that the conjugated backbone polymer formed by the elimination of D is spontaneously doped by the acidic species after elimination of D.
Chemical methods can also be used to convert
prepolymers I to VII into conjugated polymers of Formulas VIII to XIV. In these chemical methods, the precursor polymers of Formulas I to VII, either in solution or in the solid state, are treated with a chemical agent which causes elimination of D. For example, a Lewis acid can be used to form a protonic acid doped conjugated polymer from a precursor non-conjugated polymer by a Lewis-acid- catalyzed elimination reaction. Useful Lewis acids areAsX3, SbX3, PX5, PX3, BX3, AlX3 (where X is
halogen), and the like. Illustrative of such a system is poly(2,5-dibutoxyphenylene-1,4-diyl-1'-acetoxy
ethylene-1',2'-diyl), which can be converted into protonic acid doped and conductive poly(2,5-dibutoxyphenylene vinylene) by treatment with BF3 which induces
elimination of acetic acid which forms a new stronger protonic acid, H+BF3OAc-, that dopes the conjugated
polymer. It can be appreciated that mixtures of protonic acids, or mixtures of protonic acids and Lewis acids capable of inducing acid-catalyzed polymerization of suitable monomers in a suitable solvent or in pure liquid monomer can give conducting polymer composites in
non-conducting host polymers by in-situ polymerization of the monomer in the presence of a conjugated polymer.
Illustrative of useful monomers are those which polymerize by ring opening reactions. Such monomers include cyclic ethers, such as ethylene oxide, propylene oxide,
epichlorohydrin, oxetanes, 3,3-bis(chloromethyl) oxetane, tetrahydrofuran, oxepane, or a mixture of tetrahydropyran and other cyclic ethers, and the like; cyclic ethers containing more than one oxygen, such as 1,3-dioxolanes, 1,3-dioxanes, 1,3-dioxepanes, 1,3-dioxocanes,
1,3-dioxonanes, 1,3-dioxacycloundecanes,
1,3-dioxacyclotridecanes, 1,3,5-trioxanes, 1,3,5- trioxepanes, 1,3,6-trioxocanes, 1,3,5,7-tetraoxanes, 1,3,6,9-tetraoxacycloundecanes, 1,3,6,11-tetraoxacyclotri- decanes, 1,3,6,9,12-pentaoxacyclotetradecanes,
1,3,6,9,12,15-hexaoxacycloheptadecanes, and the like;
cyclic sulfides, such as thiacyclopropane,
thiacyclobutane, and the like; lactams, such as
3-ethanolactam, 3-propanolactam, 4-butanolactam,
5-pentanolactam, 6-hexanolactam, 7-heptanolactam and the like; lactones, such as γ-propiolactone, γ-butyrolactone, Υ-butyrolactone, γ-valerolactone, γ-caprolactone, and the like. Other lactones analogues, such as glycolides, lactides, ethylene carbonate, 1,3-dioxepane-7-ones,
1,5-dioxepane-7-ones, 1,4-dioxepane-7-ones, 1,4-dioxane- 2-ones, ethylene oxalate, dioxane-2, 6-diones, 1,4- thioxane-3-ones, thioxepane-2-ones, and the like; bicyclic acetals, such as 2,7-dioxabicyclo [2.2.1]heptane,
6 ,8-dioxabicyclo [3.2.1] octane, 2,7-dioxabicyclo- [4.1.0]heptane, 2,6-dioxabicyclo[4.1.0]heptane,
2,6-dioxabicyclo [3.1.1] heptane, 2,8-dioxabicyclo- [3.2.1]octane, and the like; cyclic siloxanes, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaalkylcyclotrisiloxane, octaalkyltetrasiloxane, and the like; and cyclic amines such as aziridine, azetidine, conidine, 1-azabicyclo[2.2.2] octane, 1,4-diazabicyclo- [2.2.2]octane, and the like. Illustrative of such a system is a solution of poly(3-methoxythienylene vinylene) in tetrahydrofuran (THF) to which has been added
pentafluoropropionic acid in a sufficient amount so as to dope the conjugated polymer and cause acid-catalyzed polymerization of THF. Upon removal of residual THF from the composite solution, a conductive composite film comprised of protonic acid doped poly(3-methoxythienylene vinylene) and ρoly(tetrahydrofuran) is obtained.
