WO1999016084A1 - Copolymeres sequences electriquement conducteurs contenant un polymere intrinsequement conducteur - Google Patents

Copolymeres sequences electriquement conducteurs contenant un polymere intrinsequement conducteur Download PDF

Info

Publication number
WO1999016084A1
WO1999016084A1 PCT/EP1998/005993 EP9805993W WO9916084A1 WO 1999016084 A1 WO1999016084 A1 WO 1999016084A1 EP 9805993 W EP9805993 W EP 9805993W WO 9916084 A1 WO9916084 A1 WO 9916084A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
intrinsically conductive
set forth
conductive polymer
block
Prior art date
Application number
PCT/EP1998/005993
Other languages
English (en)
Inventor
Patrick J. Kinlen
Yiwei Ding
Edward E. Remsen
Original Assignee
Zipperling Kessler & Co. (Gmbh & Co.)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zipperling Kessler & Co. (Gmbh & Co.) filed Critical Zipperling Kessler & Co. (Gmbh & Co.)
Publication of WO1999016084A1 publication Critical patent/WO1999016084A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the invention relates to intrinsically conductive polymers and, more particularly, to block copolymers comprising an intrinsically conductive polymer (ICP) and method for their synthesis.
  • ICP intrinsically conductive polymer
  • Intrinsically conductive polymers are one type of electrically conducting polymers that combine the processability properties of a polymer with the electrical conductivity of a metal. Such characteristics make ICP's excellent candidates for use in batteries, conductive coatings, paints and conductive fibers.
  • ICP's such as polyaniline.
  • ICP's had limited electrical conductivity and were often of low molecular weight.
  • doping the ICP's with protonic acids e. g. , hydrochloric acid
  • Higher molecular weights are important to impart to ICP's sufficient mechanical strength to form cohesive films and fibers.
  • Protonated polyaniline- poly(ethylene glycol)- polyaniline (abbreviated as ( PANI ) 13 - ( PEG ) ⁇ 4 -(PA ⁇ I) ) block copolymers had electrical conductivities of from 1.7 x 10 "4 S/cm to 0.62 S/cm and were insoluble in chloroform and methanol. Graft copolymers, protonated with HC1, had electrical conductivities of from 3 x 10" 4 S/cm to 1.1 S/cm, but were also insoluble in chloroform and methanol. By way of comparison, organic acid salts of polyaniline homopolymer were also prepared and reported in this study.
  • U.S. Patent No. 5,095,076 to Clement et al . reported soluble conductive polyanilines comprising two polyaniline blocks which were synthesized from a central organic group characterized as a flexible segment derived from an organic diamine.
  • the flexible diamine was preferably triethylene tetramine and the resulting polyanilines have an average molecular weight ranging from about 8,000 to about 40,000 and electrical conductivities of the material doped with para-toluene sulfonic acid is up to 12 S/cm. It is stated that the products are not copolymers and that some are soluble up to 12 grams/liter in N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the present invention is directed to a novel electrically conductive block copolymer comprising at least one polymer block that is an organic acid salt of an intrinsically conductive polymer and a non-intrinsically conductive block, the electrically conductive block copolymer having a solubility in xylene of at least about 1% wt/wt.
  • the present invention is also directed to a novel method of preparing an electrically conductive block copolymer which comprises combining a monomer of an intrinsically conductive polymer; a chemical oxidant; a non-intrinsically conductive block precursor having at least one monomer unit of a non-intrinsically conductive polymer that is covalently linked to at least one linkage group having an oxidation potential approximately equal to or less than the oxidation potential of the monomer of an intrinsically conductive polymer; water; and an organic solvent in which the organic acid, the non- intrinsically conductive polymer block precursor, the monomer of an intrinsically conductive polymer and the electrically conductive block copolymer are soluble and in which water is soluble in an amount of at least 6% wt/wt; thereby forming an electrically conductive block copolymer .
  • the present invention is further directed to a novel block copolymer made by the method described above.
  • the present invention is also directed to a nove l method of preparing an electrically conductive block copolymer which comprises applying an oxidizing electrochemical potential to a monomer of an intrinsically conductive polymer in the presence of water, a non-intrinsically conductive block having at least one monomer unit of a non-intrinsically conductive polymer that is covalently linked to at least one linkage group having an oxidation potential approximately equal to or less than the oxidation potential of the monomer of an intrinsically conductive polymer, and an organic solvent in which water is soluble in an amount of at least 6% wt/wt and in which the organic acid, the non-intrinsically conductive polymer, the monomer polymerizable into an intrinsically conductive polymer and the electrically conductive block copolymer are soluble.
  • a block copolymer made by this method is also provided.
  • an electrically conductive block copolymer in which are combined desired properties of high molecular weight ' , electrical conductivity, solubility in commonly used commercial solvents and improved compatibility with polymers which are the same as, or similar to, the repeating portion of the non-ICP; and the provision of a method for the production of such electrically conductive block copolymer having the advantageous properties described herein.
  • Figure 1 is a photomicrograph at approximately 400x of the surface of a film cast from a polyaniline- poly(propylene oxide)-polyaniline triblock copolymer illustrating the homogeneity of the copolymer particles comprising the film;
  • Figure 2 is a nuclear magnetic resonance proton spectrum of N-phenyl-4-lauramidoaniline-polyaniline diblock copolymer in deuterated dimethylsulfoxide solution showing peaks for benzyl and quinone hydrogens between 6.8 " ppm - 7.2 ppm and for- hydrogens on the aliphatic portion of N-phenyl-4-lauramidoaniline at about 1.3 ppm;
  • Figure 3 is a UV spectrum of N-pheny-1-4- lauramidoaniline-polyaniline diblock copolymer in tetrahydrofuran solution showing an absorbance maximum at about 600 nm - 650 nm;
  • Figure 4 is a schematic representation of the general structure of the subject diblock and triblock copolymers.
  • ICP monomer an intrinsically conductive polymer
  • non-ICP a non-intrinsically conductive polymer that is covalently linked to at least one linkage group, to form a block copolymer that, surprisingly, not only is electrically conductive and has a high molecular weight, but also is soluble in xylene in an amount of at least about 1% wt/wt.
  • the electrical conductivity of the block copolymer of this invention is typically at least about 10 "6 S/cm; the weight average molecular weight is typically at least about 30,000; and the block copolymer composition is soluble in chloroform as well.
  • the non-ICP component can be selected to match the characteristics of polymers with which the block copolymer is to be blended, thereby increasing the compatibility of such polymer blends.
  • the subject block copolymers can be either diblock copolymers or triblock copolymers .
  • diblock copolymers comprise one non-ICP block and one ICP block
  • triblock copolymers comprise one non-ICP block and two ICP blocks.
  • the ICP block is formed from the polymerization of ICP monomers with the polymerization initiated at a linkage group.
  • the non-ICP block comprises a non-ICP covalently linked with one linkage group (for a diblock copolymer), or two linkage groups (for a triblock copolymer ) to form a non-ICP block precursor.
  • the ICP Block ⁇ The ICP that makes up the ICP block is formed by the polymerization of an ICP monomer, or mixture of ICP monomers . Such monomers are those monomers that are capable of polymerization to form an ICP. Any aromatic heterocyclic or aniline monomer that can be polymerized into an ICP can be used.
  • ICP is intended to include any polymer having a polycon ugated n electron system and which is electrically conductive in at least one valence state. ICP's are well known and a comprehensive review of ICP technology can be found in Synthetic Metals , vols. 17 - 19, 1987; vols. 28 - 30, 1989; and vols. 40 - 42, 1991, incorporated herein by reference.
  • ICP's are, in general, dopable with an ionic dopant species to a more highly electrically conductive state.
