EP2212373A2 - Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau - Google Patents

Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau

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Publication number
EP2212373A2
EP2212373A2 EP08851293A EP08851293A EP2212373A2 EP 2212373 A2 EP2212373 A2 EP 2212373A2 EP 08851293 A EP08851293 A EP 08851293A EP 08851293 A EP08851293 A EP 08851293A EP 2212373 A2 EP2212373 A2 EP 2212373A2
Authority
EP
European Patent Office
Prior art keywords
polyaniline
substrate
acid
doped
coated substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08851293A
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German (de)
English (en)
Inventor
Karl-Heinz Pettinger
Franz-Xaver MÜLLER
Gerhard Illing
Mathias Ulbricht
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.)
Sued Chemie IP GmbH and Co KG
Original Assignee
Sued Chemie AG
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Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of EP2212373A2 publication Critical patent/EP2212373A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/91—Bacteria; Microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the invention relates to polyaniline derivatives with organosulfur units and to the use of the polyaniline derivatives in water treatment, for the purification of air, for the production of redox-flow batteries or in electrolysis.
  • the invention also relates to a process for the preparation of the novel polyaniline derivatives and substrates coated with the polyaniline derivatives.
  • Advanced Oxidation Processes generate OH radicals, which then act oxidatively on the impurities.
  • polyaniline produces active oxygen species, such as OH radicals, superoxide radical anions and the like, from the oxygen dissolved in the water and can be electrochemically regenerated.
  • ICP intrinsically conductive polymers
  • the group of ICP also includes polyaniline (PAni).
  • PAni polyaniline
  • the synthesis of polyaniline is carried out via free-radical (Min-Jong Chang, Yun-Hsin Liao, Allan S. Myerson, TK Kwei, J. Appl. Pol. Sei., Vol. 62, 1427-1428) or electrochemical polymerization from acidic solution ( BJ Hwang, R. Santhanam, CR Wu, and YW Tsai, J. Solid State Electrochem., 5: 280-286, 2001).
  • Polyaniline been used mainly as protection against corrosion, in the electronics (conductive layer in flexible PCB 's and displays), for EMI shielding, or as anti-static component.
  • Polyaniline is also described in the literature for water treatment (see for example EP 0 782 970 B1).
  • the use of polyaniline can be carried out, for example, as granules and the treatment of the waters in bulk beds.
  • Membranes in which a catalytic activity is directly combined with a special barrier structure are of particular interest in process intensification. This can be achieved by embedding a catalyst in the bulk of the membrane material or by immobilization on the outer or inner membrane surface.
  • An example of the latter variant is the catalytic detoxification of an aqueous stream (degradation of chlorinated hydrocarbons) by a porous membrane of cellulose acetate with immobilized Fe / Ni nanoparticles (Meyer DE, Wood K., Bachas LG, Bhattacharyya D., Environmental Progress 2004 ; 23: 232-242).
  • JP 2003-159596 which describes polyaniline-coated membranes for the destruction of microorganisms by active oxygen.
  • the invention was therefore based on the object to eliminate the disadvantages known in the prior art, ie to provide a polyaniline which is readily dispersible and has good adhesion to substrates and is also suitable for water treatment.
  • the object is achieved by a polyaniline comprising aniline units and organosulfur units, characterized in that the polyaniline is doped and has a number-average degree of polymerization of from about 5 to about 50
  • Also included within the scope of the invention is a process for preparing polyaniline wherein aniline and at least one organosulfur moiety are reacted in an oxidative, acid-catalyzed polymerization reaction to form a polyaniline dehydrate.
  • the invention likewise relates to a coated substrate which is coated with the polyaniline according to the invention and to a method for coating the substrate,
  • the scope of the invention also includes a coating composition which is suitable for coating the substrate.
  • the invention thus also relates to a process for the preparation of the coating composition, the process comprising the steps: a) providing a ground polyaniline according to the invention, b) optionally further grinding the polyaniline, c) producing a dispersion of the ground polyaniline and a dispersant, d) optionally treating the dispersion by energy input, in particular with ultrasound, and e) filtering.
