[go: up one dir, main page]

WO2011137457A1 - Composites nanostructurés à base de polymère conducteur et leurs procédés de préparation - Google Patents

Composites nanostructurés à base de polymère conducteur et leurs procédés de préparation Download PDF

Info

Publication number
WO2011137457A1
WO2011137457A1 PCT/US2011/034857 US2011034857W WO2011137457A1 WO 2011137457 A1 WO2011137457 A1 WO 2011137457A1 US 2011034857 W US2011034857 W US 2011034857W WO 2011137457 A1 WO2011137457 A1 WO 2011137457A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
conducting
dispersion
polymer composite
conducting polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2011/034857
Other languages
English (en)
Inventor
Christina Baker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of WO2011137457A1 publication Critical patent/WO2011137457A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • One aspect of the present disclosure relates to a solvent exchange method for the preparation of a dispersion of a conducting material in a solvent or a solvent mixture without the addition or use of surfactants and/or fillers and the solvent or solvent mixture does not disperse the dry conducting material without surfactants and/or fillers, or the solvent or solvent mixture disperses the conducting material more efficiently using this solvent exchange method than without using the solvent exchange method.
  • Another aspect of the present disclosure relates to a conducting polymer composite
  • a conducting polymer composite comprising a first material and a second material different from the first material
  • the first material comprises at least a first conducting material selected from the group consisting of conducting monomers, conducting oligomers, conducting polymers, and blends thereof
  • the first material and the second material are blended covalently and/or non- covalently
  • the composite has an enhanced processability compared to the first material or the conducting polymer or oligomer.
  • Another aspect of the present disclosure relates to a method of preparing the conducting polymer composite.
  • Figure 1 Conducting polymer composite formed by blending polystyrene and polyaniline nanofiber.
  • Figure 2 Conducting polymer composite formed by blending polymethylmethacrylate (PMMA) and polyaniline nanofiber.
  • PMMA polymethylmethacrylate
  • Figure 3 Conducting polymer composite formed by blending
  • Nylon 6,6 and polyaniline nanofiber shows the nylon threads as they were wound around a glass rod following polymerization.
  • Figure 4 Preparation scheme of conducting polymer composite formed by blending polyamide and polyaniline nanofiber covalently using polyaniline (A), diamine terminated polyaniline (B), or a derivative of either A or B (C), for partial substitution of some of the diamine in the synthesis of a polyamide.
  • One aspect of the present disclosure relates to a solvent exchange method for preparing a dispersion of a conducting material in a solvent or a solvent mixture without the use of surfactants and/or fillers, where the solvent or solvent mixture generally does not disperse a dry conducting material without the use of surfactants and/or fillers.
  • the solvent or solvent mixture provides for dispersing the conducting material more efficiently using this solvent exchange method.
  • the phrase more efficient dispersions means providing a more uniform dispersion (by, for example, having less agglomerate or small particulates in the dispersion), or providing substantially the same dispersion but in a shorter time period or under more mild conditions (e.g., lower temperature, without sonication methods) when compared to dispersing the same conducting material in the same solvent, solvent mixture or the second material without using the solvent exchange method.
  • the conducting material is dispersed while wet, such that the conducting material is never allowed to dry until dispersion is complete. This is particularly useful where the conducting material is formed or produced in a solvent system.
  • the dispersion facilitates making conducting polymer composites formed by blending the conducting material and other materials through covalent and/or non-covalent interaction, and coating formulations (mixtures of inherently conducting polymers (ICPs) with other polymers or additives for robust coatings).
  • the dispersions allow a desired mixture of the conducting material into a matrix polymer. If the ICP is well dispersed (i.e., doesn't form bundles or aggregates when mixed with another polymer), then it requires less material to achieve a desired level of conductivity and/or reach the percolation threshold of conductivity in the solid form of the composite.