  • ICP's which can be useful in this invention are intrinsically conductive homopolymers and copolymers of ICP monomers described herein. Examples o f such intrinsically conductive homopolymers include, for example, polyaniline, polyacetylene, poly-p-phenylene, poly-m-phenylene, polyphenylene sulfide, polypyrrole, polythiophene, polycarbazole, polyfuran and the like.
  • the substituted or unsubstituted aromatic heterocyclic ICP monomers useful in this invention include pyrrole and substituted pyrroles, p-phenylenes, m-phenylenes, phenylene sulfides, thiophene and substituted thiophenes, indoles, azulenes, furans, carbazoles and mixtures thereof.
  • Aromatic heterocyclic compounds for use in the present invention include the 5- membered heterocyclic compounds having the formula:
  • each of R 1 and R 2 is independently hydrogen; alkyl (e.g. methyl or ethyl ) ; aryl (e.g. pheny1 ) ; alkaryl (e.g. tolyl); or aralkyl (e.g. benzyl); or R 1 and R 2 together comprise the atoms necessary to complete a cyclic (e.g. benzo) structure; and X is -0-; -S-; or
  • R 1 , R 2 and X have the definitions set forth above.
  • substituted or unsubstituted anilines for use in this invention are of the formula:
  • n is an integer from 0 to 4
  • m is an integer from 1 to 5, provided, however, that the sum of n and m is equal to 5;
  • R 2 and R* are the same or are different and are hydrogen or are R 3 substituents; and R 3 is the same or different at each occurrence and is selected from alkyl, deuterium, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, a ino, alkylaraino, dialkylamino, aryl, alkylsulfinyl, aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, phosphonate, alkylsulfonyl, arylthio, alkylsulfonylalkyl, borate, phosphate, sulfinate, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylate, halogen, hydroxy, cyano
  • q is a positive whole number; provided that said homopolymer and copolymer includes about 10 or more recurring substituted or unsubstituted aniline aromatic moieties in the polymer backbone.
  • substituted and unsubstituted anilines are illustrative of those which can be used in the synthesis of the polyaniline block of the block copolymer of the present invention: 2-cyclohexylaniline, aniline, o-toluidine, 4-propanoaniline, 2-
  • the preferred ICP monomer is unsubstituted aniline.
  • the Non-ICP Block As shown in Figure 4, the non-ICP block is derived from a non-ICP block precursor, which is simply the compound that, upon reaction with the ICP monomer, forms the non-ICP block that is bonded to the ICP block.
  • the non-ICP block precursor comprises a non-ICP and one or two linkage groups.
  • non-ICP means any polymer other than an ICP to which a linkage group can be covalently bonded. Either thermoset or thermoplastic polymers can be used as the non-ICP.
  • the non-ICP can be either water-soluble or water-insoluble.
  • a water-insoluble non-ICP is a non-ICP that has a water solubility of less than about 1% wt/wt and a water- soluble non-ICP is a non-ICP that has a water solubility of greater than about 1% wt/wt.
  • the non-ICP of the non-ICP block has an average degree of polymerization of at least about 2, more preferably at least about 10, and most preferably at least about 20 and up to about 50 or greater, in order to provide to the block copolymer a sufficient level of the characteristics of the non-ICP.
  • degree of polymerization corresponds to non-ICP' s having weight average molecular weights of preferably at least about 100, more preferably at least about 500, and most preferably at least about 1,000 and up to about 2,500 or greater.
  • thermoset polymers suitable for use in the non-ICP block of this invention can vary widely.
  • thermoset polymers are alkyds derived from the esterification of a polybasic acid such as phthalic acid and a polyhydric alcohol such as glycol; allylics such as those produced by polymerization of diallyl phthalate, diallyl isophthalate, diallyl maleate, and diallyl chlorendate; amino resins such as those produced by addition reaction between formaldehyde and such compounds as melamine, urea, aniline, ethylene urea, sulfonamide and dicyandiamide; epoxies such as poly phenol novolak resins, diglycidyl ethers of bisphenol A and cycloaliphatic epoxies; phenolics such as resins derived from reaction of substituted and unsubstituted phenols such as cresol and phenol with an aldehyde such as formaldehyde and acetaldehyde; polyesters; silicones; and urethanes formed by reaction of
  • thermoplastic polymers for use in the composition of this invention can vary widely.
  • Illustrative of such polymers are polyesters such as polyglycolic acid, polyethylene succinate, polyethylene adipate, polytetramethylene adipate, polyethylene azelate, polyethylene sebecate, polydecamethylene adipate, polydecamethylene sebacate, poly- ⁇ , ⁇ - dimethylpropiolactone, polypivaloyl lactone, polyparahydro ybenzoate, polyethylene oxybenzoate, polyethylene isophthalate, polyethylene terephthalate, polydecamethylene terephthalate, polyhexamethylene terephthalate, poly-1, 4-cyclohexane dimethylene terephthalate, polyethylene-1, 5-naphthalate, polyethylene-2, 6-naphthalate, poly-1, 4-cyclohe ⁇ ylidene dimethyleneterephthalate and the like; polyamides such as poly-4-aminobutyric acid, poly-6-aminohexanoi
  • polyvinyl hexyl ether polyvinyl octyl ether
  • polyvinyl methyl ketone polymethyl isopropenyl ketone
  • polyvinyl formate polyvinyl acetate, polyvinyl propionate
  • polyvinyl chloroacetate polyvinyl trifluoroacetate
  • polyvinyl benzoate poly-2-vinylpyridine, polyvinylpyrrolidone, polyvinylcarbazole, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polysec.
  • poly-1,3- pentadiene( trans) poly-2-methyl-1-1, 3-butadiene( cis ) , poly 2-methyl-1, 3-butadiene( trans ) , poly-2-methyl-l, 3- butadiene(mixt. ), poly-2-tert.-butyl-l-l,3- butadiene(cis) , poly-2-chloro-l, 3-butadiene( trans) , poly- 2-chloro-l,3-butadiene(mixt.
  • polyoxides such as polymethylene oxide, polyethylene oxide, polytetramethylene oxide, polyethylene formal, polytetramethylene formal, polyacetaldehyde, polypropylene oxide, polyhexene oxide, polyoctene oxide, polytrans-2-butene oxide, polystyrene oxide, poly-3- methoxypropylene oxide, poly-3-butoxypropylene oxide, poly-3-hexoxypropylene oxide, poly-3-phenoxypropylene oxide, poly-3-chloropropylene oxide, poly-2,2- bischloromethyl-trimethylene-3-oxide, poly-2, 6-dimethyl- 1,4-phenylene oxide, PPO, poly-2, 6-diphenyl-l,4-phenylene oxide, and the like, polysulphides such as polypropylene sulphide, polyphenylene sulphide and the like; polysulfones such as poly-4,4' -isopropylidene diphenoxydi-4-phen
  • the non-ICP can also be a naturally-occuring polymer such as, for example, protein, peptide, poly amino acid, nucleic acid, cellulose, hemi-cellulose, starch, poly(lactic acid), poly(hydroxybutyrate), or the like.
  • a naturally-occuring polymer such as, for example, protein, peptide, poly amino acid, nucleic acid, cellulose, hemi-cellulose, starch, poly(lactic acid), poly(hydroxybutyrate), or the like.
  • non-ICP be selected from poly(ethylene oxide), poly(propylene oxide), poly (ethylene glycol),- or poly(acylonitrile-co-butadiene) .
  • the most preferred non-ICP 's are poly(ethylene oxide) and poly( propylene oxide) .
  • the non-ICP block includes one or two linkage groups that are covalently linked to the non-ICP.
  • the combination of the non-ICP and attached linkage groups is termed the non-ICP block "precursor".
  • the non-ICP block precursor can be purchased and used without modification, the precursor can be synthesized, if desired, from a non-ICP and at least one linkage group precursor.
  • linkage group precursor or that the linkage group is "derived from” a particular compound, it is meant simply that the linkage group is .the residue of that compound after covalently bonding with the non-ICP.
  • the linkage group is derived from, for example, para-aminodiphenylamine, or that the linkage group precursor is,- for example, para-aminodiphenylamine, what is meant is simply that para-aminodiphenylamine is covalently bonded to the non-ICP to form a linkage group.
  • the non-ICP has a terminal carboxylic acid group and is represented schematically as
  • linkage groups and their precursors are described in general in, for example, Electrochemical Reactions in Nonaqueous Systems , by Mann, C.K., and K.K. Barnes, Marcel Dekker, Inc., 1970, incorporated herein by reference.
  • the linkage group of the present invention forms a covalent bond with the non-ICP and is oxidizable by a chemical oxidant or an electrochemical potential to form a covalent bond with the ICP monomer to initiate polymerization of the ICP monomer into the ICP block.
  • the method that is used to link the linkage group to the non-ICP is not critical.
  • linkage groups can be chemically linked to a thermoset or thermoplastic polymer described above by any technique as would be readily known to those of ordinary skill and examples of such methods are described by Li et al., Synth. Met., 29:E329-E336, 1989, incorporated herein by reference.