Useful Lewis acids are those mentioned above. The conductive polymer solutions used can be either a true solution or a suspension. The polymer can be either a conjugated polymer or a non-conjugated precursor polymer which is capable of acid-catalyzed transformation into its conjugated form.
The electrically conductive forms of the polymers of Formulas XII to XXII are formed by the elimination of D from polymers of Formulas I to XI. The level of
conductivity may vary widely and is such that the
conductivity is at least about 10-8ohm-1cm-1. The
upper conductivity is not critical, and usually the highest conductivity which can be obtained is provided.
In the preferred embodiments of the invention, the
conductivity is equal to or greater than about
10-4ohm-1cm-1, and in the more preferred embodiments of the invention, the conductivity is equal to or greater than about 10-2ohm-1cm-1. In the most preferred
embodiments of the invention, the conductivity is equal to or greater than about 10-1ohm-1cm-1.
As noted above, this invention also relates to
solutions of the polymers of Formulas I to XLIV. The solvent type employed can vary widely, from polar to non-polar. Useful solvents include water and various organic solvents. In general, solvents which can be used in the practice of this invention will have a dipole moment greater than zero and less than or equal to about 5, and a dielectric constant of less than about 190.
Illustrative of useful solvents are water, alcohols, such as methanol, ethanol, propanol, trifluoroethanol, benzyl alcohol, butanol and the like, amines such as
triethylamine, tributylamine, diethylamine, pyridine, and the like, acids such as trifluoroacetic, acetic, formic, methane sulfonic, sulfuric and trifluoromethane sulfonic acids; anhydrides such as acetic anhydride, trifluoro acetic anhydride propionicanhydride and the like, sultones, such as propane sultone, butane sultone, pentane sultone and the like; alkyl alkanesulfonates such as methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate and the like;
linear and cyclic ethers such as 1,2-dimethoxyethane, dimethoxymethane, dioxane, glymes, diglymes,
tetrahydrofuran, 2-methyltetrahydrofuran, anisole, diethylether and the like; nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile and the like; hydrocarbons such as cyclohexane, pentane, hexane and cyclopentane; halocarbons such as carbon tetrachloride, dichloromethane, dichloroethylene, and 1,2-dichloroethane, trichloroethylene; aromatic solvents such as benzene, toluene, xylene, nitrobenzene and the like; ketones such as 4-methyl-pentanone, methylethylketone, acetone, and the like; carbonates such as propylene carbonate, dimethyl carbonate, ethylene carbonate and the like; esters such as methyl formate, methyl acetate, Y-butyrolactone, ethyl acetate and the like; nitroalkanes, such as nitromethane, nitroethane, nitropropane, and the like; amides such as N-ethyl formamide, N-ethyl acetamide, dimethyl formamide, dimethyl thioformamide, N,N-dimethyl acetamide,
N-methylpyrrolidinone and the like; organophosphorus compounds such as hexamethyl phosphorous triamide, diethylphosphate, triethylphosphate, trimethylphosphate and the like; and organosulfur compounds such as
sulfolane, methyl sulfolane, dimethyl sulfone, dimethyl sulfoxide, dimethyl sulfolane, glycol sulfite, tetraethylsulfamide and the like. Mixtures of such solvents can also be used as for example mixtures of sulfolane and acetonitrile, or water and methanol.
The solvent or solvent mixture selected for use in any particular situation will depend primarily on the polarity of various R1, R2, R3, R4, R5, R6,
R7, R8, R9, P1, R2, R10, R11, R12, R13,
R14, R14, R16 and/or R17 substituents, and/or the
state of the polymer, i.e. eliminated or uneliminated. In general, more polar compositions will require solvents with higher dielectric constants and dipole moments
(within the above specified range). Conversely, less polar compositions will require solvents with lower dielectric constants and dipole moments (within the above specified ranges).