  • polyaniline which is doped and has sulfur in the main polymer chain, for water treatment, in particular water purification and / or
  • the invention relates to a polyaniline which comprises aniline units and organosulfur units and is characterized in that the polyaniline is doped and has a number-average degree of polymerization of from about 5 to about 50, preferably from about 8 to about 35, more preferably from about 8 to about 30.
  • Polyaniline is a conjugated polymer consisting of oxidative and acid-catalyzed coupled aniline monomers.
  • Polyaniline may be doped (Emeraldine salt, ES).
  • the dopant is the acid anion
  • in the basic medium is the base form (Emeraldine base, EB).
  • Polyaniline is also a redox-active material: Emeraldine salt can change its color and its conductivity under the influence of different media or a shift in the electrical potential. Undoped polyaniline appears blue, doped polyaniline green, and the reduced forms yellowish.
  • the degree of oxidation and the degree of doping, the dopant and the pH of the surrounding medium substantially determine the electrochemical and electrical properties of the polyanion, such as the position of the redox systems and the conductivity.
  • oxidation and reduction refer to the oxidation state of the carbon of the polymer chain. This is known as doping the polymer when anions are attached to the nitrogen to form a poly cation. This is an acid-base reaction.
  • Emeiaidme Bas Em ⁇ ratdine SsJz
  • the doping can be done with any acid.
  • Preferred acids are sulfonic acids and acids with bulky substituents. Particularly preferred is alkylbenzenesulfonic acid and, in particular
  • Dodecylbenzenesulfonic acid (Ci 2 alkyl benzene).
  • the acid should preferably have a pKs ⁇ 5, particularly preferably ⁇ 4, in aqueous solution.
  • the degree of doping of the polyanilines according to the invention is usually below 50%, preferably below 35% and in particular at about 25%.
  • the degree of doping can be determined by the methods known in the art, for example by titration. This can be done in accordance with DIN 53402 (determination of the acid number).
  • the mathematical determination is also possible, the degree of doping resulting from the molar ratio of nitrogen atoms in the polyaniline main chain to the equivalents of the dopant used.
  • the polyanilines of the invention are coupled with organosulfur units.
  • organosulfur moieties are thiols, and generally all thiols known in the art can be used.
  • the thiol polyanilines according to the invention can be represented by the formula PAni-S-R.
  • PAni stands for polyaniline
  • each of the abovementioned alkyl radicals independently of one another contains 1 to 20 carbon atoms, preferably 1 to 15 and in particular 1 to 12 carbon atoms, may be straight- or branched-chain and optionally substituted by -SO3H, -SCVAlkalikation (especially -S ⁇ 3 ⁇ Na + ), -CO 2 H, -halogen (particularly F, Cl or Br), hydroxy, amino, amino-Ci -2 o alkyl, amino (Ci -2 o-alkyl) 2, -CO 2 -C -20 -Al ky I, -Ci -20- alkyl, -N H-CO-Ci -20 -alkyl, -Si (Ci-3-alkyl) 3 may be mono- or polysubstituted and wherein each of the above-mentioned aryl groups independently may be phenyl or naphthyl, both by -SO 3 H, -SO 3 " Alkalikation (especially
  • radicals -S-R are alkylthiols having 1 to 16 carbon atoms or thiobenzene and thionaphthalene. Particularly preferred is dodecanethiol.
  • organosulfur moieties for example the said thiols, are linked via their sulfur atom to the terminal end, preferably to the aromatic terminal end, of the polyanil in chain.
  • aniline monomer both the unsubstituted aniline and substituted aniline or combinations thereof can be used.
  • the aniline derivatives can e.g. Carry substituents with hydrocarbon radicals, e.g. 2-methylaniline, aniline-2-sulphonic acid, aniline-3-sulphonic acid or similar compounds. These copolymers show modified properties e.g. in the redox and solubility behavior.
  • the new polyanilines are characterized by a small molecular chain length.
  • the reason for this is to be found in the production process of the novel polyanilines wherein aniline and at least one organosulfur unit are reacted in a oxidative, acid-catalyzed polymerization reaction to a polyaniline derivative.