  • the linkage group when the linkage group is derived from an amine, such amine group could be added by nucleophilic addition such as, for example, the addition of p-aminodiphenylamine to a polymer having a terminal isocyanate group; or to a polymer with a terminal carboxylic acid group, as shown above.
  • the terminal amine groups could be added by nucleophilic substitution to a non-ICP by, for example, the combination of p-aminodiphenylamine with a polymer having an epoxy end group.
  • the non-ICP block precursor can be bonded to one or two linkage groups. If the non- ICP is bonded to only one linkage group, the non-ICP preferably has at least one non-ICP monomer unit and polymerization of the ICP monomer can be initiated at the linkage group to form a diblock copolymer. However, if the non-ICP is bonded to two linkage groups, then the ICP monomer can commence polymerization on each of these linkage groups to form a copolymer having three blocks as the triblock polymer is shown in Fig. 4.
  • the linkage group has an oxidation potential that is approximately equal to or less than the oxidation potential of the ICP monomer. In fact, it is most preferred that the oxidation potential of the linkage group be lower than that of the ICP monomer to maximize the amount of block copolymer formed.
  • the oxidation potential of the linkage group is lower than the oxidation potential of the ICP monomer, the ICP monomer generally commences polymerization at the linkage group on the non-ICP block rather than forming a homopolymer containing only the ICP monomer.
  • the oxidation potential of the linkage group can be equal to, or even somewhat higher than that of the ICP monomer and the formation of the copolymer will still take place.
  • the oxidation potential of the linkage group may be about 10% to 15% higher than that of the ICP monomer and appreciable copolymer will still be formed.
  • the oxidation potential of the linkage group when the oxidation potential of the linkage group is described as being approximately equal to or less than the oxidation potential of the ICP monomer, it is meant that the oxidation potential of the linkage group compared to that of the ICP monomer is such that formation of the copolymer takes place.
  • the linkage group ' s oxidation potential can range from lower than the oxidation potential of the ICP monomer to about 10% - 15% above such value, to even greater than 15% above such value so long as formation of the copolymer takes place.
  • the oxidation potential of the linkage group of the present invention is also lower than that of any organic solvent that is present when the polymerization is carried out.
  • the linkage group is bonded to the non-ICP at or near an end of the non-ICP; that is, the linkage group should be a terminal group.
  • the linkage group is preferably at or near either end or terminal of the non-ICP.
  • the non- ICP block precursor has two linkage groups, one of the linkage groups is preferably at or near each of the terminals of the non-ICP.
  • the linkage group is also capable of being incorporated into the polymer chain of the block copolymer.
  • Linkage groups that are useful in the present invention can be derived from precursors such as carbonyl compounds, quinones, halogenated compounds, phenols, alkoxides, ethers, amines, amides, ammonium salts, heterocyclic aromatic compounds such as thiophenes, pyrroles, furans, azulenes, carbazoles, purines, and the like; viologens such as N-methyl-viologen; acetylenes, thiols, or phosphate containing compounds such as phosphates, phosphines and the like by covalently bonding such precursors to the non-ICP.
  • precursors such as carbonyl compounds, quinones, halogenated compounds, phenols, alkoxides, ethers, amines, amides, ammonium salts, heterocyclic aromatic compounds such as thiophenes, pyrroles, furans, azulenes, carbazoles, purines, and the
  • Preferred linkage groups are derived by covalently linking such compounds as anilines, thiophenes, pyrroles and amine groups to the non-ICP.
  • Preferred amine groups are p- aminodiphenylamine, N,N * -diphenylhydrazine, benzidine, p- phenoxyaniline, p-phenylaminediamine, p-phenylenediamine, hydroquinone , N,N * -diphenylamine and higher oligomers of aniline and its derivatives.
  • the most preferred amine group is p-aminodiphenylamine and the preferred linkage group is that derived from p-aminodiphenylamine.
  • the method of preparing the block copolymers of this invention comprises polymerizing at least one ICP block from ICP monomers with the polymerization initiated at a linkage group of a non-ICP block.
  • the polymerization can be driven by a chemical oxidant or by an electrochemical potential. If the chemical oxidant is water-soluble, the reaction is carried out in the presence of water, an organic acid and a suitable organic solvent.
  • Organic acids suitable for use in this invention are those which are capable of doping the ICP as it forms during polymerization to form an ICP salt.
  • the ICP block of the present invention is synthesized as the salt of an organic acid and needs no doping after synthesis to form such salt.
  • Organic acids suitable for use can be water-soluble or water-insoluble.
  • organic acids having a solubility in water of at least about 10% wt/wt are referred to as water-soluble and those having a solubility in water of less than about 1% wt/wt are deemed water-insoluble.
  • the organic acids suitable for use in the method of the present invention include organic sulfonic acids, organic phosphorous-containing acids, carboxylic acids, or mixtures thereof.
  • Preferred organic sulfonic acids are dodecylbenzene sulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalenedisulfonic acid, p-toluene sulfonic acid, or mixtures thereof.
  • the preferred organic acid is dinonylnaphthalenesulfoni ⁇ acid.
  • Preferred ICP salts of the invention include the para-toluene sulfonic acid salt of polyaniline, the dodecylbenzene sulfonic acid salt of polyaniline and the dinonylnaphthalene sulfonic acid salt of polyaniline.
  • Organic solvents that are useful herein are those in which water is soluble in an amount of at least about 6% wt/wt.
  • the ICP monomer is preferably soluble in the organic solvent in an amount of at least about 5% wt/wt.
  • the organic acid is preferably soluble in the organic solvent in an amount of at least about 10% wt/wt and preferably in an amount of at least about 25% wt/wt or higher.
  • the non-ICP block precursor is preferably soluble in the organic solvent in an amount of at least about 1% wt/wt and preferably in an amount of at least about 5% wt/wt.
  • the block copolymer is preferably soluble in the organic solvent in an amount of at least about 1% wt/wt relative to the weight of the organic solvent, more preferably at least about 5% wt/wt, and most preferably, at least about 10% wt/wt.
  • the organic solvent be capable of forming a mixture with the ICP monomer, the non-ICP block precursor, the organic acid and water, when those components are admixed in suitable amounts at the start of the polymerization. It will be understood that such mixture can be an emulsion, a colloidal solution, a suspension, a dispersion, or a true solution.
  • Organic solvents that can be used include, for example, alcohols, glycols and ethers that meet the above criteria.
  • Preferred organic solvents include, 2- butoxyethanol, propylene glycol, butyl ether, 1-butanol, 1-hexanol, diethyl ether and mixtures thereof and the most preferred organic solvent is 2-butoxyethanol.
  • the block copolymer can be prepared by oxidative polymerization using a chemical oxidant.
  • Chemical oxidants are well known in the art. (For example, see Cao et al., Polymer . 30 : 2305-2311, 1989;
  • the chemical oxidant can be either water-soluble or organic-soluble.
  • water-soluble with respect to a chemical oxidant means that the oxidant is soluble in water in an amount of at least about 5% wt/wt.
  • organic-soluble with respect to a chemical oxidant means that the oxidant is soluble in an organic solvent, such as toluene, in an amount of at least about 5% wt/wt.
  • Water-soluble chemical oxidants can be any of a number of oxidizing agents including chemicals such as ammonium peroxydisulfate, potassium dichromate, potassium iodate, ferric chloride, potassium permanganate, potassium bromate or potassium chlorate.
  • the preferred water-soluble chemical oxidant is ammonium peroxydisulfate.
  • Organic-soluble chemical oxidants useful in the present invention include such chemicals as 2, 3-dichloro-5, 6- dicyano-p-benzoquinone, 2,3-dichloro-5, 6-dicyano-l, 4- benzoquinone, 2,3,5, 6-tetra-cyano-benzoquinone, tetrachloro-l,4-benzoquinone, 7,7,8,8- tetracyanoquinodimethane, p-benzoquinone, or o- benzoquinone.