  • a dispersion of a material in a desired solvent is prepared by a solvent exchange method comprising:
  • material can be conductive materials (e.g. conducting monomers, conducting oligomers, conducting polymers, and blends thereof) and non-conductive materials (e.g. non-conducting
  • blend means a mixture formed or to form a mixture of two materials through covalent interactions and/or non-covalent interactions.
  • dispersion means a liquid-solid system, e.g., suspension, solution and swelled mixture; “disperse” means suspend, dissolve or swell a solid into a liquid to form dispersion. And, as set forth above, some methods disclosed herein will provide a more efficient dispersion when compared to prior art methods without the need for surfactants and/or fillers.
  • a solvent can be a solvent, a mixture of more than one solvent, or a solution (e.g. aqueous solution).
  • Examples of conducting monomers include, without limitation, aniline, thiophene, pyrrole, and phenylene.
  • Examples of conducting oligomer and conducting polymers include, without limitation, oligomers and polymers comprising the same or different conducting monomers, and derivatives thereof.
  • Derivatives of oligomers and polymers can be chemically modified derivatives and/or physically modified derivatives. Chemical modification may occur within the backbone, at an end of the backbone or on the sidechain of the oligomers and polymers. Physical modifications include, for example, doped polymers and oligomers, and nanostructured polymers and oligomers (e.g. nanofibers). Examples of physically and/or chemically modified derivatives of conducting oligomers and polymers include, without limitation, doped and undoped polyaniline, doped and undoped
  • polythiophene doped and undoped polypyrrole, doped and undoped polyparaphenylene, doped and undoped oligoaniline, doped and undoped oligothiophene, doped and undoped oligopyrrole, doped and undoped oligoparaphenylene, doped and undoped polyaniline nanofibers, doped and undoped polythiophene nanofibers, doped and undoped polypyrrole nanofibers, doped and undoped polyparaphenylene nanofibers, alkyl functionalized derivatives thereof, sulfonate functionalized derivatives thereof, amine functionalized derivatives thereof, carbonyl functionalized derivatives thereof, hydroxyl functionalized derivatives thereof, carboxylic acid
  • non-conducting polymers include, without limitation, polyacrylamide, polyester, polyacrylate polymers, polyacrylate esters, polyacrylic acid, polyacrylonitrile, polyamic acids, polyaryl sulfonates, polybutadiene, polyamide, Nylon 6, Nylon 6,6, Nylon 6,8, polyphthalamide, aromatic polyamide, cellulose, cellulose triacetate, polyethylene oxide, polyisobutene, polyisoprene, polymethacrylate esters, polymethacrylic acids, polyphenylene sulfone, polypropylene oxide, polysiloxanes,
  • PMMA polymethylmethacrylate
  • PVA polystyrene
  • PSSA polystyrene sulfonic acid
  • acrylic acid polyvinyl butyryl
  • polyvinyl chloride polyvinyl carbazole
  • polyvinylidine chloride polyvinylidine fluoride
  • poly(N-vinyl pyrrolidone) polymers of substituted ethylene, derivatives thereof, and blends thereof.
  • Examples of the desired solvents include, without limitation, water, aqueous solutions, sulfuric acid, alcohols (e.g. ethanol, methanol, isopropanol), toluene, ketones (e.g. methyl ethyl ketone, acetone), halogenated solvents (e.g. chlorinated hydrocarbons such as carbon tetrachloride, chloroform; trichloroethanol, trifluoroacetic acid,
  • alcohols e.g. ethanol, methanol, isopropanol
  • ketones e.g. methyl ethyl ketone, acetone
  • halogenated solvents e.g. chlorinated hydrocarbons such as carbon tetrachloride, chloroform; trichloroethanol, trifluoroacetic acid
  • conductive materials that are dispersed in a solvent (e.g., water) or other reacting liquid can be dispersed in a solvent or other reacting liquid of choice if not substantially dried prior to further processing.
  • a solvent e.g., water
  • Conventional methods such as rotary-evaporation (rotavap), using a fully dried filter cake, freeze drying, etc. cause too much particle aggregation and cannot fully disperse the material following complete drying.
  • the conducting polymers or oligomers are dispersed in the chosen solvent, they can be blended with another polymer that is dispersed in the same or a miscible solvent.
  • the original solvent is fully removed to provide a stable dispersion for the formation of the conducting polymer nanostructures in the new dispersion.
  • solvent exchange of a dispersion of is accomplished by filtration, centrifugation or dialysis based solvent exchange methods.
  • a filtration based solvent exchange method comprises filtering the dispersion to form a cake and then dispersing the cake into a desired solvent.