In general, solvents chosen for use with polymers having relatively polar substituents will usually have a dipole moment of from about 0.3 to about 5.0, preferably from about 1.8 to about 5.0; and a dielectric constant of from about 10 to about 190, preferably from about 20 to about 100. Illustrative of such solvents are alcohols, such as methanol, ethanol, isopropanol, and the like;
linear and cyclic ethers, such as tetrahydrofuran,
tetrahydropyran, 2-methyltetrahydrofuran, diethylether, diglyme, glyme and the like; halocarbons such as
chloroform, 1,2-dichloroethane, dichloromethane and he like; amides, such as dimethylformamide,
N,N-dimethylacetamide, N-methyl pyrrolidone and the like; substituted aromatics, such as xylene, anisole, toluene and the like; nitriles, such as acetonitrile,
propionitrile, benzonitrile, butyronitrile, and the like; sulfoxides and other sulfur containing solvents such as dimethylsulfoxide and the like; nitro substituted alkanes and aromatics such as nitromethane, nitropropane,
nitrobenzene and the like; and carbonates such as
propylene carbonate, ethylene carbonate and the like, and water or mixtures thereof. In general solvents chosen for use with polymers having relatively non-polar substituents will have a dipole moment of from about 0 to about 3.0, preferably from about 0 to about 2.5; and a dielectric constant of from about 2.0 to about 50, preferably from about 2.0 to about 35. Illustrative of such solvents are halocarbons such as dichloromethane, and the like; aromatic solvents such as toluene, xylene, benzene and the like; cyclic and linear ethers such as dimethoxyethane, tetrahydrofuran and the like; esters such as ethylacetate, methyl formate and the like; sulfoxides, such as dimethylsulfoxide and the like; cyclic and linear amides, such as dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide and the like; and ketones such as acetone and the like and mixtures thereof.
In general, 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 with doped or undoped polymers. These viscous
embodiments of the invention may be particularly useful for silkscreening, extruding fibers, and for applying thick film coatings on substrates. For other
applications, it may be preferred, however, to use
sufficient liquid solvent to lower the viscosity of the gel or solution to a point where it flows at least
sufficiently to conform to a container shape or mold or set up as a coating in a reasonable short period of time, e.g., in 30 minutes or less. Preferably, the solvent is present in sufficient amounts to lower the viscosity of the solution to less than about 2,000 centipoise, and more preferably from about 1 to about 1000 centipoise.
In addition to the essential copolymer or homopolymer and solvent, whichever is applicable, the solutions of this invention can include other optional ingredients and mixtures thereof which either dissolve or do not dissolve in the solution. The nature of such optional ingredients can vary widely, and include those materials which are known to those of skill in the art for inclusion in polymer articles. In the case of dissolvable components, 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 other conventional polymers such as polyacrylonitrile, polyvinylidene chloride, polyethylene oxide, polystyrene, nylon, polyvinylsulfonic acid,
cellulose acetate butyrate, polypropylene, polyethylene, cellulose acetate, polyphenylene oxides, polycarbonates, polyacrylates, and the like. In the case of nonsoluble components, materials may be present which either fill or form a substrate for the conductive polymer cast from the solution. These non-soluble components include other polymers such as polyacetylene which may become conductive upon doping, graphite, carbons, metal conductors,
reinforcing fibers and inert fillers (such as clays and glass).
The method of forming the solutions of this invention is not critical and can vary widely. For example, the solution of this invention can be prepared merely by dissolving the desired amount of the polymer in a solvent in which it is soluble such as water, toluene or
nitrobenzene. Or, solutions can be formed by directly polymerizing the monomers and/or eliminating D from polymers in the solvent.
Various methods are contemplated for using the solution of the present invention. For example, it is contemplated to remove the solvent from the solution to allow the copolymer or homopolymer to solidify. The solvent can be removed from the solution through use of any conventional solvent removal method but is removed preferably by evaporation. Alternatively, the solvent can be removed by extraction with an extractant in which the solvent is substantially more soluble than the polymer.