  • an organic-soluble chemical oxidant is 2, 3-dichloro-5, 6-dicyano-p-benzoquinone.
  • polymerization of the ICP monomer can be accomplished by electrochemical oxidation initiated by applying an electrochemical potential to the reaction mixture.
  • electrochemical oxidative polymerization techniques are well known in the art and are generally described, for example, in J. Chem . Soc . , Faraday Trans. I, 82: 2385-2400, 1986; J. Electrochem. Soc , 130 ( 7 ) : 1508-1509, 1983; Electrochem. Acta, 27 ( 1 ) : 61-65, 1982; and J. Chem. Soc. Chem. Commun. , 1199, 1984.
  • the method of making the electrically conductive block copolymer comprises a procedure having the following steps:
  • the reaction mixture is prepared by admixing in any suitable manner the ICP monomer, the non- ICP block precursor, water, the organic acid and the organic solvent, into an aqueous mixture in the relative amounts described herein.
  • the organic solvent is added to the reaction mixture in an amount of about 1.0 to 100 moles of the organic solvent per mole of ICP monomer, more preferably in an amount of about 4 to 80 moles of the organic solvent per mole of ICP monomer, and most preferably in an amount of about 6 to 62 moles of the organic solvent per mole of ICP monomer.
  • the non-ICP block precursor can be added to the reaction mixture in any amount selected from a wide range, but preferably from about 0.1 x 10" 3 to 200 x 10" 3 moles of the non-ICP block precursor, based on a weight average molecular weight of the non-ICP, is added per mole of ICP monomer, more preferably, about 0.5 x 10" 3 to 150 x 10 "3 moles per mole of ICP monomer, and most preferably about 1 x 10" 3 to 100 x 10" 3 moles per mole of ICP monomer.
  • the organic acid is added to the reaction mixture in an amount of about 0.04 - 5.0 moles of organic acid per mole of ICP monomer, or, more preferably, an amount of about 0.1 to 3.0 moles per mole of ICP monomer, or most preferably about 0.2 - 1.8 moles per mole of ICP monomer.
  • the amount of such chemical oxidant which is added to the reaction mixture is about 0.05 - 10.0 moles per mole of ICP monomer, or more preferably, about 0.2 - 3.0 moles per mole of ICP monomer, or most preferably, about 0.4 - 1.25 moles per mole of ICP monomer.
  • Water is present in the reaction mixture in an amount of about 10 - 1000 moles of water per mole of ICP monomer, or more preferably, about 50 - 600 moles per mole of ICP monomer, or most preferably, about 100 - 460 moles per mole of ICP monomer.
  • the type of reactor is not critical, it should be of a type in which controlled agitation can be provided to the solution on a continuous basis and in which the reactor contents can be maintained at a controlled temperature. Since the reaction is expected to be exothermic, the reactor should have a jacket or coils suitable for removing heat and maintaining reactor contents at or below ambient temperature; more specifically to maintain a temperature of from about 0 ⁇ C to about 20°C. While the material of construction of the reactor and wetted surfaces is not critical, such materials should be reasonably chemically inert to the reactants and should not participate in or affect the desired reaction.
  • the chemical oxidant can be added, or the electrochemical potential can be imposed. If the chemical oxidant is water-soluble, such as, for example, ammonium persulfate, it is often added slowly in a water solution to the reaction mixture while the reaction mixture is stirred vigorously. If the chemical oxidant is organic-soluble, it may be added slowly in a toluene solution. Alternatively, the oxidant can be first added to the mixture and the ICP monomer can be slowly added with agitation. In either case, such addition continues until the reaction is brought to the desired level of completion.
  • water-soluble such as, for example, ammonium persulfate
  • the chemical oxidant is organic-soluble, it may be added slowly in a toluene solution.
  • the oxidant can be first added to the mixture and the ICP monomer can be slowly added with agitation. In either case, such addition continues until the reaction is brought to the desired level of completion.
  • a predetermined amount of oxidant is added to the reaction mixture over a predetermined time period, such as, for example, 30 minutes.
  • the reaction can be allowed to proceed for a significant time, such as, for example, over 50 hours, while temperature and agitation are maintained.
  • a significant time such as, for example, over 50 hours, while temperature and agitation are maintained.
  • the reaction mixture cleanly separates into aqueous and organic liquid phases.
  • the conductive block copolymer product, along with the organic acid, among other components, will separate into the organic phase, whereas the aqueous phase will be largely devoid of the conductive block copolymer.
  • the block copolymer in the organic phase can be easily separated from the aqueous phase by any of a number of conventiona l phase separation processes, such as, for example, decanting, continuous-flow centrifugation, selective drawing off one phase, or the like. After the organic phase is separated, it can be washed with hot or cold water or any other desired solvent to remove unreacted ICP monomer, byproducts, or other undesirable materials.
  • the conductive block copolymer can either be used directly from the organic solution, extracted into another solvent such as, for example, xylene, or separated from the solution as a solid. If it is desirable to use the conductive block copolymer directly from the organic solution, such solution can be applied as a film or coating and the solvent removed by evaporation. Alternatively, the solution could be mixed into a spinning dope for the formation of wet spun or solution spun fibers.
  • the polymer can be precipitated by adding methanol, or other suitable solvent, to the organic phase.
  • the solid conductive block copolymer can be separated from the liquid by decanting, centrifugation, filtration or the like, and any remaining solvent can be removed by drying or evaporation.
  • the solid conductive block polymer can then be used in any manner mentioned above, or can be blended with other polymers, or formed into any useful article, such as films, fibers, coatings and the like by any conventional means used for such purposes.
  • the copolymer of the present invention is a block copolymer in that it is a polymer comprising molecules in which there is a linear arrangement of blocks, a block being defined as a portion of a polymer molecule in which the monomeric units have at least one constitutional or configurational feature absent from the adjacent portions.
  • the distinguishing feature is constitutional, i.e., each of the blocks comprises units derived from a characteristic species of monomer.
  • the block copolymer of the present invention comprises at least one block of an organic acid salt of an ICP (the "ICP block") covalently linked to a non-ICP block through a linkage group in the non-ICP block.
  • the molecular weight of the block copolymer is the sum of the molecular weight contributions of the non-ICP block, including any linkage groups, and the one or more ICP blocks.
  • the molecular weight contribution of the ICP blocks can be calculated by subtracting the molecular weight contributions of the non-ICP block, including any linkage groups, from the molecular weight of the block copolymer.
  • the ICP block preferably has a number average molecular weight of at least about 2,000, more preferably at least about 5,000 and most preferably at least about 10,000 or higher.
  • the molecular weight, or chain length of the ICP block is determined by the type and amount of reactants and the reaction conditions. For example, a higher ratio of ICP monomer to non-ICP in the reaction mixture would be expected to yield a higher chain length for the ICP segments of the block copolymer.
  • the characteristics of both ICP and non-ICP blocks contribute to the characteristics of the block copolymer. For example, a non-ICP block of poly( ethylene oxide) can increase the water solubility of the block copolymer, while poly(propylene oxide) can increase the solubility of the block copolymer in organic solvents.
  • the growth of the ICP chain of the ICP block modifies the solubility characteristics of the copolymer and enhances such characteristics as electrical conductivity and insolubility in conventional organic solvents .
  • the compatibility of the block copolymer with other polymers in polymer blends also depends on the relative sizes of the ICP block and non-ICP block. For example, the compatibility of a polyaniline-poly( ethylene oxide )- polyaniline block copolymer with a polymer such as polyethylene in a polymer blend may be reduced as the size of the polyaniline blocks increases.