  • the cake should be kept wet throughout the processing, and the cake is preferably not allowed to get to the point of cracking during filtration.
  • the desired solvent is miscible with the first solvent.
  • the low concentration of the first solvent allows a semi-stable dispersion.
  • the method further comprises rinsing the filter cake with the desired solvent (at least once and preferably three times or more) prior to dispersing the filter cake into the desired solvent. The latter method is preferred when the desired solvent and the first solvent are not adequately miscible, when the first solvent is incompatible with the end application, or the dispersion in the desired solvent is not adequately stable.
  • a dialysis based solvent exchange method comprises adding the polymer dispersion to a dialysis bag with either end of the bag closed off; immersing the bag into a large (typically >10 times) volume of the desired solvent.
  • the mixture can be mixed, or left to sit unmixed for a period of time (e.g., 24 hours) until a sufficient amount of the first solvent is removed. At this point the solvent is poured off and more of the desired final solvent is added. This process can be repeated twice, thrice or more until a sufficient amount of the first solvent is removed.
  • a centrifugation based solvent exchange method comprises spinning the dispersion until a pellet is formed; decanting the supernatant; and adding the desired solvent.
  • the spinning-decanting-adding process can be repeated twice, thrice or more until a satisfying amount of the first solvent is removed. This process results in dispersions with good stability, particularly when transferring conducting polymers/oligomers dispersed in water to other polar solvents such as alcohols (e.g., ethanol, methanol, isopropanol), and ketones (e.g. methyl ethyl ketone, acetone).
  • alcohols e.g., ethanol, methanol, isopropanol
  • ketones e.g. methyl ethyl ketone, acetone
  • Another aspect of the present disclosure relates to a conducting polymer composite comprising a first material and a second material different from the first material.
  • the first material comprises at least a first conducting material selected from the group consisting of conducting monomers, conducting oligomers, conducting polymers, and blends thereof.
  • the second material comprises at least a first non-conducting material. The first material and the second material are blended together through covalent interactions and/or non-covalent interactions.
  • the composite has an enhanced processability compared to the first material or the conducting polymer or oligomer.
  • the conducting polymer composite can be sufficiently dispersed in a solvent or a solvent mixture at a higher level of dispersion (e.g., a more efficient dispersion) than would otherwise be possible without using the disclosed methods and that cannot now be achieved without the use of surfactants and/or fillers.
  • a higher level of dispersion e.g., a more efficient dispersion
  • the first material and the second material are independently selected from the group consisting of conducting materials, non-conducting materials and any blends thereof.
  • the mass ratio of the first material and the second material can be from about 5:1 to about 1 :500, from about 1 :1 to about 1 :50, from about 1 :1 to about 1 :1 0, from about 1 :1 to about 1 :5, from about 1 :2 to about 1 :1 00, from about 1 :2 to about 1 :50, from about 1 :2 to about 1 :10, and from about 1 :2 to about 1 :5.
  • the mass ratio of the first conducting material and the first non-conducting material can be from about 5:1 to about 1 :500, from about 1 :1 to about 1 :50, from about 1 :1 to about 1 :1 0, from about 1 :1 to about 1 :5, from about 1 :2 to about 1 :1 00, from about 1 :2 to about 1 :50, from about 1 :2 to about 1 :1 0, and from about 1 :2 to about 1 :5.
  • a conducting polymer composite is formed by blending a first material and a second material through covalent interaction.
  • the first material or a part thereof may be incorporated into the backbones and/or the side chains of the second material, or a part thereof.
  • non-covalent interactions may also exist during the formation of the covalently-blended conducting polymer composite.
  • Examples of the first conducting material include, without limitation, doped and undoped polyaniline, doped and undoped
  • polythiophene doped and undoped polypyrrole, doped and undoped polyparaphenylene, doped and undoped oligoaniline, doped and undoped oligothiophene, doped and undoped oligopyrrole, doped and undoped oligoparaphenylene, doped and undoped polyaniline nanofibers, doped and undoped polythiophene nanofibers, doped and undoped polypyrrole nanofibers, doped and undoped polyparaphenylene nanofibers, alkyl functionalized derivatives thereof, sulfonate functionalized derivatives thereof, amine functionalized derivatives thereof, hydroxyl functionalized derivatives thereof, carbonyl functionalized derivatives thereof, carboxylic acid functionalized derivatives thereof, and blends thereof.