As will be appreciated by those skilled in polymer processing, the ability to form polymer articles by
removing a solvent from a solution enables one to prepare articles of a wide variety of shapes and sizes. Thus, for example, by removing volatiles from the present solution spread on a surface, films and coatings of any desired thickness can be prepared. By extruding the solution through a die, fibers or films can be made. Similarly, by removing volatiles from the solution in a mold of various shapes, shaped articles conforming in shape to the mold can be prepared. It will be appreciated that some
shrinkage might occur between the solution in its last flowable state to the final article, but such shrinkage is conventionally accounted for in molding polymers from solution. It is also contemplated that, once a solution is formed, a partial or substantial removal of solvent will occur prior to placing the solution on a surface or in a mold, with the final venting of solvent occurring on the surface or in the mold. It is contemplated that, if additional soluble components are introduced into the solution, they will, unless also volatile, be present in the shaped article formed. If the fourth component is a non-volatile liquid, then the removal of volatile
components may leave a new liquid or plasticized form of doped conducting polymer or neutral polymer. If the additonal components are volatile, then foamed or expanded cellular forms of the polymer may be formed.
The polymers of Formula I to XI or blends of such polymers and one or more thermoplastic polymers can also be melt processed into useful articles using conventional melt processing techniques. For example, if a blend is used, the various components are granulated, and the granulated components mixed dry in a tumbler, Banbury mixer or other suitable mixer. The components of the blend are usually mixed until the blend is uniform or as homogenous as possible. The blend is then heated above the melting point of at least one of the polymeric components preferably with mixing. Such treatment may cause elimination of D and formation of conductive polymers XII to XXII as a conductive blend with one or more thermoplastic polymers. For example, the blend may be conventionally melted by heating in a conventional extruder. As will be appreciated by those of skill in polymer processing, the ability of a polymer to be melt processed allows for the manufacture articles of a wide variety of shapes merely by placing the melt in a mold of the desired shape and cooling the melt below the melting point of at least one of the polymer components. For example, by spreading a melt on a surface and cooling, films of any desired thickness can be fabricated.
Similarly fibers and films can be made by extruding the melt through a suitable die, and shaped articles can be formed by placing a melt into a mold having the desired shape and cooling the melt below the melting point of one or more of the polymeric components.
The polymers of Formulas I to XXII can be fabricated alone or as blends with one or more thermoplastic
polymers. Useful thermoplastic polymers may vary widely. Illustrative of useful polymers are those formed by
polymerization of unsaturated monomers such as
polypropylene, polyethylene, poly(octadiene), polyiso- butylene, ρoly(pentene), poly(styrene), poly(2-methyl styrene), poly(4-methylstyrene), poly(hexene), poly(methyl- hexene), poly(butylene), poly(methylpentene),
ρoly(4-methylpentene), poly(vinyl-cyclopentane),
poly(vinylcyclohexane), poly(vinylnaphthalene),
poly(vinylchloride), poly(vinyl fluoride), poly-
(vinylidene fluoride), poly(vinyl alcohol), poly(acrylo- nitrile), poly(vinyl acetate), poly(vinylmethylether), poly(methylacrylate), ρoly(methylmethacrylate), acrylo- nitrile-butadiene-styrene copolymer, polyacrylamide, and the like. Also illustrative of useful thermoplastic polymers are polyamides and polyesters such as the
copolyamides of 30% hexamethylene diammonium isophthalate and 70% hexamethylene diammonium adipate, the copolyamide of up to 30% bis(4-aminobutyric acid) (nylon 4), poly
7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid) (nylon 8), poly(6-aminohexanoic acid) (nylon 6), poly(hexamethylene adipamide) (nylon 6,6),
poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7),
ρoly(octamethylene suberamide) (nylon 8,8),
poly(hexamethylene sebacamide) (nylon 6,10),
poly(nonamethylene azelamide) (nylon 9,9),
poly(decamethylene azelamide) (nylon 10,9), poly(deca- methylene sebacamide) (nylon 10,10), poly[bis(4-amino- cyclohexyl)methane-1,10-decanedicarboxamide], poly(m- xylylene adipamide), poly(p-xylylene sebacamide),