  • the non-ICP block includes at least one monomer unit of a non-ICP and, if the copolymer includes more than one ICP block, the non-ICP block comprises a non-ICP of at least two monomer units and preferably at least four monomer units.
  • the emulsion polymerization method of polymerizing the ICP of the ICP block results in a copolymer with higher solubility in organic solvents than a copolymer comprising an ICP polymerized by conventional aqueous methods.
  • the electrically conductive block copolymer of the present invention is soluble in xylene in an amount of 1% wt/wt, or greater, preferably in an amount of 2% wt/wt, or greater, more preferably in an amount of 5% wt/wt, or greater, and most preferably in an amount of 10% wt/wt, or greater.
  • This advantage gives increased organic solubility to copolymers having relatively large non-ICP blocks of hydrophylic polymers such as poly( ethylene oxide) and also having relatively high molecular weight ICP blocks.
  • a polyaniline- poly(ethylene oxide)- polyaniline triblock copolymer polymerized by emulsion polymerization methods previously described herein in the presence of water, 2- butoxyethanol and dinonylnaphthalenesulfonic acid results in a copolymer that is 1% wt/wt soluble in chloroform when the degree of polymerization of the poly( ethylene oxide) is at least about 25, more preferably at least about 50 and most preferably at least about 100 and the molecular weight of each polyaniline salt block is at least about 2,000.
  • the ability to form a copolymer with a combination of properties is advantageous when it is desired to obtain compatibility with other polymers chemically similar to poly(ethylene oxide) while maintaining useful levels of conductivity and tensile properties.
  • the copolymers of the present invention may be used for any application where the electrical conductivity properties of an ICP are desirable.
  • the copolymers may be used as components of paints, films, fibers, coatings, molded articles, electrodes, or the like. They may also be advantageously used in corrosion- resistant paints and coatings, or anti-static additives or coatings, or in conductive adhesives.
  • the following examples describe preferred embodiments of the present invention. Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the specification or practice of the invention as disclosed herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow the examples. In the examples which follow, all percentages are given on a weight basis unless otherwise indicated.
  • DNNSA Dinonylnaphthalene sulfonic acid
  • 2-butoxyethanol 69 g; 0.58 mole
  • Aniline 14.85 g; 0.09 mole
  • ammonium peroxydisulfate (25.6 g; 0.112 moles), in 25 ml (1.39 mole) water was added dropwise to the reactor over a 30 minute period. After two hours the solution turned from brown to blue-green. The solution was stirred at 2° - 3"C for 51 hours. After the stirring was stopped, a green organic layer separated cleanly to the top of the mixture. The water layer was removed with a syringe and the organic layer was washed twice with 200 ml portions of water. Interestingly, no exotherm was observed after one day as is typically observed in the polymerization of aniline alone.
  • the molecular weight of the block copolymer was determined by gel permeation chromatography (GPC) coupled with a refractive index detector. Two Ultrastyragel columns with mean permeabilities of 10 5 Angstroms and 10 3 Angstroms were used at a flow rate of 0.5 ml/min and at a controlled temperature of 45 ⁇ C. N-methyl pyrrolidone (NMP) solution containing 0.02 N ammonium formate was used as GPC eluent or solvent. The block copolymers containing polyaniline were treated with ammonium formate as a modifier to maintain the ICP salt in the deprotonated state and to reduce polymer binding to the column. The molecular weight of the copolymer was measured by GPC.
  • GPC gel permeation chromatography
  • the GPC columns were calibrated by twelve polystyrene standards with weight average molecular weights (M Jardin) ranging from l.lxlO 6 to 3000 g/mole.
  • the copolymer of this example indicated a weight average molecular weight (Mschreib) of 126,500 and a number average molecular weight (Mschreib) of 84,300 and having a polydispersity (M ⁇ ,,) of 1.5.
  • the chromatogram did not show a peak for PEO, indicating the product is not a mixture of polyaniline and PEO. A portion of the polymer was precipitated with methanol and dried in air to yield a dark green powder.
  • the polymer was found to be very soluble in toluene, xylenes, tetrahydrofuran (THF) and chloroform.
  • the absorbance maximum ( ⁇ aax ) was found to be 755 nm in THF.
  • EXAMPLE 4 This example illustrates the electrical conductivity of a film cast from PANDA-PEO-PANDA triblock copolymer.
  • the triblock copolymer of Example 2 was solubilized in THF and a thin film was cast onto a Mylar® plastic sheet on which two, spaced gold electrodes were deposited.
  • the THF was evaporated and the resistance, width and thickness of the film were measured.
  • the conductivity of the film was calculated to be 8 x 10 "3 S/cm.
  • This example illustrates the synthesis of a PANTSA and poly(propylene oxide) (PPO) triblock copolymer (PANTSA-PPO-PANTSA) in the presence of n-butanol.
  • n-butanol 60 ml; 0.66 mole, available from Fisher Scientific
  • pTSA para-toluene sulfonic acid
  • ammonium peroxidisulfate (NH ⁇ ) 2 S 2 O a , (2.16 g; 0.0095 mole) was added and the material became a dark green emulsion.
  • aniline (1.0 g; 0.0107 mole ) , available from Acros, was added and the emulsion became dark blue.
  • the aqueous phase was removed and the solid copolymer was washed with 50 ml of deionized water.
  • the emulsion was washed with 100 ml DI water and the aqueous phase again removed.
  • the electrical conductivity of the film was measured at 1.0 S/cm by the method described in Example 4. After drying in a vacuum oven at 60°C for 40 hrs, the electrical conductivity of the film was measured at 4 S/cm.
  • the polydispersity was 2.1.
  • a photomicrograph of the film taken at about 400x, shown in Figure 1 illustrates the homogeneous size of the copolymer particles composing the film. Only one peak was observed on a gel permeation chromatogram (GPC) of the material, indicating the lack of homopolymer in the copolymer product.
  • GPC gel permeation chromatogram
  • EXAMPLE 6 This example illustrates the synthesis of a PANDBSA-PPO-PANDBSA triblock copolymer polymerized in the presence of n-butanol.
  • Poly(propylene oxide), terminated on each end with p-aminodiphenylamine, (M Rico 4,000) (1.25 g); n- butanol (60 ml; 0.66 mole); dodecylbenzenesulfonic acid (DBSA), (4.67 g, 0.0143 mol ) ; and deionized water (20 ml; 1.11 mole) were added to a 150 ml flask. The mixture became a light green emulsion.
  • DBSA dodecylbenzenesulfonic acid
  • ammonium peroxidisulfate,- (NH 4 ) 2 S 2 0 8 , (3.08 g; 0.0135 mol) was added and the emulsion stirred at 0 - 5°C for 7 min until most of the salt dissolved.
  • aniline 1.0 ml; 0.011 mol
  • the slurry was stirred at 0 - 5°C for another 14 hrs and at room temperature for an additional 8 hours.
  • the aqueous phase was removed by pipette and the organic phase washed twice with 50 ml portions of DI water. A green emulsion product was obtained (48 g ) .
  • the polydispersity of the copolymer was 1.8.
  • the polyaniline block of the copolymer could be easily converted to the base form.
  • To a 10 ml test tube were added the green emulsion (2.0 g), methanol (4.0 g) and triisopropylamine (0.20 g) .
  • the slurry became blue (indicating formation of the emeraldine base form of polyaniline), and a blue precipitate was separated by centrifugation.
  • EXAMPLE 7 This example illustrates the synthesis of a PANDBSA-PPO-PANDBSA triblock copolymer polymerized in the presence of n-butanol as in Example 6, except at different concentrations and ratios of reactants and with different recovery technique.
  • the mixture became a green emulsion after 20 min. and was stirred at 0° - 5°C for an additional 17 hrs.
  • the resulting green emulsion was poured into excess methanol ( 700 ml ) and the precipitated product was collected by vacuum filtration and washed with methanol (3 x 100 ml). After drying in air for 3 hrs . a green powder product (8.8 g ) was obtained.
  • EXAMPLE 8 This example illustrates the synthesis of a PANTSA poly(propylene glycol) (PPG) triblock copolymer (PANTSA- PPG-PANTSA) polymerized in the presence of n-butanol.
  • the mixture changed from a light green emulsion to a blue emulsion and then turned into a brown emulsion.
  • the mixture was stirred at 5 ⁇ C for 16 hrs. and at room temperature for an additional 10 hrs. Then more ammonium peroxidisulfate (0.7 g, 0.00307 moles) was added to the emulsion and it was stirred at room temperature for 24 hours.