  • the oligomers' degrees of polymerizations are 4 or larger.
  • the second material comprises monomers, and/or oligomers and/or polymers having functional groups that can form covalent bond with the first material, e.g. carbonyl groups, amine groups, alcohol groups, and carboxylic acid groups.
  • first non-conducting material of the second material include, without limitation, polyamide, aromatic polyamides, Nylon 6,6, Nylon 6,8, Nylon 6, polymers comprising polyamide monomers (e.g. caprolactam, hexamethylene diamine, adipic acid, terephthalic acid, and other polyamide monomers), paraphenylenediamine, polyphthalamide, polyurethane, polyester, monomers thereof, and blends thereof.
  • a functional group of the first material may be protected to avoid formation of undesired covalent bonds among the first material and/or between the first material and the second material.
  • an amine group of polyaniline may be protected via conventional organic chemistry.
  • a conducting polymer composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer nanostructured composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer nanostructured composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer nanostructured composite comprising a first material and a second material is prepared by a method comprising:
  • a pre-polymer dispersion comprising the first material and the second material in a first desired solvent may be further converted to a dispersion in a second desired solvent before covalently blending the first material and the second material at a condition sufficient to form the conducting polymer composite.
  • a desired solvent e.g. the first desired solvent and the second desired solvent
  • the desired solvents include, without limitation, water, aqueous solutions, sulfuric acid, alcohols (e.g. ethanol, methanol, isopropanol), toluene, ketones (e.g. methyl ethyl ketone, acetone), halogenated solvents (e.g. chlorinated hydrocarbons such as carbon tetrachloride, chloroform;
  • the first desired solvent and the second desired solvent can be the same or different.
  • the first pre-polymer dispersion can be prepared from a first dispersion comprising the first material and a first solvent according to the solvent exchange method described supra.
  • the first solvent can be a solvent that disperse, dissolve and/or swell the first and/or the second material sufficiently, e.g. without limitation, alcohols (including ethanol, methanol or isopropanol), DMSO, HFIP, m-cresol, NMP, acetone or a combination thereof.
  • the first solvent may be another solvent that does not disperse, dissolve and/or swell the first material sufficiently after the material is in a dry state.
  • the first dispersion may be prepared by changing the solvent of a dispersion comprising the first material more than once using the solvent exchange method described supra.
  • the first desired solvent and the first solvent can be miscible or non-miscible.
  • the conducting polymer composite is a polyamide conducting polymer composite.
  • the first material comprises a first conducting material.
  • the second material comprises a polyamide (e.g. Nylon 6,6, Nylon 6,8, Nylon 6, polyphthalamide, aromatic polyamide), oligoamide, monomer to form a polyamide (e.g. hexamethylene diaminem adipic acid, caprolactam, polyphthalamide, terephthalic acid,
  • the first material is combined with one of the monomers of polyamide in solution prior to polyamide formation ( Figure 4, the first material is an inherently conducting polymer, conducting oligomer or conducting polymer nanofibers, e.g. polyaniline, polythiophene, polypyrrole, oligoaniline, oligothiophene, oligopyrrole, polyaniline nanofibers,
  • polythiophene nanofibers and polypyrrole nanofibers.
  • the formed polyamide is incorporated with the first material during polymerization.
  • the first material can be chemically modified with functional groups (e.g. alkyl, amine, alcohol, sulfonate, carbonyl or carboxylic acid groups) through the use of functionalized oligomer initiators or
  • the first material comprises a
  • nanostructured form e.g. nanofibers
  • Polyaniline and other conducting polymers typically require much effort to disperse them in solvents other than the limited solvents used to fully dissolve the polymers.