ρoly(2,2,2-trimethylhexamethylene tere-phthalamide), poly(piperazine sebacamide), poly(metha-phenylene
isophthalamide) (Nomex), poly(p-phenylene terephthalamide) (Kevlar), poly(11-amino-undecanoic acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12),
polyhexamethylene isophthalamide, polyhexamethylene
terephthalamide, poly(9-aminononanoic acid) (nylon 9), polycaproamide, poly(ethylene terephthalate), poly(cyclo- hexylenedimethylene, terephthalate), poly(ethylene
dodecate), ρoly(butylene terephthalate, ρoly[ethylene(2,7- naphthalate)], ρoly(methaphenylene isophthalate), poly- (glycolic acid), poly(ethylene succinate), poly(ethylene adipate), poly(ethylene sebacate), poly(decamethylene azelate), poly(decamethylene azipate), poly(decamethylene sebacate), ρoly(dimethylpropiolactone), poly(para- hydroxybenzoate) (Ekonol), poly(ethylene oxybenzoate)
(A-tell), poly(ethylene isophthalate), poly(tetramethylene terephthalate), poly(hexamethylene terephthalate), poly- (decaethylene terephthalate), poly(l,4-cyclohexane
dimethylene terephthalate) (trans), ρoly(ethylene 1,5- naphthalate), poly(ethylene 2,6-naphthalate), poiy(1,4- cyclohexylidene dimethylene terephthalate) (Kodel) (cis), poly(1,4-cyclohexylidene dimethylene terephthalate)
(Kodel) (trans), poly(phenyl sulfide), poly(phenylene oxide), poly(carbonates) such as poly[methane bis(4-phenyl) carbonate], and poly[2,2-propane bis(4-phenyl) carbonate].
This invention has many uses. For example, the conductive polymers of this invention can be used in the fabrication of conductive articles such as housings for sensitive electronic equipment as for example microprocessors; infrared, radio wave, and microwave absorbing shields; flexible electrical conducting
connectors; antistatic coatings; conductive bearings and brushes and semiconducting photoconductor junctions. It is contemplated that the conductive solutions of this invention will be used in the fabrication of the articles of this invention and as liquid conductors or
semiconductors much in the way that liquid mercury is used in various devices. Examples of such devices include gravity switches, fluid level detecting devices and other electrical or electronic switches and sensors.
The following specific examples are present to illustrate the invention and are not to be construed as limitations thereon.
EXAMPLE I
1,4-Xylene bis(tetramethylene sulfonium chloride) (5g; 14.2 m mole) and 0.296 g of 2 , 5-dimethoxy-1,4- xylene bis (tetramethylene sulfonium chloride) (0.71 m mole) was dissolved in 37.5 ml of H2O). The solution (0.4 M) was filtered and then degassed by N2 for 3h.
After cooling in ice bath for half an hour, a 0.4 M degassed NaOH (0.6 g NaOH in 37.4 ml H2O) solution was syringed into the above bissulfonium salt mixture to start the polymerization. After 20 minutes, the reaction mixture was diluted by 130 ml of H2O and neutralized by 1 M HCl to about pH7.
The resulting solution (about 200 ml) was dialyzed against deionized water from 3 to 5 days. About half of the dialyzed solution was cast into a precursor film, which was then thermally converted into the fully
eliminated and conjugated conducting polymer. The
elemental analysis of this conjugated polymer was: C(90.22%), H(6.01%), 0(3.77%). This result is consistamt with 13% dimethoxy-substituted monomeric units plus 87% unsubstituted monomeric units. Intrinsic viscosity was measured to be 4.62 dl/g. About 10 ml of the above precursor polymer solution was mixed with 3 ml aqueous solution of disodium salt of 1,3-benzene disulfonic acid (1 g, 3.5 m mole). A white fibril-like polymer precipitate was obtained. After rinsing with 5 ml de-ionized water, the polymer was finger-pressed (between two glass slides) into a porous sheet-like material. The pressed polymer was then dried at room temperature overnight under dynamic vacuum.
The dried polymer was then heated (ca. 100-150°C) for 3 to 5 minutes under vacuum. A black-brown film
(thickness about 60 microns) was obtained. The
conductivity of this film was measured to be 5 x 10-4 Scm-1. EXAMPLE 2
The bissulfonium salt, 2,5-dimethoxy-1,4-xylene bis (tetramethylene sulfonium chloride (1 g; 2.4 m mole), was dissolved in 6 ml of deionized water (0.4 M), and degassed by N2 for about 4h. After cooling the solution for half an hour, a 0.4 M degassed NaOH aqueous solution (0.097 g in 6 ml H2O; 0.4 M) was added. A cloudy
polymer gel was formed within 1 to 2 minutes. The
polymerization was allowed to processed for 10 minutes, then 150 ml de-ionized water was added to dissolve the gel. The resulting solution was neutralized with 1 M HCl to pH 7. About 2 to 3 ml of pyridine was added to help stabilize the solution against gel formation.