  • the organic layer that separated to the top of the mixture was collected and washed with DI water (2 x 20 ml ) .
  • EXAMPLE 10 This example illustrates the synthesis of a PANDA poly(acrylonitrile-co-butadiene) (PAB) triblock copolymer ( PANDA-PAB-PANDA) polymerized in the presence of 2- butoxyethanol .
  • PAB poly(acrylonitrile-co-butadiene)
  • DNNSA 105 g, 0.223 moles
  • 2-butoxyethanol 105 g with the DNNSA plus an additional 240 ml, 2.72 moles total
  • aniline 13.6 g, 0.146 moles
  • 81 g, 2.1 x 10 -2 moles di-amino terminated
  • DI water 600 ml, 33.33 moles
  • the material was soluble in NMP, THF and dimethylacetamide (DMAC). A 10% wt/wt solution in DMAC was prepared.
  • EXAMPLE 11 This example illustrates the synthesis of a PANDA- PEO diblock copolymer polymerized in the presence of 2- butoxyethanol .
  • a bottom aqueous layer ( 100 ml ) was removed by a syringe and the organic layer was poured into excess methanol ( 500 ml ) to precipitate the polymer.
  • the precipitated polymer was collected by vacuum filtration and washed with 400 ml methanol . After drying in air, a dark, black powder (14.6 g) was collected.
  • a solution of the material in tetrahydrofuran (THF) showed a ⁇ Bax at 763 nm at room temperature. The powder was partially soluble in methylethyl ketone and soluble in THF/hexane mixture.
  • EXAMPLE 12 This example illustrates the synthesis of the PANDA and N-phenyl-lauramidoaniline diblock copolymer ( PANDA-(N-phenyl-lauramidoaniline ) ) polymerized in the presence of n-butanol.
  • N-phenyl-4-lauramidoaniline (CH 3 (CH 2 ) 10 C0-ADPA) , (0.39 g, 0.00106 moles), n-butanol (60 ml, 0.655 moles), pTSA 3.3 g, 0.0173 moles) and 20 ml DI water were added to a 150 ml flask.
  • the mixture was initially a blue emulsion, but after 30 min. in an ice bath, a gray powder precipitated from the mixture. The precipitate re- dissolved upon warming the mixture to room temperature.
  • Ammonium peroxidisulfate (3.36 g, 0.0147 moles) was added and, after stirring at room temperature for 2 min. , the mixture became a green emulsion.
  • a film was cast from the green emulsion onto a Mylar® sheet having two spaced, gold stripe electrodes.
  • the electrical conductivity was calculated to be 0.7 S/cm.
  • the copolymer synthesized as described above was dedoped and characterized by nuclear magnetic resonance (NMR) spectroscopy.
  • NMR nuclear magnetic resonance
  • the green polymer emulsion (10 g), methanol (10 g, 0.3125 moles), and tri-iso-propylamine (1.3 g, 0.0146 moles) were added to a 100 ml round flask equipped with a magnetic stirring bar. After stirring at room temperature for 30 min. the slurry was placed in three tubes and centrifuged. The top liquid layer was decanted off. Methanol (7 ml, 0.174 moles) was added to each tube with mixing and the top liquid layer decanted off after recentrifuging. This wash was repeated.
  • the peak at about 0.8 ppm is assigned to the terminal methyl group of the N-phenyl-4- lauramidoaniline (NPLA); the peak.. at about 1.3. is assigned to the alkyl group of the NPLA; the peak between 2.2 ppm and 2.4 ppm is assigned to the hydrogen on the - CH 2 C0- of NPLA.
  • the large peak at about 2.5 is assigned to DMSO; the large peak at about 3.1 is assigned to water; the two large peaks at about 3.4 and 4.1 are the residual solvent and the low, broad peak at about 7.0 is assigned to polyaniline.
  • the NMR spectra demonstrates the presence of polyaniline and N-phenyl-4-lauramidoaniline in the solid copolymer.
  • the copolymer was then dissolved in tetrahydrofuran (THF) and its UV spectra was obtained.
  • THF tetrahydrofuran
  • the solution was filtered through a 0.45 micron filter and the UV spectra from 250 nm - 900 nm was obtained on a Perkin-Elmer Lambda-6 UV-Vis spectrophotometer.
  • the reaction described above was repeated, except that 97% dodecylbenzenesulfonic acid (10.01 g, 0.03 moles), was used in place of the D ⁇ SA. After 25 hours, the solution was poured into methanol ( 800 ml ) containing 30 ml water.
  • the precipitated material was collected by vacuum filtration, washed with three aliquoets (each 100 ml) of methanol and air dried for 24 hours. 4.7 g of black solids was collected.
  • the product was soluble in THF an d in NMP (with 0.02 N ammonium formate ) .
  • EXAMPLE 15 This compares the properties of a polyaniline- poly( ethylene glycol)- polyaniline triblock copolymer of the present invention with a copolymer prepared by the method of Japanese Patent Publication 6-256509 to Oka and using the same non-ICP block.
  • the purpose of this example is to provide a direct comparison between a triblock copolymer prepared by the emulsion polymerization method of the present invention and a copolymer produced by the method disclosed in Japanese Pat. Publ. No. 6-256509 to Oka.
  • the same aniline and non-ICP block were used in each method and the non-ICP block was selected to be very similar to that used in one example of the Oka Publication.
  • An amine- terminated poly( ethylene glycol) having a molecular weight of about 500 was used in this example compared with Example No. 1 of the Oka publication, in which an amine-terminated poly(ethylene glycol) having a molecular weight of about 400 was used.
  • Poly( ethylene glycol) (0.85 g, of o,o'-Bis(2- aminopropyl) polyethylene glycol, PEG500, available from Fluka Chemical Co.), deionized water (300 ml), aniline (8.5 g), dinonylnaphalenesulfonic acid (DNNSA; 69.5 g), 2-butoxyethanol (69.5 g), (a 50:50 solution of DNNSA in 2-butoxyethanol is available as Nacure® 1051 from King Industries, Inc.), were added to a 1 liter jacketed glass kettle reactor in an ice bath and cooled to 0° - 2 ⁇ C.
  • the product was soluble i -THF.
  • a film was then cast from the copolymer (0.05 g) in a solution of THF (1.0 g) and the conductivity was measured by the method described in Example 4.
  • the film had a conductivity of 4 x 10" 3 S/cm.
  • solubility of the copolymer was then determined in xylenes and chloroform.
  • Two samples of the solid copolymer (each 0.12 g) were mixed separately with xylenes (1.01 g, from Fisher Scientific) and with chloroform (1.01 g, from Burdick & Jackson). All of the solid polymer was dissolved in each solution to produce clear, green solutions. This indicates that the solubility of the DNNSA-doped (PANI )-(PEG500)-( PANI ) copolymer of the present invention is at least 10% wt/wt in xylenes and in chloroform.
  • Poly(ethylene glycol), (1.0 g, of o,o'-Bis(2- aminopropyl) polyethylene glycol, PEG500, available from Fluka Chemical Co.), deionized water (30 ml) and ammonium peroxidisulfate (24.5 g), were added to a 250 ml flask equipped with a magnetic stirrer and the mixture became a clear, colorless solution at room temperature. Upon cooling the solution in an ice bath for 30 min. , some solids precipitated. Aniline (10 g) was added to a solution of concentrated HC1 (50 ml of 12.1 N acid) and DI water (50 ml ) . The solution became light brown and upon cooling in an ice bath for 30 min.
  • the product was partially soluble in THF.
  • a solution of the material in THF was used to determine the molecular weight of the copolymer by the GPC method described in Example 1.
  • One half of the product (5.5 g ) was de-doped by mixing it with 150 ml of 5% wt/wt aqueous ammonium hydroxide solution and stirring for 2 hours.
  • the other half of the product (5.5 g) was purified by slurrying with 100 ml THF and stirring for 2 hours .
  • the solids were collected by vacuum filtration, washed three times with THF (3 x 80 ml) and air dried for 2 hours.
  • Films were cast from the de-doped copolymer (0.05 g) in a solution of THF (1.0 g), and from the de-doped copolymer (0.05 g) in a solution of THF (5.0 g) and Nacure® 1051 (0.1 g).
  • the conductivity of these films was measured by the method described in Example 4.
  • the film containing the de-doped copolymer was non- conductive.
  • the resistance of the film cast from the dedoped copolymer that had been doped with DNNSA post- synthesis was close to the sensitivity limit of the meter ( 1 x 10" 9 Ohms ) , which would correspond to a conductivity of less than 1 x 10 " ⁇ S/cm.
  • the solubility of the de-doped copolymer and of the de-doped copolymer after re-doping with DNNSA were determined in xylene and chloroform.
  • Another mixture was prepared of the de-doped copolymer (0.0191 g) and xylenes (9.5 g) as described above, except that Nacure® 1052 (0.05 g), was added to re-dope the copolymer with DNNSA.
  • a mixture was prepared of the de-doped copolymer (0.0295 g) with chloroform (15 g) and DNNSA (0.075 g). After thorough mixing, undissolved particles remained in the mixture, indicating that the solubility of the copolymer re-doped with DNNSA was less than 1% wt/wt.