  • the typical solvents include N- methyl pyrrolidinone, m-cresol, DMF and a few others. These solvents fully dissolve the polymer and the polymer is often needed at higher percentage rates to achieve the percolation threshold to achieve conductivity in a blend. Utilizing the nanofibullar forms of polyaniline or other conducting polymers allows dispersion in a broad range of solvents, and incorporation at low loading levels to achieve conductivity.
  • An alternative method involves dispersion of a first material comprising polyaniline nanofibers into a solvent (e.g. water) with a second material comprising one (or more) of the monomers used to synthesize a matrix or structural polymer (e.g. polyamides).
  • a polyamide is synthesized using an interfacial polymerization with a diol in the acid phase and a diamine in an organic phase.
  • Polyaniline can be
  • polyaniline with additional amine groups will be taken up in place of the polyamide's diamine monomer for covalent incorporation of the polyaniline nanofibers into the polyamide during formation.
  • a conducting polymer composite comprising Nylon 6,6 and polyaniline nanofiber has been synthesized, with polyaniline incorporated while drawing the nylon. This combination can result in covalent and non-covalent incorporation of the polyaniline into the polyamide matrix.
  • the conducting polymer composite is prepared by mixing polyaniline nanofiber dispersions. [0053] ii) non-covalent blending
  • a conducting polymer composite is prepared by blending a first material and a second material through non- covalent interactions.
  • a conducting polymer composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer composite comprising a first material and a second material is prepared by a method comprising:
  • a conducting polymer composite comprising a first material and a second material is prepared by a method comprising:
  • the preparation of a conducting polymer composite further comprises a high energy mixing (e.g. sonication) to facilitate blending of the first and the second material.
  • a high energy mixing e.g. sonication
  • the first pre-dispersion can be prepared from a first dispersion comprising the first material and a first solvent according to the solvent exchange method below.
  • the first solvent can disperse, dissolve and/or swell the first material sufficiently, e.g. without limitation, alcohols (e.g.
  • the first solvent may be another solvent that does not disperse, dissolve and/or swell the first material sufficiently after the material is in a dry state.
  • the first dispersion may be prepared by changing a solvent of a dispersion comprising the first material more than once using the solvent exchange method described supra.
  • the first and/or second desired solvent and the first solvent can be miscible or non-miscible.
  • the first material and the second material can disperse in the same or miscible solvents such as water, aqueous solutions, sulfuric acid, alcohols (e.g. ethanol, methanol,
  • isopropanol toluene, ketones (e.g. methyl ethyl ketone, acetone), chlorinated solvents (e.g. chlorinated hydrocarbons such as carbon tetrachloride, chloroform; trichloroethanol; trifluoroacetic acid, hexafluoroacetic acid), THF, DMF, DMSO, glycols, m-cresol, NMP, polar solvents, and a combination thereof.
  • ketones e.g. methyl ethyl ketone, acetone
  • chlorinated solvents e.g. chlorinated hydrocarbons such as carbon tetrachloride, chloroform; trichloroethanol; trifluoroacetic acid, hexafluoroacetic acid
  • aqueous dispersions can be used to form blends of conducting polymer (e.g. polyaniline) with PVA, PSSA, poly acrylic acid and other water soluble polymers.
  • conducting polymer e.g. polyaniline
  • PVA polyaniline
  • PSSA poly acrylic acid
  • water soluble polymers may be useful additives for improved coatings, dispersion stability, end-product stability, shelf-life or matrix compatibility as necessary.
  • the first material is polyaniline nanofibers
  • the second material comprises a polyamide (e.g. Nylon 6, Nylon 6,6, Nylon 6,8, polyphthalamide, aromatic polyamide)
  • the first desired solvent is sulfuric acid.
  • the first material is polyaniline nanofiber
  • the second material is PMMA and/or polystyrene
  • the first desired solvent is acetone.
  • the conducting polymer composite is prepared using doped or undoped polyaniline nanofibers, or derivatives of polyaniline nanofibers.
  • the first material comprises a conducting polymer
  • the second material comprises a filler polymer
  • examples include, without limitation, polyacrylamide, polyester, polyacrylate polymers, polyacrylate esters, polyacrylic acid, polyacrylonitrile, polyamic acids, polyaryl sulfonates, polybutadiene, polyamide, Nylon 6, Nylon 6,6, Nylon 6,8, polyphthalamide, aromatic polyamide, cellulose, cellulose tracetate, polyethylene oxide, polyisobutene, polyisoprene, polymethacrylate esters, polymethacrylic acids, polyphenylene sulfone, polypropylene oxide, polysiloxanes, PMMA, polystyrene, polyurethanes, polyvinyl acetates, PVA, PSSA, poly acrylic acid, polyvinyl butyryl, polyvinyl chloride, polyvinyl carbazole, polyvinylidine chloride, polyvinylidine fluoride, poly(N-vinyl)