The polymer solution was then placed into dialysis tubes having a molecular weight cutoff of 6000-8000.
These were then dialyzed against 2 to 3 liters of water containing about 5 ml pyridine. The dialysis solutions were changed every day for 3 to 5 days.
Casting the above precursor polymer solution gave a transparent, light yellow-green film having a thickness of 19 microns.
This non-conductive, non-conjugated precursor polymer film was then placed at room temperature in a zip-lock bag and sealed. After sitting at room temperature for about 2 weeks, the film was found to have become non-transparent and conductive, with a green metallic luster.
The conductivity was measured to be 10-2 Scm-1, which is comparable to that of a fully eliminated
poly(dimethoxyphenylene vinylene) polymer film doped with
HCl.

Claims

WHAT IS CLAIMED IS:
1. A homopolymer or copolymer comprising
recurring units selected from the group consisting of units of the following Formulas I to XI:
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
a composition comprising said homopolymer or copolymer and solutions of said composition, homopolymer, copolymer or a combination thereof wherein:
m, n, o and p are the same or different and are integers, and are selected such that m or the sum of n, o and p is greater than about 20; with the proviso that at least one of n or o is not zero;
q is an integer from 0 to about 4;
D is a leaving group with the proviso that at least about 1 mole % of D leaving groups based on the total moles of D leaving groups is a moiety which on elimination from said polymer forms a non-oxidizing protonic acid having a pKa in aqueous or non-aqueous medium equal to or less than about 4, or is a zwitterionic moiety comprising a positively charged moiety and a negatively charged moiety, at least one of which is bonded to said polymeric backbone, said anionic moiety being the conjugate base of a strong non-oxidizing protonic acid having a pKa equal to or less than about 4, which forms said acid on elimination or a moiety which on elimination forms a species which can be converted into acid;
R1, R2, R3, R4, R5, R6' R7' R8, R9, R10, R11, R12,
R13 and R14 are the same or different at each occurrence and are hydrogen or isotopes thereof, halogen, hydroxyl, cyano, alkyl, alkenyl, aryl, alkoxy, cycloalkyl,
cycloalkenyl, alkanoyl, alkylthio, aryloxy,
alkylthioalkyl, alkynyl, alkylaryl, arylalkyl, amido, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylamino, diarylamino, alkylamino, dialkylamino, alkylarylamino, arylthio, heteroaryl, arylsulfinyl, alkoxycarbonyl, boric acid, boric acid salts, arylsulfonyl, carboxyiic acid, carboxyiic acid esters, carboxyiic acid anhydride, carboxyiic acid salts, halogen, nitro, phosphoric acid, phosphoric acid salts, cyano, sulfonic acid, sulfonic acid salts, amino, or epoxy moieties, or a moiety of the formula:
-(OR15)rOR16 or -R15-(OR15)rOR16 wherein:
R15 is a divalent alkylene moiety having from 1 to about 7 carbon atoms;
R16 is alkyl having from 1 to about 20 carbon atoms; and
r is a natural number from 1 to about 50; or any of
R1 and R2, or R3 and R4, or R5 and R6, or R7 and R8, or R9 and R10, or R11 and R12, or R13 and R14, or R15 and R16, substituents taken together are 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 divalent heteroatoms of nitrogen, sulfur, sulfinyl, phosphorous, selenium, sulfonyl or oxygen, one or more degrees of unsaturation or a combination thereof; and
X1 and X2 are the same or different and are S, O, Se, NR17, or PR17, wherein R17 is hydrogen, R1, alkylaryl, arylalkyl, alkyl or aryl.