Abstract

Copolymère séquencé électriquement conducteur composé d'une séquence polymère non intrinsèquement conductrice liée à au moins une séquence polymère intrinsèquement conductrice par un groupe de liaison. La séquence polymère intrinsèquement conductrice est polymérisée en tant que sel d'un acide organique. Le copolymère séquencé possède un poids moléculaire élevé, est électriquement conducteur lorsqu'il est synthétisé et possède une solubilité dans le xylène d'au moins environ 1 % en poids. Un procédé de production desdits copolymères séquencés est également décrit.
PCT/EP1998/005993 1997-09-25 1998-09-22 Copolymeres sequences electriquement conducteurs contenant un polymere intrinsequement conducteur WO1999016084A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93784197A 1997-09-25 1997-09-25
US08/937,841 1997-09-25

Publications (1)

Publication Number Publication Date
WO1999016084A1 true WO1999016084A1 (fr) 1999-04-01

Family

ID=25470484

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/005993 WO1999016084A1 (fr) 1997-09-25 1998-09-22 Copolymeres sequences electriquement conducteurs contenant un polymere intrinsequement conducteur

Country Status (1)

Country Link
WO (1) WO1999016084A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001035717A2 (fr) * 1999-11-15 2001-05-25 General Electric Company Procede direct de preparation de polyaniline dopee, produit ainsi prepare et articles resineux contenant ce produit
EP1481014A1 (fr) * 2001-08-31 2004-12-01 Tda Research, Inc. Copolymeres sequences poly(heteroaromatiques) presentant une conductivite electrique
US7361728B1 (en) 2004-09-30 2008-04-22 Tda Research, Inc. Electrically conducting materials from branched end-capping intermediates
WO2009040626A2 (fr) * 2007-09-25 2009-04-02 Toyota Jidosha Kabushiki Kaisha Matériau à base de métal traité contre la rouille et procédé pour traiter contre la rouille une surface du matériau à base de métal
DE102007047633A1 (de) 2007-10-04 2009-04-09 Henkel Ag & Co. Kgaa Vernetzbare Polymere mit heteroaromatischen Gruppen
US7687582B1 (en) 2001-08-31 2010-03-30 Tda Research, Inc. Methods of production, purification, and processing of poly(heteroaromatic) block copolymers with improved solubility or dispersability
WO2021007029A1 (fr) * 2019-07-10 2021-01-14 Covestro Llc Polyéthers et leur utilisation dans la production de mousses de polyuréthane souples

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095076A (en) * 1990-11-05 1992-03-10 Lockheed Corporation Preparation of highly soluble conductive polymer materials
US5227092A (en) * 1991-07-10 1993-07-13 Allied-Signal Inc. Process for forming conjugated backbone block copolymers
JPH06256509A (ja) * 1993-03-01 1994-09-13 Tomoegawa Paper Co Ltd ポリアニリン−ポリエーテルブロック共重合体およびその製造方法
US5635563A (en) * 1991-04-01 1997-06-03 Tomoegawa Paper Co., Ltd. Polyaniline derivatives and their production process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095076A (en) * 1990-11-05 1992-03-10 Lockheed Corporation Preparation of highly soluble conductive polymer materials
US5635563A (en) * 1991-04-01 1997-06-03 Tomoegawa Paper Co., Ltd. Polyaniline derivatives and their production process
US5227092A (en) * 1991-07-10 1993-07-13 Allied-Signal Inc. Process for forming conjugated backbone block copolymers
JPH06256509A (ja) * 1993-03-01 1994-09-13 Tomoegawa Paper Co Ltd ポリアニリン−ポリエーテルブロック共重合体およびその製造方法