  • the filler polymer is dispersed in a second desired solvent, and is blended with the conducting polymer dispersed in a first desired solvent.
  • the first desired solvent can be the same solvent as the second desired solvent, a miscible solvent(s) of the second desired solvent, a combination of miscible solvents of the second desired solvent, or a combination thereof.
  • the miscible solvent include, without limitation, water, aqueous solutions, sulfuric acid, alcohols (e.g. ethanol, methanol, isopropanol), toluene, ketones (e.g. methyl ethyl ketone, acetone), chlorinated solvents (e.g.
  • chlorinated hydrocarbons such as carbon tetrachloride, chloroform; trichloroethanol; trifluoroacetic acid, hexafluoroacetic acid), THF, DMF, DMSO, glycols, tricresol, NMP, polar solvents, and a combination thereof.
  • a conducting polymer composite is dispersed in a desired solvent
  • the dispersion can be used for further processed such as for coating and/or blends with other polymers. These methods are used to blend or coat conducting polymers with or onto other polymers, nanoparticles and substrates through the use of an appropriate solvent system.
  • a dispersion of a conducting polymer composite in one solvent can be converted to a dispersion in another solvent using the solvent exchange method as described supra.
  • Low polarity polymers/oligomers may be more difficult to blend with conducting polymers/oligomers as the low polarity polymers/oligomers tend to be soluble in non-polar solvents, which do not typically disperse conducting polymers/oligomers (e.g. polyaniline nanofibers and conducting polymer nanofibers).
  • conducting polymers/oligomers e.g. polyaniline nanofibers and conducting polymer nanofibers.
  • a 10% w/w solution of Nylon 6,6 was made by dissolving the nylon in 50% concentrated sulfuric acid and 50% deionized water, and mixing for 12 hours.
  • Polyaniline nanofiber dispersion (1 g, at a concentration of >20% w/w in water) was added to 10 g of the 10% w/w solution of nylon and mixed well. The mixture was cast to form a film and dried, or washed by centrifugation, dialysis or filtration prior to further use. Centrifugation was used to transfer the mixture to another solvent and/or remove excess acid. Removal of excess water under vacuum and/or elevated temperatures was used to increase the polymer chain length and strength of the nylon.
  • a polymethylmethacrylate and polyaniline nanofiber blend was prepared by dissolving 20 g PMMA and 1 g of a polyaniline nanofiber filter cake (> 5% w/w) into 50 ml_ acetone and 2.5 ml_ 1 M HCI. The polyaniline blended into the polymer well and was allowed to dry in a 20 ml_ vial ( Figure 2).
  • Example 4 A polystyrene and polyaniline nanofiber blend was made by adding 20 g polystyrene and 1 g polyaniline nanofiber filter cake (> 5% w/w) into 50 ml_ acetone and 2.5 ml_ 1 M HCI. The swollen polyaniline and polystyrene blend was separated from acetone, dried partially as a film and then transferred to a 20 ml_ vial to fully dry (Figure 3).
  • Nylon 6,6 was dissolved in sulfuric acid and combined with polyaniline nanofibers with high energy mixing (e.g. sonication) at a 10:1 mass ratio.
  • Nylon 6 was dissolved in sulfuric acid and combined with polyaniline nanofibers with high energy mixing (e.g. sonication) at a 10:1 mass ratio.
  • PVA was blended with polyaniline nanofibers in water to provide a dispersion of polyaniline nanofibers and polyvinyl alcohol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Dans un mode de réalisation, un procédé d'échange de solvant pour la préparation d'une dispersion d'une matière conductrice dans un solvant voulu est fourni consistant à se procurer une première dispersion de matière conductrice dans un premier solvant, la matière conductrice n'ayant pas été dans un état sec avant sa dispersion dans le premier solvant, et à se procurer une seconde dispersion de la matière conductrice dans le solvant voulu par échange du premier solvant avec le solvant voulu tout en conservant la matière conductrice humide, la matière conductrice étant plus efficacement dispersée dans le solvant voulu par comparaison avec la dispersion de la matière conductrice dans un état sec dans le solvant voulu.
PCT/US2011/034857 2010-04-30 2011-05-02 Composites nanostructurés à base de polymère conducteur et leurs procédés de préparation Ceased WO2011137457A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33031110P 2010-04-30 2010-04-30
US61/330,311 2010-04-30