2. A homopolymer or copolymer according to claim 1 wherein:
R1 to R4 are the same or different at each occurrence and are hydrogen; hydroxyl; alkyl containing from 1 to about 20 carbon atoms; phenyl; alkenyl containing from 2 to about 20 carbon atoms; alkylphenyl or phenylalkyl each containing from about 7 to about 20 carbon atoms;
alkylthio or alkoxy each containing from 1 to about 20 carbon atoms; alkylamino, dialkylamino, diarylamino, arylamino and alkylarylamino; alkoxyalkyl having from 2 to about 20 carbon atoms; substituted phenyl or substituted alkyl having from 1 to about 20 carbon atoms wherein permissible substituents are epoxy, nitro, cyano, amino, sulfonic acid and salts thereof, phosphoric acid and salts thereof, carboxyiic acid and salts thereof or halo groups; moiety of the formula: -(OR15)rOR16 or -R15-(OR15)rOR16 whererin:
R15 is alkylene having from 1 to about 4 carbon atoms;
R16 is alkyl having from 1 to about 10 carbon atoms; and
r is a natural number from 1 to about 25; or any of R1 and R2, or R3 and R4 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 which may include one or more degrees of unsaturation and heteroatoms of divalent oxygen or sulfur.
3. A homopolymer or copolymer according to claim 2 wherein:
R1, R2, R3 and R4 are the same or different at each occurrence and are hydrogen, alkoxyalkyl, alkoxy,
alkythio, alkyl, or moieties of the formula:
-(OR15)rOR16 or -R15-(OR15)rOR16 wherein:
R15 is alkylene of about 2 to about 3 carbon atoms;
R16 is alkyl of from 1 to about 3 carbon atoms; and r is a natural number from 1 to about 10.
4. A homopolymer of copolymer according to claim 3 wherein R1, R2, R3 and R4 are the same or different at each occurrence and are alkyl, alkoxy or hydrogen.
5. A homopolymer or copolymer according to claim 1 wherein R5 to R12 are the same or different at each occurrence and are hydrogen or alkyl having from 1 to about 12 carbon atoms.
6. A homopolymer of copolymer according to claim 1 wherein X1 and X2 are O, S or -NR17 wherein R17 is hydrogen, alkyl of from 1 to about 12 carbon atoms or aryl from 6 to about 12 carbon atoms.
7. A homopolymer or copolymer according to claim 1 wherein D is selected from the group consisting of
moieties of the formula:
-OSOR1, R1CO2-, -OSO3R1, -OSiR1R2R3 -OR1,
-OPO(OR1)(OR2), -+SR1R2,Z-, -N+R1R2R3· Z-, -P+R1R2R3· Z-, -S+(O)R1R2· Z-, and -+N(O)R1R2,Z-;
Z is an anion of a non-oxidizing protonic acid; and R1, R2 and R3 are the same or different at each occurrence and are hydrogen, or substituted or
unsubstituted alkoxyalkyl, aryl, alkanoyl, alkoxyaryl, alkyl, aroyl, arylsulfonyl, alkanesulfonyl, alkylaryl, or arylalkyl wherein permissible substituents are one or more carboxyiic acid groups, sulfonic acid groups, alkyl, alkoxy, carboxyiic acid salts or sulfonic acid salts.
8. A homopolymer or copolymer according to claim 7 wherein D is a moiety of the formula -+NR1R2R3 · Z".
9. A polymer according to claim 8 wherein -+NR1R2R3, wherein -+NR1R2R3 is pyridinium and Z- is an anion.
10. A homopolymer or copolymer solution comprising:
(a) a solvent selected from the group consisting of water, an organic solvent and a mixture thereof; and
(b) one or more of the homopolymers or copolymers of claim 1.
11. A method of forming an article which comprises the steps of:
(a) forming the solution of claim 10; and
(b) removing the solvent from the solution as the polymer solute solidifies to form the solidified polymer having the shape of said article.
12. A method of forming a conductive article which process comprises the steps of:
(a) forming the solution of claim 10;
(b) removing from the solution the solvent as the polymer solute solidifies;
(c) treating said solidified polymer to eliminate the species of the formula D forming a protonic acid species selected from the group consisting of HZ and DH converting said solidified polymer into a homopolymer or random or block copolymer having regular or random units of the following formulas XII to XXII:
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
forming a polymer doped with said protonic acid species to a conductivity of at least about 10-8S/cm.
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