  • the organosulfur moiety probably acts as a molecular mass regulator through chain termination. Due to the relatively small degree of polymerization and the resulting short Molecule chain lengths can be relatively easy to disperse the polyanilines according to the invention, resulting in a very fine and homogeneous dispersion, which is ideal as a coating composition.
  • Substrates coated with such a coating composition exhibit a more uniform coating with a lower level of coarse particles, for example agglomerates, whereby such a coating on a substrate is consequently stable over an extended period of time. Cracking and chipping of entire coating parts can thus be prevented to a significant degree and the catalytic function of the coated substrate maintained.
  • the degree of polymerization of the polyanilines is possible by conventional methods of determination (gel permeation chromatography, GPC), but an exact determination requires a polyaniline standard.
  • the degree of polymerization is determined by the molecular weight of MALDI-TOF, which is a so-called absolute method and gives a relatively accurate result.
  • the degree of polymerization can also be easily determined by the N / S atomic ratio.
  • the polyaniline has an N / S atomic ratio of 5: 1 to 50: 1, more preferably 8: 1 to 35: 1, and most preferably 8: 1 to 30: 1, in the polyaniline backbone.
  • the N / S atomic ratio relates exclusively to the nitrogen and sulfur atoms present in the polyaniline main chain, that is to say the backbone of the polymer, so that, when considering the atomic ratio, any nitrogen and / or sulfur atoms present in the side chain are disregarded ,
  • sulfonic acid groups which are found for reasons of self-doping and adjustment of the solubility of the polyaniline depending on the route of synthesis in the side chain.
  • the N / S atomic ratio can be determined by the methods known in the art, in particular via a CHNS elemental analysis. Possible nitrogen and sulfur atoms in the side chain of the polyaniline (eg sulfonic acids) are also detected in a CHNS elemental analysis and Therefore, taking into account further parameters, such as the ratio of starting materials used, measured values from MALDI-TOF mass spectrometry and, if appropriate, relevant analytical data such as FT-IR, Raman and NMR data, must be excluded.
  • the polyaniline comprises an acid group.
  • such acid groups are usually in the side chain, that is, for example, attached to the aromatic of the aniline, which self-doping polyanilines are obtained by the acid group. Therefore, in the PAni synthesis preferably aniline-2-sulfonic acid or aniline-3-sulfonic acid is used in addition to aniline as a comonomer. It therefore no longer requires the addition of an acid for doping.
  • Self-doping polyanilines are already known in the art and can be prepared, for example, by sulfonation of polyaniline (J.Yue, AJ Epstein, J. Am. Chem.
  • a particularly preferred embodiment is provided when an aliphatic thiol is attached to the aromatic terminal end of the polyaniline backbone, the polyaniline has a number average degree of polymerization of from about 5 to about 30, and has sulfonic acid groups on the aniline moieties.
  • the polyanilines of the invention are prepared by a process wherein aniline and at least one organosulfur moiety are reacted in an oxidative, acid-catalyzed polymerization reaction to form a polyaniline derivative.
  • the polymerization process is particularly preferably a precipitation polymerization. It is in the method according to the invention is preferred if an organosulfur unit, as has already been defined above, is used. Preferably, therefore, the polymerization is carried out in the presence of a thiol HSR, wherein R is as defined above for PAni-SR. Particularly preferred is dodecanethiol (DCT).
  • any acid can be used as the acid for the acid-catalyzed reaction.
  • the acid should have a pKs ⁇ 5, more preferably ⁇ 4.
  • the oxidative acid-catalyzed polymerization reaction process further requires an oxidizing agent, using oxidizing agents known in the art. Examples include hydrogen peroxide, potassium peroxodisulfate, ammonium peroxodisulfate,
  • Substrates which can be coated with the polyaniline according to the invention are, for example, an electrode, a packed bed, a membrane
  • Preferred substrates are graphite and carbon fiber fabric and stainless steel. Further preferred is, for example, a combination of a membrane as a cathode, for example a
  • Hollow fiber membrane as a cathode Preferred support materials are organic polymers, polymer compositions, inorganic materials or composite materials.
  • the advantage of the polyanilines according to the invention is that, in contrast to the prior art, they can be applied to both conductive and non-conductive substrates.
  • Membrane separations are increasingly becoming key technologies in water treatment.
  • the separation and separation efficiency of the membrane is determined by the structure of the barrier layer: water desalination or separation of low molecular weight substances by reverse osmosis or nanofiltration is based on membranes with nonporous barrier layers, whereas membranes with porous layers are used for the separation of macromolecules or colloidal substances by ultrafiltration or microfiltration separating layers be used.
  • Typical microfiltration membranes have release effective pores in the range between 0.1 and 1 ⁇ m; Compared to conventional filter materials, these pores are smaller and the inner surfaces are significantly larger.
  • Membranes which can be used according to the invention can be classified as follows:
  • membrane material organic polymers, inorganic materials (oxides, ceramics, metals), composite materials of various materials; Diaphragm cross-section: isotropic ("symmetrical"), integral anisotropic
  • phase separation phase separation
  • sol-gel processes thermal degradation, interfacial reaction, stretching, extrusion, nuclear tracking, microfiltration
  • Membrane shape flat membrane, hollow fiber or capillary, hollow capsule.
  • microfiltration membranes are made of organic polymers such as e.g. non-conductive polysulfone or non-conductive polypropylene.
  • the pore size distribution across the membrane cross-section is either isotropic or slightly anisotropic.
  • variants of the phase separation of polymer solutions preferably induced by a non-solvent-induced phase separation (NIPS) or by cooling into an unstable region (TIPS) dominate among the preparation processes.
  • NIPS non-solvent-induced phase separation
  • TIPS unstable region
  • both flat membranes (in spiral wound modules or plate modules) and capillary membranes are common.
  • a polyaniline which is doped and contains sulfur in the polyaniline chain is suitable for water treatment and / or air purification, and thus can Purposes are used.
  • a polyaniline as described above can be used for water treatment and / or for the purification of air.
  • the water treatment and / or the purification of air includes the removal of organic and inorganic pollutants, bacteria, viruses, microorganisms and / or parasites, so both a cleaning, and to a certain extent a sterilization / sterilization of water or air.
  • OH radicals active oxygen species
  • organic or inorganic pollutants can be oxidized by the OH radicals, for example, and thus rendered harmless.
  • anilines of the invention can also be used advantageously in redox-flow batteries and in electrolysis systems.
  • a coating composition is also required for the production of a coated substrate, which is why the scope of the invention also includes a process for the preparation of a coating composition, the process comprising the steps:
  • Polyaniline like all ICP, is usually insoluble and has no melting point or other softening behavior. For this reason, polyaniline can not be processed like ordinary thermoplastic polymers. Processing therefore takes place via the finest distribution (dispersion) in solvents or dispersants. The starting point for many applications are therefore polyaniline dispersions.
  • polyaniline In order to process polyaniline, the polyaniline is dispersed in powder form in solvents.
  • the starting point for further processing are the polyaniline dispersions prepared in this way. From such dispersions can
  • Layers on a substrate are the better, the smaller the particles and the more homogeneous the distribution of the polyaniline in the dispersant.
  • the quality of the layer is determined by the particle size and nature of the layer
  • agglomerates in ⁇ m size occur. This may be due to unfavorable polymerization conditions or to the choice of solvent or dispersant or dispersing method.
  • the aim should be to produce as homogeneous a dispersion as possible with particle sizes ⁇ 1 ⁇ m.
  • the particle size can be determined by a standard method, "Dynamic Laser Light Scattering". The advantages in the production and processing of such a dispersion arise from:
  • the polyaniline should be doped. It has proved to be particularly advantageous if the polyaniline after step e.) Of the process according to the invention, the filtration, is re-doped with Alkybenzolsulfonklare. Particularly preferred is dodecylbenzenesulfonic acid (DBS). It may be advantageous, the Coating composition after doping a further energy input, in particular a further ultrasonic treatment to undergo. Possible agglomerates formed in the doping can be redispersed again. By doping the doping level can be adjusted exactly. This is otherwise difficult with the doping, which is present directly after the synthesis. By precisely adjusting the degree of doping, the conductivity of the polyaniline can thus also be adapted to the required conditions.
  • DBS dodecylbenzenesulfonic acid
  • the coating of a substrate with a coating composition according to the invention is usually carried out by applying the coating composition to the substrate by methods known in the art and then drying the coating. Possible application methods are, for example, dipping, doctoring, spraying, gravure printing, overlaying and stripping, reverse roll and spin coating, painting or application with a roller and the like.
  • Such a coated substrate for example a coated membrane
  • a purification reactor for the treatment of water and / or for the purification of air.
  • the scope of the invention thus also includes a purification reactor, the reactor having a reaction chamber with inlet opening and outlet opening for the medium to be cleaned, at least one, in particular one, two, three or more coated substrates according to the invention, at least one, in particular one, two, three or more counter-electrodes, and optionally at least one, in particular one, two, three or more separating means between the coated substrate (s) and the anode (s).
  • An inventive laboratory construction can be seen, for example, Figure 1, wherein the reference electrode is necessary only for the laboratory setup.
  • the counter electrode (s) can be used with inexpensive materials such as stainless steel as a carrier material and current collector.
  • the electrodes can be designed as flat sheets, perforated sheets, wires, loose beds or stretched metals. The use of carbon fleeces is also possible.
  • the electrochemically active substance is the polyaniline derivative. Direct synthesis on the electrodes of monomers is industrially attractive. In addition, care is taken in the process development to apply coatings of the already synthesized polymer on the electrodes. For this purpose, established thick film coating processes are known in which the polyaniline film is possibly cast directly onto metal foils with one or more intermediate layers of a conductive adhesion promoter. The coated films can then work as a sheet, stretched or in thread form as working electrodes. Particularly attractive is the combination of polyaniline with hollow fiber membranes.
  • the polyaniline may be present as a layer or doping on or in the polymer.
  • the distance between the anode and cathode to avoid short circuits can be made by separators, diaphragms or spacers. Hydrophilic nonwovens or fabrics, such as e.g. from PPS, on. These are used as supporting membranes in reverse osmosis technical use. It is also possible to equip prefabricated electrodes with separator membranes by reprecipitation.
  • Potentiostatic operation with a three-electrode arrangement has been used on a laboratory scale for process development.
  • the electrochemical parameters can be determined.
  • the potential of a saturated calomel electrode is used.
  • a diaphragm separates this reference electrode from the water (or air) to be treated.
  • diaphragms tend to become blocked by crystallization or colonization with microbes.
  • the transition from potentiostatic to galvanostatic operation is conceivable.
  • the control loops are simplified, but greater emphasis is placed on the homogeneous distribution of the electric fields in the reactor design.
  • the laboratory structure is sketched in principle.
  • the centerpiece is an electrochemical cell with exchangeable electrodes. These allow the use of different coatings and substrates.
  • the electrodes are driven by a potentiostat which makes a corresponding polarization of the electrodes.
  • a potentiostat which makes a corresponding polarization of the electrodes.
  • polyaniline can be used as a coating or constituent of
  • the oxidant solution is prepared as follows: 11 g (48 mmol) of ammonium peroxodisulfate (APS) are weighed in and subsequently made up to 30 ml with deionized water. The solution is transferred to a dropping funnel.
  • APS ammonium peroxodisulfate
  • reaction mixture continues to react for about 5 hours.
  • Step 6 Rinse with 1 L of deionized water.
  • the filter cake is placed in a beaker after washing and dried to constant weight in a vacuum oven.
  • Figure 2 shows polyaniline DCT immediately after synthesis, magnification 100 fold.
  • the polymerization product is present as loosely agglomerated particles; larger agglomerates (1 -10 ⁇ m) are easily recognizable, which decay into finer particles ( ⁇ 1 ⁇ m) when the slide is moved mechanically.
  • FIG. 3 shows an IR spectrum of the polyaniline DCT base.
  • the labeled regions identify the DCT component in the polyaniline.
  • the starting material for dispersions is the powder of the non-conductive base form of polyaniline (EB).
  • the dispersion prepared in step 1 is hereinafter called PAni-EB-NMP 2.5% (w / v) parent dispersion.
  • the mixture is homogenized for at least 30 minutes in an ultrasonic bath at 50 ° C. and filtered through a cellulose filter in order to remove any agglomerates which may have formed during the preparation.
  • This dispersion is called PAni-ES-DBS-NMP 2% (w / v) parent dispersion
  • the dispersion prepared under 2) can be diluted with other solvents or solvent mixtures as needed to adjust the concentration, the flow or the wetting properties and is then ready for coating or for incorporation into other substances.
  • Example 3 Preparation Example, Coating of Steel Sheet:
  • a cleaned and degreased film section is placed on the flat support surface, over which a doctor is pulled away.
  • the squeegee has a width (inside) of 73 mm; this width determines the width of the coating on the steel sheet.
  • the gap width between substrate and doctor blade is 50 ⁇ m.
  • the squeegee is placed behind the slider on the substrate; into the interior of the doctor blade is added 1 ml of 1% (w / v) dispersion.
  • the doctor blade is subsequently pulled over the steel foil and a thin film of the coating dispersion remains on the substrate.
  • the solvent is evaporated at 200 0 C (setting on the hair dryer). After evaporation of the solvent, the remaining solvent residues are evaporated at 120 0 C in a vacuum oven. This gives a green shimmering polyaniline layer with a thickness of about 200-1000 nm.
  • a microfiltration membrane made of polypropylene (flat membrane 2EHF, Membrana GmbH) with a nominal pore size (cut-off) of 0.4 microns and a specific surface area of 25 m 2 / g is installed in a filter holder made of Teflon (diameter 47 mm) and using a peristaltic pump flushed through successively with the following solutions (in each case 1 mL / min):
  • Stabilizer SLOTONIP 64 (Schlötter), and 1, 5 mL reductor SLOTONIP 66 (Schlötter), made up of 25 mL water (25 0 C), for 20 min.
  • the membrane is dried in a vacuum oven at 45 0 C. Characterization is carried out by SEM, nitrogen adsorption (BET), permporometry and measurements of water permeability.
  • Example 4.2 Preparation of a conductive membrane doped with conductive carbon black and PAn i by precipitation-agent-induced phase separation
  • a solution of 12% by weight of polyethersulfone in a mixture of NMP and triethylene glycol (ratio 2: 1, v / v) is prepared (stirring at 45 ° C. for about 3 hours). Subsequently, 6 wt .-% Leitruß and 10 wt .-% of a 2% PAni dispersion, each based on the total solution added. After 10 min. Dispersing in an ultrasonic bath, the solution is stirred for a further 1 h at 45 0 C. Subsequently, using a doctor blade, a 250 ⁇ m thick film of the polymer solution is produced on a polished glass plate. After a residence time of 30 sec.
  • the precipitation takes place in a bath of ultrapure water with a content of 25% by volume of NMP. After a residence time of 1 h in the precipitation bath, the membrane is transferred to a washing bath of ultrapure water, which is exchanged twice at intervals of ⁇ 4 or -16 hours. The membrane thus produced is then treated by solvent exchange (water -> ethanol) and then dried.
  • the layer thickness of the membrane is about 200 microns.
  • Characterization is carried out by SEM, nitrogen adsorption (BET), permporometry and measurements of water permeability.
  • FIG. 4 shows a laboratory reactor for generating OH radicals:
  • the sample is dried at 110 ° C. overnight.
  • Counter electrode Stainless steel electrode 1 .4301, surface like working electrode
  • Reference electrode saturated calomel electrode A Abbssttaanndd A AEb // GUEb :: 2 mm, check for possible short circuits with
  • the working electrode is polarized in each case for 2 min (120 s) to - 700 mV against a saturated calomel electrode and the RNO concentration is monitored by means of an inline photometer.
  • the RNO signals are shifted for about 1 minute due to the time delay effects between the electrocatalytic chamber and the photometer probe.
  • Figure 5 shows the RNO concentration in the pulsed polarization degradation experiment of the polyaniline working electrode.
  • the absorption signal at 438 nm pulsates in parallel and reproducibly with the applied polarization.

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Abstract

L'invention concerne une polyaniline, comprenant des unités d'aniline et des unités de soufre organique, caractérisée en ce que la polyaniline est dopée et présente un degré de polymérisation moyen en nombre d'environ 5 à environ 50. L'invention concerne également un procédé de fabrication de polyaniline, sachant que de l'aniline et au moins une unité de soufre organique sont transformées en un dérivé de polyaniline par une réaction de polymérisation oxydante par catalyse acide. L'invention concerne aussi un substrat revêtu, qui est revêtu de la polyaniline selon l'invention, ainsi qu'un procédé de revêtement du substrat. L'invention concerne encore une composition de revêtement qui convient pour revêtir le substrat. L'invention concerne ainsi également un procédé de fabrication de la composition de revêtement. L'invention concerne également l'utilisation de polyaniline, qui est dopée et qui présente du soufre dans la chaîne principale polymérique, pour le traitement de l'eau et/ou pour la purification d'air, ainsi qu'un réacteur d'épuration pour la mise en œuvre du procédé d'épuration.
EP08851293A 2007-11-23 2008-11-20 Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau Withdrawn EP2212373A2 (fr)

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DE200710056423 DE102007056423A1 (de) 2007-11-23 2007-11-23 Herstellung und Verwendung neuer Polyaniline zur Wasserbehandlung
PCT/EP2008/065909 WO2009065892A2 (fr) 2007-11-23 2008-11-20 Fabrication et utilisation de nouvelles polyanilines pour le traitement de l'eau

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CN (1) CN101910249A (fr)
AU (1) AU2008327879A1 (fr)
BR (1) BRPI0819821A8 (fr)
CA (1) CA2705409A1 (fr)
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WO2010068839A2 (fr) * 2008-12-11 2010-06-17 The Regents Of The University Of California Compositions de membrane et procédés de fabrication et d'utilisation associés
CN102044648B (zh) * 2009-10-16 2013-04-10 大连融科储能技术发展有限公司 聚芳基醚苯并咪唑离子交换膜及其制备和全钒液流电池
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CA2887556C (fr) 2012-10-12 2021-01-12 The Regents Of The University Of California Membranes en polyaniline ayant une hydrophilie accrue
ES2893539T3 (es) 2013-05-15 2022-02-09 Univ California Membranas de polianilina formadas por inversión de fases para aplicaciones de ósmosis directa
WO2015157227A1 (fr) * 2014-04-08 2015-10-15 The Regents Of The University Of California Membranes de filtration hydrophiles résistant au chlore à base de polyaniline
CN104312255B (zh) * 2014-10-29 2016-06-01 湖北大学 一种水性聚丙烯酸掺杂聚苯胺缓蚀剂及其制备方法
US10274451B2 (en) * 2015-02-18 2019-04-30 Santa Clara University Affordable electrochemical detection of environmental contaminants
DE102015005732A1 (de) * 2015-05-07 2016-11-10 Forschungszentrum Jülich GmbH Kohlenstoffhaltige Membrane für die Wasser- und Gastrennung
CN104909435B (zh) * 2015-06-03 2017-03-01 湖南大学 一种氨基乙酸掺杂聚苯胺修饰电极及其制备方法和应用
CN106563573B (zh) * 2015-10-12 2019-10-11 国电科学技术研究院 一种改性聚苯胺湿式静电除尘器阳极模块
TWI568491B (zh) * 2015-12-31 2017-02-01 財團法人工業技術研究院 過濾材料
RU2641278C1 (ru) * 2016-10-19 2018-01-16 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") Способ получения водного раствора полианилина
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CN110639438B (zh) * 2019-08-16 2021-08-20 华东理工大学 一种聚苯胺中空微球的制备及回收电子垃圾中的贵金属及其再利用的方法

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US20100307974A1 (en) 2010-12-09
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JP2011505441A (ja) 2011-02-24
DE102007056423A1 (de) 2009-06-04
KR20100089882A (ko) 2010-08-12
WO2009065892A3 (fr) 2009-09-24
CA2705409A1 (fr) 2009-05-28
CN101910249A (zh) 2010-12-08
WO2009065892A2 (fr) 2009-05-28
RU2010125616A (ru) 2011-12-27
BRPI0819821A8 (pt) 2016-04-26
BRPI0819821A2 (pt) 2015-05-26
AU2008327879A1 (en) 2009-05-28

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