Publications (1)

Publication Number Publication Date
WO2011137457A1 true WO2011137457A1 (fr) 2011-11-03

Family

ID=44861955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/034857 Ceased WO2011137457A1 (fr) 2010-04-30 2011-05-02 Composites nanostructurés à base de polymère conducteur et leurs procédés de préparation

Country Status (1)

Country Link
WO (1) WO2011137457A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822282A (zh) * 2018-05-28 2018-11-16 上海大学 一种导电聚合物及其制备方法
CN109932760A (zh) * 2019-04-02 2019-06-25 上海第二工业大学 一种透明胶体光子晶体膜的制备方法
CN116120593A (zh) * 2022-12-21 2023-05-16 东华大学 一种聚乙烯醇-苯胺四聚体有机水凝胶纤维及其制备方法和应用
CN116622039A (zh) * 2023-07-26 2023-08-22 上海宇昂水性新材料科技股份有限公司 一种乙烯基吡咯烷酮嵌段共聚物及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020004556A1 (en) * 1998-10-23 2002-01-10 Foulger Stephen H. Crosslinked conducting polymer composite materials and method of making same
US20030088032A1 (en) * 2001-08-31 2003-05-08 Luebben Silvia Devito Poly(heteroaromatic) block copolymers with electrical conductivity
US20070045590A1 (en) * 2005-08-26 2007-03-01 Council Of Scientific And Industrial Research Process for preparation of conductive polymer dispersion
US20070194286A1 (en) * 2006-02-17 2007-08-23 The Regents Of The University Of California Fabrication of polyaniline nanofiber dispersions and films
US7354532B2 (en) * 2004-04-13 2008-04-08 E.I. Du Pont De Nemours And Company Compositions of electrically conductive polymers and non-polymeric fluorinated organic acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020004556A1 (en) * 1998-10-23 2002-01-10 Foulger Stephen H. Crosslinked conducting polymer composite materials and method of making same
US20030088032A1 (en) * 2001-08-31 2003-05-08 Luebben Silvia Devito Poly(heteroaromatic) block copolymers with electrical conductivity
US7354532B2 (en) * 2004-04-13 2008-04-08 E.I. Du Pont De Nemours And Company Compositions of electrically conductive polymers and non-polymeric fluorinated organic acids
US20070045590A1 (en) * 2005-08-26 2007-03-01 Council Of Scientific And Industrial Research Process for preparation of conductive polymer dispersion
US20070194286A1 (en) * 2006-02-17 2007-08-23 The Regents Of The University Of California Fabrication of polyaniline nanofiber dispersions and films

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822282A (zh) * 2018-05-28 2018-11-16 上海大学 一种导电聚合物及其制备方法
CN108822282B (zh) * 2018-05-28 2020-11-24 上海大学 一种导电聚合物及其制备方法
CN109932760A (zh) * 2019-04-02 2019-06-25 上海第二工业大学 一种透明胶体光子晶体膜的制备方法
CN109932760B (zh) * 2019-04-02 2021-05-25 上海第二工业大学 一种透明胶体光子晶体膜的制备方法
CN116120593A (zh) * 2022-12-21 2023-05-16 东华大学 一种聚乙烯醇-苯胺四聚体有机水凝胶纤维及其制备方法和应用
CN116622039A (zh) * 2023-07-26 2023-08-22 上海宇昂水性新材料科技股份有限公司 一种乙烯基吡咯烷酮嵌段共聚物及其制备方法和应用
CN116622039B (zh) * 2023-07-26 2023-10-24 上海宇昂水性新材料科技股份有限公司 一种乙烯基吡咯烷酮嵌段共聚物及其制备方法和应用

Similar Documents

Publication Publication Date Title
US20210331231A1 (en) Metal form containing dispersed aerogel particles impregnated with polymers and a method of producing the same
CN101124251B (zh) 在离子液体中的聚合物溶解和共混物形成
FR2793252A1 (fr) Copolyamide hyperbranche, composition a base de ce copolyamide hyperbranche et procede d'obtention de ce dernier
KR101406597B1 (ko) 그래핀-고분자 수지 복합체 분말 및 섬유 제조방법
Liu et al. Fabrication of degradable polymer microspheres via pH-responsive chitosan-based Pickering emulsion photopolymerization
CN101746769B (zh) 聚酰胺层状硅酸盐组合物
WO2011137457A1 (fr) Composites nanostructurés à base de polymère conducteur et leurs procédés de préparation
CN102040695A (zh) 水溶性聚乙烯吡咯烷酮接枝聚苯胺共聚物制备方法
WO2011144321A1 (fr) Composition de polymère contenant du graphène
CN105017750A (zh) 一种水性芳族聚酰胺乳液、制备方法及其应用
CN116479583A (zh) 共价有机框架复合纳米纤维电致变色膜及其制备和应用
WO2020104303A1 (fr) Procédé de préparation d'une fibre fonctionnelle
CN101200510A (zh) 一种可溶性有机高分子导电材料及其制法
Tan et al. Rigid-rod molecular composites via ionic interactions
CN110628052B (zh) 石墨烯分散液、石墨烯/聚合物复合材料及其制备方法
CN103183888A (zh) 碳纳米管复合材料的制备方法
CN104593901A (zh) 一种聚酰胺接枝碳纳米管复合纤维的制备方法
CN110396730B (zh) 一种导电聚苯胺共混纤维及其制备方法和应用
CN112029273A (zh) 具有石墨烯-碳纳米管复合结构的导电尼龙母粒及其制备方法
JP4415341B2 (ja) ポリピロール系導電性塗料
CN113956652B (zh) 一种抗静电母料制备方法及抗静电母料
US20090014920A1 (en) Polymer filaments
CN116875027A (zh) 介电阻燃复合材料及其制备方法
WO2004055096A1 (fr) Production de fines particules poreuses de polyimide
Lapworth et al. Thermally responsive gels formed from highly branched poly (N-isopropyl acrylamide) s with either carboxylic acid or trihistidine end groups

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11775716

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11775716

Country of ref document: EP

Kind code of ref document: A1