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
FRANCOIS B ET AL: "Block-copolymers with conjugated segments: synthesis and structural characterization", PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY OF SYNTHETIC METALS (ICSM'94). PART 1;SEOUL, SOUTH KOREA JUL 24-29 1994, vol. 69, no. 1-3 part 1, 24 July 1994 (1994-07-24), Synth Met;Synthetic Metals; Polymers Mar 1 1995 Elsevier Science S.A., Lausanne, Switzerland, pages 463 - 466, XP002091473 *
FRANCOIS B ET AL: "Polystyrene-polythiophene block copolymers (PS-PT) synthesis characterization and doping", PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY OF SYNTHETIC METALS, PART 5 (OF 6);GOTEBORG, SWED AUG 12-18 1992, vol. 57, no. 1 part 5, 12 August 1992 (1992-08-12), Synth Met;Synthetic Metals; Processing of Polymers, Applications, Langmuir-Blodgett Films, Non-linear Optics, and Polymer Electronics Apr 12 1993 Publ by Elsevier Sequoia SA, Lausanne 1, Switz, pages 3489 - 3494, XP002091471 *
LI SUZHEN ET AL: "Synthesis and characterization of soluble polyaniline", PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY OF SYNTHETIC METALS - ICSM '88;SANTA FE, NM, USA JUN 26-JUL 2 1988, vol. 29, no. 1, 26 June 1988 (1988-06-26), Synth Met Mar 7 1989, pages 329 - 336, XP002091469 *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 656 (C - 1286) 13 December 1994 (1994-12-13) *
VAN HUTTEN P F ET AL: "Structure of thiophene-based regioregular polymers and block copolymers and its influence on luminescence spectra", J PHYS CHEM;JOURNAL OF PHYSICAL CHEMISTRY MAR 9 1995 ACS, WASHINGTON, DC, USA, vol. 99, no. 10, 9 March 1995 (1995-03-09), pages 3218 - 3224, XP002091472 *
ZHANG G P ET AL: "Electrically conductive blocked copolymer of polyaniline and poly(p-phenylene-terephthalamide)", PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON SCIENCE AND TECHNOLOGY OF SYNTHETIC METALS - ICSM '90;TUEBINGEN, GERMANY SEP 2-7 1990, vol. 41, no. 1-2, 2 September 1990 (1990-09-02), Synth Met;Synthetic Metals Apr 30 1991, pages 251 - 254, XP002091470 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001035717A2 (fr) * 1999-11-15 2001-05-25 General Electric Company Procede direct de preparation de polyaniline dopee, produit ainsi prepare et articles resineux contenant ce produit
WO2001035717A3 (fr) * 1999-11-15 2001-11-29 Gen Electric Procede direct de preparation de polyaniline dopee, produit ainsi prepare et articles resineux contenant ce produit
EP1481014A1 (fr) * 2001-08-31 2004-12-01 Tda Research, Inc. Copolymeres sequences poly(heteroaromatiques) presentant une conductivite electrique
EP1481014A4 (fr) * 2001-08-31 2005-08-03 Tda Research Inc Copolymeres sequences poly(heteroaromatiques) presentant une conductivite electrique
US7279534B2 (en) 2001-08-31 2007-10-09 Tda Research, Inc. Poly(heteroaromatic) block copolymers with electrical conductivity
US7687582B1 (en) 2001-08-31 2010-03-30 Tda Research, Inc. Methods of production, purification, and processing of poly(heteroaromatic) block copolymers with improved solubility or dispersability
US7361728B1 (en) 2004-09-30 2008-04-22 Tda Research, Inc. Electrically conducting materials from branched end-capping intermediates
WO2009040626A2 (fr) * 2007-09-25 2009-04-02 Toyota Jidosha Kabushiki Kaisha Matériau à base de métal traité contre la rouille et procédé pour traiter contre la rouille une surface du matériau à base de métal
WO2009040626A3 (fr) * 2007-09-25 2009-07-02 Toyota Motor Co Ltd Matériau à base de métal traité contre la rouille et procédé pour traiter contre la rouille une surface du matériau à base de métal
DE102007047633A1 (de) 2007-10-04 2009-04-09 Henkel Ag & Co. Kgaa Vernetzbare Polymere mit heteroaromatischen Gruppen
WO2021007029A1 (fr) * 2019-07-10 2021-01-14 Covestro Llc Polyéthers et leur utilisation dans la production de mousses de polyuréthane souples
CN114080411A (zh) * 2019-07-10 2022-02-22 科思创有限公司 聚醚及其在制备柔性聚氨酯泡沫中的用途

Similar Documents

Publication Publication Date Title
KR100295528B1 (ko) 전기전도성중합체및그의전구체를해응집시키는산화/환원방법및이에의한제품의제조방법
US7064178B2 (en) Soluble self-orienting materials and conductive polymer compositions having the same
US5804649A (en) Water-soluble self acid-doped polyaniline, method of preparation thereof, and polymer blends made therefrom
JP3066431B2 (ja) 導電性高分子複合物の製造方法
WO1999016084A1 (fr) Copolymeres sequences electriquement conducteurs contenant un polymere intrinsequement conducteur
US4548738A (en) Electrically conducting complexes of poly (3,6-N-alkylcarbazolyl alkenes) and method of making
Hua et al. Synthesis of a water‐soluble diblock copolymer of polysulfonic diphenyl aniline and poly (ethylene oxide)
JPH10120782A (ja) 枝分かれ構造を有する導電性重合体およびその前駆物質、ならびにその応用
Kim et al. Aromatic and rigid rod polyelectrolytes based on sulfonated poly (benzobisthiazoles)
KR100648893B1 (ko) 전기전도도가 우수한 폴리아닐린 및 그 제조 방법
KR20050108107A (ko) 전기전도도 및 유기용매에 대한 용해성이 향상된 전도성고분자 및 그 제조 방법
JP2704587B2 (ja) ポリアニリン−ポリエーテルブロック共重合体およびその製造方法
JP2949554B2 (ja) 複合成形体およびその製造方法
WO2008072858A1 (fr) Procédé de préparation de polyaniline conductrice par polymérisation en dispersion auto-stabilisée à régulation de température
JP2942785B2 (ja) 有機重合体溶液
JPH0757802B2 (ja) ポリアニリン誘導体の製造方法
Li et al. Facile synthesis of oxidative copolymers from aminoquinoline and anisidine
JPS61159423A (ja) 細工しやすい電気的活性ポリマ−
JP2843938B2 (ja) 導電性有機重合体組成物フイルム及びその製造方法
Leuninger et al. Poly (phenylene sulfide–phenyleneamine–phenyleneamine)(PPSAA)—a soluble model for polyaniline
JP2683996B2 (ja) ポリアニリン誘導体およびその製造方法
JP2841123B2 (ja) ポリアニリン誘導体の製造方法
JPH04372623A (ja) ポリアニリン誘導体およびその製造方法
JP2683995B2 (ja) ポリアニリン誘導体およびその製造方法
Savitha et al. Poly (o-toluidine-co-o-chloroaniline) copolymers: Effect of polymerization conditions on the properties of the copolymers

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA