WO2015004283A1 - Suspension contenant du graphène, procédé de préparation de cette suspension, feuillets de graphène et leur utilisation - Google Patents

Suspension contenant du graphène, procédé de préparation de cette suspension, feuillets de graphène et leur utilisation Download PDF

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Publication number
WO2015004283A1
WO2015004283A1 PCT/EP2014/064984 EP2014064984W WO2015004283A1 WO 2015004283 A1 WO2015004283 A1 WO 2015004283A1 EP 2014064984 W EP2014064984 W EP 2014064984W WO 2015004283 A1 WO2015004283 A1 WO 2015004283A1
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alkyl
group
ethoxylated
groups
unsubstituted
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PCT/EP2014/064984
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German (de)
English (en)
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Alexandra Schneider
Sebastian HILDEBRAND
Christian Wolfrum
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Eckart Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to graphene platelets and their suspension comprising a water-miscible solvent, a process for their preparation and their use. Furthermore, the present invention relates to a kit for use in the preparation and handling of graphene and its use.
  • US 7,892,514 B2 discloses a process for producing a graphene material by intercalating halogen in graphite structures.
  • the graphite to halogen compounds at a temperature above the melting point or
  • Halogen compounds intercalate into the graphite structure. This is followed by heating above the boiling point of the halogen, resulting in delamination of graphene-containing platelets.
  • US 2009/0028777 A1 discloses a process for producing delaminated graphite, flexible graphite and nanoscale graphene plate.
  • Manufacturing process is based on an intercalation step, which is understood as a chemical oxidation by means of a carboxylic acid and hydrogen peroxide.
  • an intercalation step which is understood as a chemical oxidation by means of a carboxylic acid and hydrogen peroxide.
  • the intercalation product is heated, if necessary under the action of mechanical forces.
  • US 7,914,844 B2 discloses a process for preparing a dispersion of reduced graphene oxide nanoplatelets, wherein isocyanate-treated
  • Graphene oxide nanoplatelets in the presence of a reducing agent and a polymer.
  • a reducing agent for example, hydrazine hydrate in water or ⁇ , ⁇ -dimethylhydrazine can be used in organic solvent.
  • WO 201 1/070026 A2 discloses a carbon particle granule which comprises
  • the primary particles include graphite material and / or singular carbon nanotubes (CNT) and / or carbon nanofibers (CNF) and / or high-carbon nanoparticles
  • the additive may be formed as a surfactant and / or polymer and / or monomer and / or polyelectrolyte.
  • US 2010/0022422 A1 describes a process for wet milling of graphite using solvent and dispersant.
  • Dispersant may contain a lipophilic hydrocarbon group and a polar hydrophilic group.
  • the dispersants typically used in the automotive industry are used, which are to be universally usable for the production of carbon nanotubes, graphite flakes, carbon fibers and carbon particles.
  • the special bonding properties of graphite and the special challenges of graphene require optimized processes. So are other modifications of the carbon such as carbon black, diamond or carbon nanotubes (carbon nanotubes), for example due to their nature,
  • carbon black is an amorphous modification.
  • Diamond is a high-strength, covalent lattice structure that lacks a delocalized ⁇ bonding system, such as soot.
  • Carbon nanotubes are considered as one-dimensional bodies whose delocalized ⁇ bonding system has a very high curvature. The same applies of course to other layer structures whose composition differs from that of graphite.
  • Providing a suspension comprising a water-miscible solvent, graphene platelets, at least one additive and at least one adjuvant,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium Compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the at least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • Cx-Cy means that the group in question has x to y carbon atoms
  • Cx + means that the group in question has at least x
  • the object underlying the invention is also achieved by providing a method for producing a graphite suspension, the method comprising the following steps:
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected; polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium Compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected and selected
  • step b) wherein in steps a1) or a2) or a1) and a2) and optionally in step b) at least one adjuvant according to formula (H 1) is added,
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the at least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms; polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the object underlying the invention is further solved by the provision of graphene plates, which are produced according to the inventive method.
  • the graphene platelets are in a water-miscible solvent, preferably in an aqueous solvent, more preferably in water, than
  • the at least one additive to be used according to the invention and the at least one adjuvant can be present for example in the form of a kit.
  • the inventive graphene platelets preferably in the form of a suspension, can be used in the production of electronic materials, electronic objects such as electronic circuits and capacitors such as supercaps (supercapacitors), electrically conductive films, chemical sensors, optical Materials and composite materials, such as reinforced and / or electrically conductive plastics, batteries and membranes used.
  • electronic materials electronic objects such as electronic circuits and capacitors such as supercaps (supercapacitors), electrically conductive films, chemical sensors, optical Materials and composite materials, such as reinforced and / or electrically conductive plastics, batteries and membranes used.
  • graphene platelets is understood as meaning structures which comprise both a single graphene monolayer and a plurality of superimposed graphene layers
  • graphene does not have a spherical or tubular structure, but has a substantially planar structure.
  • the term graphene platelet also means substantially planar structures which are characterized by a small number of graphene monolayers arranged one above the other. This is
  • an intensity ratio of the 2D peak to the G peak in the Raman spectrum which in the graphene platelets according to the invention is preferably in a range from 0.5 to 3, more preferably in a range from 0.5 to 2.
  • the intensity ratio of the 2D peak to the G peak is in
  • Raman spectrum of the inventive graphene platelets in a range from 0.65 to 1.9.
  • the graphically advantageous properties such as the electrical conductivity or the mechanical stability thereof produced and / or graphene-containing objects such as membranes, are monolayer
  • Graphene monolayers good results, for example, in terms of electrical conductivity or mechanical stability can be achieved. These suspensions can be easily prepared and thus enable use on an industrial scale.
  • unsubstituted in the sense of the present invention means that no other groups are attached to an atom or a structure other than hydrogen.
  • the inventive combination of at least one additive and at least one excipient is particularly well suited to aqueous
  • Graphene platelet suspensions is preferably at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, based in each case on the total weight of the solvent.
  • Long-term stability in the context of the present invention is understood to mean, for example, that no noticeable impairment of the properties of the suspension is observed over a period of 30 or even 60 days in the absence of mechanical input of energy.
  • the long-term stability can be detected, for example, by means of absorption spectroscopy.
  • the suspensions of the invention preferably show a loss of absorption of more than 20% after 60 days, more preferably a loss of less than 15%, even more preferably a loss of less than 10%.
  • the graphene platelets Since the suspension according to the invention with graphene platelets and the graphene platelets according to the invention are not produced by means of a combination of oxidation and reduction, the graphene platelets have only a low oxide content. This low oxide content can not be achieved, for example, with the production process according to Hummer or process variants thereof, since the respective reduction is always incomplete. Furthermore, correspondingly produced graphene plates have a large number of defects, which irreparably damages the ⁇ -electron system of the graphene.
  • the oxygen content in the graphene platelets is preferably less than 1.5% by weight, more preferably less than 1.2% by weight and even more preferably less than 0.9% by weight, based in each case on the total weight of the dry graphene platelets without additives.
  • the determination of the oxygen content of the graphene can, for example, by means of
  • Elemental analysis and / or X-ray photoelectron spectroscopy (XPS), with XPS being preferred.
  • the determination of the oxygen content of the samples by XPS can for example be done with a PHI 5600 ESCA system.
  • the spectra are recorded with a resolution of 0.1 eV and a matching energy of 10 eV.
  • the samples are analyzed by means of an Ar + ion beam at an acceleration voltage of
  • Graphene platelet according to the invention and can be generally attributed to the high quality of the inventive graphene platelets, is the half-width of the 2D peak.
  • the half width is determined by Raman spectroscopy analogous to
  • the half width indicates the width of the 2D peak, which is usually 2698 cm “1 ⁇ 50 cm “ 1 , at which the curve has dropped to half of the maximum.
  • the half width is at most 75 cm -1 , more preferably at most 65 cm -1 and even more preferably at most 55 cm -1 .
  • the half width of the 2D peak is in a range of 35 to 65 cm -1 , more preferably in the range of 38 to 60 cm -1 and even more preferably in the range of 41 to 56 cm -1 .
  • suspensions according to the invention having graphene platelets as well as graphene platelets according to the invention which have a particular ratio of the 2D peak, which is usually 2698 cm “1 ⁇ 50 cm “ 1 , to the G peak, which is usually at 1587 cm “1 ⁇ 50 cm “ 1 , im Raman spectrum have.
  • the intensity ratio of the 2D peak to the G peak is in the range of 0.5 to 3, preferably in the range of 0.6 to 2, and more preferably in the range of 0.7 to 1.5 preferably at an excitation wavelength of 532 nm.
  • Graphene platelets and thus, for example, the particular suitability for uses in which the electrical conductivity plays a special role.
  • the intensity ratio of the 2D peak to the G peak in the Raman spectrum is in a range of 0.5 to 3 and the half width of the 2D peak is in a range of 35 to 75 cm -1 , preferably the intensity ratio of the 2D peak to the G peak in the range of 0.6 to 2 and the half width of the 2D peak in the range of 38 to 65 cm -1 and more preferably the intensity ratio of the 2D peak to the G peak in FIG Range of 0.7 to 1.5, and the half width of the 2D peak in the range of 41 to 55 cm "1 lies.
  • the Raman measurement is preferably carried out by means of a confocal Ramanspektroskopes the company Horiba Jobin Yvon LabRAM Aramis.
  • the excitation wavelength is included
  • the suspension according to the invention is applied after a centrifugation step by means of spin coating on Si0 2 wafers.
  • the values of the intensity ratios and the half width are averaged from a statistically meaningful number of individual measurements.
  • the arithmetic mean of the values is formed from at least 50 randomly selected graphene platelets, preferably 50 randomly selected graphene platelets.
  • the centrifugation is carried out by means of the centrifuge MIKRO 200 from Hettich. The suspension is centrifuged for 10 minutes at 15000 rpm (21382 g) before the supernatant is measured.
  • the 2D band provides a characteristic clue to the sp 2 network in the graphene plane.
  • the symmetry and the half-width of the 2D band give hints on the degree of delamination of the graphene platelets. So the 2D band is one
  • Origin of OriginLab is described by means of a single Lorentz function with a correlation factor R 2 of at least 0.995 in the region of the maximum ⁇ twice the half width and has a half width of ⁇ 35 cm "1.
  • R 2 correlation factor
  • R 2 Correlation factor
  • such materials have a larger half width of the 2D band.
  • a half-width of 70-80 cm -1 is expected according to the literature.
  • the I (D) / I (G) ratio (intensity ratio of the 2D peak to G peak) corresponds to the sp 3 / sp 2 ratio and thus describes the defect density of the material within the graphene plane.
  • a high I (D) / I (G) ratio may also be due to edge effects.
  • Measurements such as Raman and AFM (Atomic Force Microscopy) are preferably carried out at the identical location of a sample applied to the Si0 2 wafer. According to the invention it is further preferred that in the inventive
  • Suspensions containing graphene platelets have an average size of at least 50 nm, preferably of at least 500 nm, more preferably of at least 1 ⁇ .
  • Graphene platelets are determined by plotting the graphene platelets on a support and determining the size of the graphene platelets by means of TEM (TEM: Transmission Electron Microscopy). This will consist of at least 100 randomly selected
  • Graphene platelets preferably 100 randomly selected graphene platelets, the arithmetic mean of the longest diameter and of the perpendicular thereto
  • the graphene sheets according to the invention usually comprise a mixture of
  • Graphene platelet-containing suspensions may also be present to a limited extent
  • Graphene plate is preferably in a range of 0.5 to 5 nm, more preferably 0.55 to 4 nm, even more preferably 0.6 to 3 nm, and still more preferably 0.65 to 2 nm Thickness of the in the invention
  • Suspension contained graphene plate can, for example by means of Atomic force microscopy, wherein the arithmetic mean of the thickness of
  • Carbon layers of preferably at least 50 graphene plates is determined.
  • Graphene platelets containing suspensions offer an outstanding combination of ease of manufacture, good handleability and outstanding product properties.
  • the additive according to the invention to be used according to formula (I) has a water solubility of at least 0.05 g / l, preferably of at least 0.1 g / l, and more preferably of at least 1 g / l.
  • the aforementioned water solubility indicates how many grams of the additive are soluble in water at 20 ° C without modification of the pH.
  • the water solubility of the additive is at most 200 g / l, preferably at most 150 g / l and more preferably at most 125 g / l.
  • the at least one additive to be used according to the invention has a water solubility from a range of 0.05 g / l to 200 g / l, preferably in the range of 0.1 g / l to 150 g / l and more preferably in the range of 1 g / l to 125 g / l.
  • the at least one additive to be used according to the invention is preferably used in a total amount which is at least 1% by weight, more preferably at least 2% by weight and even more preferably at least 5% by weight of additive, in each case based on the weight the graphene platelets.
  • more than one additive for example of two or three additives, they may each be present in the amounts indicated above.
  • the total amount of the additive or the additives in the suspension is at most 5,000% by weight, more preferably at most 3,000% by weight and even more preferably at most 1,000% by weight, each based on the weight of the graphene sheets .
  • the total amount of the additive or additives in the suspension is between 1 and 300,000% by weight, more preferably between 2 and 100,000% by weight, and more preferably between 5 and 5,000% by weight, more preferably between 10 and 1000% by weight, more preferably between 20 and 500% by weight, based in each case on the weight of the graphene platelets.
  • the amount of additive used according to the invention is determined according to methods known to the person skilled in the art, such as NMR spectroscopy, IR spectroscopy,
  • Raman spectroscopy and gas chromatography are coupled with
  • Mass spectrometry and / or flame ionization detector In this case, the sample is pretreated in accordance with the manufacturer's instructions and, for example, a separate determination of the additives and / or auxiliaries adhered to the graphene platelets and of the additives and / or auxiliaries present in the suspension solution is carried out. It is also possible, for example, to carry out a targeted washing down of the substances to be used according to the invention from the graphene platelets as a constituent.
  • Excipient amount can also be done gravimetrically, for example. It was found that the graphene plates decompose relatively late and therefore
  • Thermogravimetrisch the amount of other adhering components can be determined. Before the determination, of course, the solvent of the suspension must be removed, for example by means of distillation processes.
  • the graphene platelets in the suspension are in a concentration of at least 0.04 g / l, more preferably at least 0.045 g / l, even more preferably at least 0.055 g / l, more preferably at least 0.07 g / l, more preferably at least 0.1 g / l, before.
  • Highly concentrated graphene platelet suspensions are desirable in terms of transportation and storage.
  • highly concentrated graphene platelet slurries are also advantageous in the application, since smaller amounts of solvent must be handled and removed by drying.
  • the inventive combinations of the specified additives and auxiliaries can achieve significant improvements in the comminution of graphite and production of graphene platelets.
  • the conventional comminution of graphite has a choice between insufficient delamination or over-crushing of the graphene sheets, which in either case does not provide the desired graphene properties.
  • the specific combinations of compounds which can be obtained in accordance with the invention it is surprisingly possible to produce high-quality graphene platelets in a cost-effective manner, in particular without complex processes.
  • the combination of the at least one additive and the at least one adjuvant as specified in claim 1, 13 or 15 is essential.
  • the specified combination of at least one additive and at least one adjuvant it becomes possible to reduce, for example, the costs of the starting materials, the comminution time and / or the requirements for production devices and / or to improve the flexibility of production, reproducibility and / or quality and to effect a variety of applicability of the obtained graphene platelets.
  • a suspension comprising a water-miscible, preferably aqueous, solvent, graphene plate, at least one additive and at least one auxiliary,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the at least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • Preferred examples of the at least one adjuvant are tetramethylammonium, tetraethylammonium, tetrabutylammonium, triethyl-n-butylammonium, tri (n-propyl) (vinyl) ammonium, (vinylbenzyl) (trimethyl) ammonium or combinations thereof.
  • the R a1 of the at least one adjuvant (H1) are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, and unsubstituted C 2 -C 8 alkynyl groups, more preferably from the group consisting of unsubstituted C 1 -C 6 alkyl groups, unsubstituted C 2 -C 6 alkenyl groups and unsubstituted C 2 -C 6 alkynyl groups, and even more preferably from the group consisting of unsubstituted C 1 -C 4 alkyl groups, unsubstituted C 2 -C 4
  • R a1 are independently selected from unsubstituted C 1 -C 8 alkyl groups, more preferably from unsubstituted C 1 -C 6 alkyl groups and even more preferably from C 1 -C 4 alkyl groups.
  • the at least one adjuvant is a compound according to formula (H2),
  • R a2 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups
  • R b2 is selected from the group consisting of unsubstituted C 2 -C 4 alkenyl groups and unsubstituted C 2 -C 4 alkynyl groups
  • x is 3 or 4.
  • the R a2 be independently selected from unsubstituted C 1 -C 6 alkyl groups, more preferably from unsubstituted C 1 -C 4 alkyl groups, even more preferably from unsubstituted C 1 -C 3 alkyl groups.
  • x is 4.
  • the substituents of the at least one additive and of the at least one adjuvant may each be selected independently of each other, unless stated otherwise. Examples of these groups are the abovementioned substituents R a1 or R a2 , R b2 , etc. This includes the groups introduced below. Furthermore, in the case of further execution positions, it is preferred for the at least one adjuvant to be a compound according to formula (H3),
  • R a3 are independently selected from the group consisting of unsubstituted C 1 -C 4 alkyl groups
  • R b2 is selected from the group consisting of unsubstituted C 5 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups
  • R's are independently selected from the group consisting of unsubstituted C 1 -C 4 alkyl groups
  • R b2 is selected from the group consisting of unsubstituted C 5 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups and unsubstituted C 2 -C 8 Alkynyl groups, and where y is 3 or 4.
  • alkyl radicals may be straight-chain or branched alkyl radicals, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 1-methylpropyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3
  • alkenyl radicals and alkynyl radicals may be straight-chain or branched alkenyl radicals or alkinyl radicals, as indicated above for the alkyl radicals, with the exception of methyl, which contain at least one double bond or triple bond.
  • the suspension comprises at least two adjuvants according to formula (H1), (H2), (H3) or mixtures thereof, wherein the at least two adjuvants are different from one another.
  • At least one auxiliary according to formula (H1), formula (H2) and / or formula (H3) at least 3 R a1 , at least 3 R a2 or
  • At least 2 include, preferably at least 3, R a1, R a2 and R a3 are each at least 2 carbon atoms. examples for this are
  • Tetraethylammonium or (tributyl) (methyl) ammonium Tetraethylammonium or (tributyl) (methyl) ammonium.
  • the amount of the at least one adjuvant is at least 30% by weight, more preferably at least 50% by weight and even more preferably at least 70% by weight, based in each case on the weight of the graphite used.
  • the weight of the at least one adjuvant is at most 300% by weight, more preferably at most 250% by weight and even more preferably at most 200% by weight, based in each case on the weight of the graphite used.
  • counterions of the ammonium ion used according to the invention as auxiliary (e) can be used.
  • examples are F “ , CI “ , Br “ , I “ , OH “ , BF 4 “ , S0 4 2 “ , C0 3 2” , P0 4 3 “ , N0 3 “ , Cr0 4 2 “ , Mn0 4 " and Carboxylations such as citrate ions and acetate ions.
  • Particularly preferred are, for example, OH “ , S0 4 2” , C0 3 2 " , P0 4 3” , N0 3 " , citrate ions and acetate ions.
  • the at least one additive used according to the invention is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds; Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the at least one additive used according to the invention is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids, wherein the
  • Fatty acids independently have 10 to 25 carbon atoms
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the block copolymers of ethylene oxide (EO) and propylene oxide (PO) used as an additive are not triblock polymers having a
  • composition of EO: PO: EO 20:70:20 with a deviation of up to 10% each, the respective ratios being molar ratios.
  • fatty acids is understood as meaning fatty acids having 10 to 25 carbon atoms, in particular acyclic, aliphatic C 10 -C 25 -monocarboxylic acids
  • the fatty acids are preferably acyclic aliphatic C 12 -C 20 -monocarboxylic acids, such as stearic acid and oleic acid
  • the carbon atom of the carboxyl group is in the aforementioned number of
  • N-alkylbetaines For the purposes of the present invention, the term "N-alkylbetaines" is used
  • the N-alkyl betaines have two alkyl groups of 1 to 20 carbon atoms arranged to form a positively charged quaternary nitrogen. These two alkyl groups may be the same or different.
  • two identical alkyl groups are arranged on the nitrogen atom, which are preferably both methyl or ethyl, preferably methyl.
  • N-alkylbetaine is also understood to mean alkylbetaines which contain more than one (number: 1) alkyl-substituted nitrogen atom, for example 2, 3 or 4
  • Nitrogen atoms preferably each with two
  • Alkyl groups each having 1 to 20 carbon atoms is substituted, preferably in each case two ethyl groups, more preferably in each case two methyl groups, to form a positively charged quaternary nitrogen.
  • sorbitan trifatty acids means sorbitan derivatives which have been esterified with three fatty acid molecules which are defined as above.
  • An example is sorbitan trioleate.
  • a particularly preferred group of the poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) - ammonium) compounds are the poly ((4-vinylbenzyl) (trimethyl) ammonium) compounds.
  • a preferred group of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds are the (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds.
  • a preferred group of the (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds are those of the (C 10 -C 20 -alkyl) (dimethyl) (benzyl) ammonium compounds.
  • a preferred group of the C10 + acyclic aliphatic alcohols are the C10-C25 acyclic aliphatic alcohols.
  • a preferred group of C7 + acyclic aliphatic amines are the C7-C25 acyclic aliphatic amines
  • polymeric surfactants is understood to mean surfactants which have at least two, preferably at least three, more preferably at least four, more preferably at least ten, more preferably at least 25, more preferably at least 50, identical repeating units polymeric surfactants have proven to be very advantageous, in particular in connection with the process according to the invention, and constitute a particularly preferred group of additives according to the invention.
  • the polymeric surfactants become
  • naphthalenesulfonic acid-formaldehyde condensates polyvinyl alcohols, lignin sulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO), more preferably from the group consisting of Naphthalinsulfonklaformaldehydkondensaten, lignosulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO ), and more preferably from the group consisting of naphthalenesulfonic acid-formaldehyde condensates and block copolymers of ethylene oxide and propylene oxide.
  • block copolymers of ethylene oxide and propylene oxide which do not use triblock polymers with a
  • Composition of EO: PO: EO 20:70:20 with a deviation of up to 10% each, the ratios being molar ratios. With a deviation of up to 10%, it is meant that the molar ratios can vary independently of one another by up to 10%.
  • no triblock polymers are used in which the first EO polymer is in a range of 18 to 22, the PO polymer in a range of 63 to 77 and the second EO polymer in a range of 18 to 22.
  • Triblock polymers used are the two EO polymers terminal and the PO polymer centered.
  • naphthalenesulfonic acid formaldehyde condensates are understood as meaning condensation products of naphthalenesulfonic acid and its derivatives and formaldehyde.
  • An example of this is Tamol NN 4501.
  • Tamol NN 4501 and the analogous structures have proven to be particularly advantageous additives according to the invention.
  • the Naphthalinsulfonklaformaldehydkondensate no linear chain with 2 to 10 atoms.
  • Cellulosederivate understood that are partially or completely etherified with unsubstituted or substituted alkanol compounds.
  • the etherified with unsubstituted or substituted alkanol compounds Preferably, the
  • Examples of preferred alkanol compounds are methanol, ethanol, 1, 2-dihydroxypropane and 1, 3-dihydroxypropane.
  • (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds is understood as meaning ammonium compounds which have at least one C 1 -C 25 -alkyl group and at least one polyalkylene oxide group
  • the "(C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds have 1 to 200, more preferably 2 to 100, even more preferably 5 to 50, alkylene oxide groups.
  • Alkylene oxide groups are preferably ethylene oxide groups and / or propylene oxide groups.
  • block polymers of ethylene oxide and propylene oxide are meant polymers composed of blocks of ethylene oxide and propylene oxide units.
  • An example of this is Pluronic F68.
  • These polymers also proved to be very advantageous according to the invention, also because they offer, for example, a good combination of price and performance.
  • Used propylene oxide units which are not triblock polymers having a composition of EO: PO: EO 20:70:20 with a deviation of up to 10%, wherein the ratios are molar ratios.
  • the block polymers used according to the invention have a molecular weight of at most 5000 g / mol, more preferably from more than 120 to 4500 g / mol, or of at least 6500 g / mol. According to another preferred embodiment, the molecular weight of the block polymer is less than 10,000 g / mol.
  • Polycationic compounds are polymers which have a plurality of cationic groups.
  • the polycationic invention is a polycationic invention.
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • the polycationic compounds are preferably selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary Vinylpyridines, homopolymers and copolymers based on alkylamine monomers,
  • Homopolymers and copolymers based on allylamine monomers are preferably selected from the group consisting of homopolymers and copolymers based on Diallyldialkylammoniummonomeren and homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamidmonomeren and mixtures thereof.
  • Particularly preferred in further embodiments are the homopolymers and copolymers based on diallyldialkylammonium monomers such as polydilallyldi (C 1 -C 3) alkylammonium compounds.
  • copolymer based on ..: means in the sense of the invention that at least 50 wt .-%, more preferably at least
  • the monomers are selected from the group of specified monomers, wherein the statement "wt .-%" on the Total weight of the copolymer relates.
  • the corresponding copolymers consist essentially or completely of the specified monomers. Homopolymers are naturally composed of only one monomer species.
  • diallyldialkylammonium monomers examples include polydilallyldi (C 1 -C 3) alkylammonium compounds such as polydilallyldimethylammonium chloride
  • polyDADMAC polydiallyldiethylammonium chloride
  • polyDADEAC polydiallyldiethylammonium chloride
  • PolyDADMAB Polydiallyldimethylammonium bromide
  • Polydilallyldiethylammonium bromide (polyDADEAB). Particularly preferred are:
  • (Meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof are polymers based on ((meth) acryloxy (C 1 -C 3 -alkyl)) di (C 1 -C 3 -alkyl) ammonium compounds, ((meth) acrylamido (C 1 -C 3 -alkyl )) di (C 1 -C 3 -alkyl) ammonium compounds, ((meth) acryloxy (C 1 -C 3 -alkyl)) tri (C 1 -C 3 -alkyl) ammonium compounds and ((meth) acrylamido (C 1 -C 3 -alkyl)) tri ( C1-C3-alkyl) - ammonium compounds, wherein the alkyl groups are preferably selected from methyl groups, ethyl groups and mixtures thereof as in (meth) acryloxyethyl- dimethylammonium compounds and
  • halides such as chlorides.
  • Examples of the ((meth) acryloxy (C 1 -C 3 -alkyl)) di (C 1 -C 3 -alkyl) ammonium compounds are poly ((meth) acryloyloxy (C 1 -C 3 -alkyl) di (C 1 -C 3 -alkyl) amine hydrochlorides.
  • Polyaminhydrochloride Other embodiments are preferably homopolymers of allylamines.
  • quaternary vinylpyridines are (C 1 -C 3 -alkyl) vinylpyridine compounds wherein the alkyl group is preferably a methyl group.
  • the alkyl groups of the poly (meth) acryloyloxyalkyldialkylamine hydrochlorides, the (meth) acryloyloxyalkyldialkylamine hydrochloride-acrylamide copolymers or poly (meth) acryloyl oxyalkyltrialkylammonium compounds are, for example, C 1 -C 10 -alkyl groups.
  • the poly (meth) acryloyloxyalkyltrialkylammonium compounds may be present as halides such as chlorides.
  • a preferred group of monomers and copolymers based on the alkylamines are polyethyleneimines such as polyethyleneimine hydrochlorides.
  • the polycationic compounds according to the invention preferably have at least 5, more preferably at least 10, even more preferably at least 100, even more preferably at least 150 cationic groups.
  • the cationic groups may be positioned in the polymer backbone and / or bound to the polymer backbone via the side chains.
  • the number average molecular weight of the polycationic compounds is preferably in the range of 1,000 to 10,000,000 g / mol, more preferably in the range of 5,000 to 2,000,000 g / mol, even more preferably in the range of 10,000 to 300,000 g / mol, more preferably in the range of 10,000 to 80,000 g / mol.
  • the polycationic compounds have a Fikentscher K value in the range of 15 to 60, more preferably in the range of 17 to 50, at 20 ° C.
  • the K value is calculated according to the following formula:
  • K K value according to Fikentscher
  • ⁇ ⁇ relative viscosity (dynamic viscosity of the solution / dynamic viscosity of the solvent)
  • c mass concentration of polymer in solution in g / cm 3 .
  • ammonium compounds are preferably selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds, more preferably from the group of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds.
  • ethoxylates (s) is understood in the context of the present invention to mean compounds which are reacted with ethylene glycol or Polyethylene glycol etherified or esterified.
  • the ethoxylated compounds be selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines, more preferably from the group consisting of ethoxylated (C 1 -C 25 alkyl) phenols, ethoxylated C 10 + acyclic aliphatic alcohols and ethoxylated C 7 + acyclic aliphatic amines, and even more preferably from the group consisting of ethoxylated C
  • the alkyl group of the ethoxylated (C 1 -C 25 alkyl) phenols is preferably a C 7 -C 25 alkyl group, and more preferably a C 9 -C 20 alkyl group.
  • the ethoxylated C7 + acyclic aliphatic amines are preferably ethoxylated C7-C25 acyclic aliphatic amines, more preferably ethoxylated C9-C21 acyclic aliphatic amines, even more preferably ethoxylated C10-C18 acyclic aliphatic amines.
  • the ethoxylated C10 + acyclic aliphatic alcohols are acyclic aliphatic alcohols, more preferably ethoxylated C12-C23 acyclic aliphatic alcohols.
  • Examples of C10 + acyclic aliphatic alcohols are tridecanol and 1-hydroxyeicosan.
  • the sulfonic acid derivatives likewise represent a preferred group of additives according to the invention.
  • the sulfonic acid derivatives according to the invention are preferably selected from the group consisting of C10 -C 25 alkyl sulfonates and C 10 -C 25 acyclic aliphatic sulfates, more preferably from the group consisting of C 10 -C 25 acyclic aliphatic sulfates.
  • acyclic aliphatic sulfates is meant compounds in which the sulfate group is directly attached to an alkyl group, alkenyl group or alkynyl group, an example of an acyclic aliphatic sulfate
  • the at least one additive used may also be a block copolymer of ethylene oxide and propylene oxide, but this does not
  • Triblock polymer having a middle block of propylene oxide and two blocks of ethylene oxide at the ends, in which the molar ratio of ethylene oxide (EO):
  • Propylene oxide (PO): ethylene oxide (EO) is 20:70:20, wherein the molar ratios can vary in each case by up to 10%. The ratio refers to the
  • the potential 10% variation in molar ratios means that any number of ratios can independently vary up or down by up to 10%. Examples of such aberrant ratios are 18:70:20, 22:77:18 or 21: 5:63:19.
  • the additives are not selected from block copolymers of ethylene oxide and propylene oxide having a molecular weight greater than 5000 g / mol to less than 6500 g / mol.
  • the block polymers of ethylene oxide and propylene oxide have also proved to be a very advantageous group of additives according to the invention.
  • the at least one additive used according to the invention is selected from
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, lignin sulfonates and block copolymers of ethylene oxide and propylene oxide;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 alkyl) (tri (C 1 -C 3 alkyl)) ammonium compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic aliphatic sulfates and C10-C25 alkyl sulfonates;
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols and
  • the at least one additive used according to the invention is selected from the group consisting of
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, lignin sulfonates and block copolymers of ethylene oxide and propylene oxide;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 alkyl) (tri (C 1 -C 3 alkyl)) ammonium compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic aliphatic sulfates and C10-C25 alkyl sulfonates;
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols and
  • the at least one additive used according to the invention is selected from the group consisting of naphthalene.
  • sulfonic acid-formaldehyde condensates lignosulfonates, block copolymers of ethylene oxide and propylene oxide, (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, C 10 -C 25 acyclic aliphatic sulfates, ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated C 10 + acyclic aliphatic alcohols and ethoxylated C 7 + acyclic
  • aliphatic amines more preferably from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, block copolymers of ethylene oxide and propylene oxide, (C12-C25-alkyl) (tri (C1-C3-alkyl)) ammonium compounds, C10-C25 acyclic aliphatic sulfates, ethoxylated C10 + acyclic aliphatic Alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the used as an additive it is preferred in the aforementioned embodiments that the used as an additive
  • the solvent used in the process according to the invention and contained in the suspensions according to the invention is miscible with water. Under a
  • Water-miscible solvent in the context of the present invention is understood to mean that at least 100 g of the relevant solvent can be dissolved in 1 l of water at 20 ° C., preferably that the solvent is immiscible with water at 20 ° C.
  • the term "miscible” in the sense of the present invention understood that no phase separation occurs.
  • each component of the solvent which is present in an amount of at least 5% by weight in and as a solvent constitutes a water-miscible solvent in the context of the present invention.
  • the water-miscible solvent be at least 90% by weight, preferably at least 95% by weight, more preferably at least 99% by weight and even more preferably at least 99.9% by weight of solvents consists whose dipole moment greater than 3.5 ⁇ 10 "30 cm.
  • the water-miscible solvent has a dipole moment of at least 4 ⁇ 10" 30 cm, more preferably at least 4.5 ⁇ 10 "30 cm, and even more preferably has at least 5 ⁇ 10 "30 Cm, in each case based on the total weight of the water-miscible solvent without additives and auxiliaries.
  • the water-miscible solvent selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol, acetone, ethylene glycol, butyl glycol and mixtures thereof.
  • At least 95% by weight, preferably at least 99% by weight of the water-miscible solvent is selected from the group consisting of water, ethanol, isopropanol, acetone, butylglycol and mixtures thereof, based in each case on Total weight of the water-miscible solvent without additives and
  • the content of organic solvent in the suspensions according to the invention is kept very low, so that preferably only traces are contained.
  • the solvent is selected from the group consisting of ethanol, water and mixtures thereof.
  • the term "aqueous” is understood to mean that the aqueous solvent present in the suspension according to the invention or used in the process according to the invention is at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight and even more preferably at least 99% by weight of water, in each case based on the total weight of the water-miscible solvent without additives and auxiliaries.
  • the solvent consists of at least 99.9 wt .-% of water or preferably only traces of other solvents, based on the total weight of the water-miscible solvent without additives and auxiliaries.
  • the at least one additive used according to the invention is disregarded in the abovementioned quantities of the solvents, even if the relevant additive is isolated as a liquid.
  • the solvent used in the invention comprises at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt% and even more preferably at least 35 wt% water, respectively based on the total weight of the water-miscible solvent without additives and auxiliaries.
  • the method according to the invention comprises the following steps in one variant:
  • Homogenizer or combinations thereof at least partially in the presence of at least one additive to obtain graphene platelets,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected, and
  • step a) wherein in step a) and / or in step b) at least one adjuvant according to formula (H1) is added,
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, unsubstituted C 2 -C 8 alkynyl groups, phenyl groups and phenyl (C 1 -C 3 alkyl) groups, wherein the
  • Phenyl groups and phenyl (C 1 -C 3 alkyl) groups may be unsubstituted or substituted with unsubstituted C 1 -C 3 alkyl groups or unsubstituted C 1 -C 3 vinyl groups.
  • the at least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected.
  • the at least one additive can be added in step a) and / or step b). It is essential that the crushing of the graphite takes place at least partially in the presence of the at least one additive and / or the at least one adjuvant.
  • the at least one additive, the at least one adjuvant or their combination is selected according to one of the preceding embodiments.
  • the at least one additive is added only in the course of the comminution step b). In this process variant, less additive appears to be required to produce a qualitatively comparable
  • this process variant is particularly suitable for example for expensive additives or for cases in which the amount of additive in the Graphenplättchensuspension and optionally in a subsequent
  • the at least one additive is added both in step a) and in step b).
  • the at least one adjuvant is likewise added both in step a) and in step b).
  • the at least one adjuvant is already added in the course of step a).
  • a polymeric surfactant as Additive it has proved to be particularly advantageous to add the at least one excipient in a first crushing step before the at least one additive is added. It has surprisingly been found that by this means the defect density of the obtained graphene platelets can be significantly reduced.
  • the method according to the invention comprises the following steps:
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide copolymers.
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected, added and added
  • step b) wherein in steps a1) or a2) or al) and a2) and optionally in step b) at least one adjuvant according to formula (HI) is added,
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • At least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds; Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the aforementioned block copolymers of ethylene oxide and propylene oxide are selected from the group consisting of block copolymers of ethylene oxide and propylene oxide having a molecular weight of at most 5000 g / mol, preferably greater than 120 to 4500 g / mol, or block copolymers of ethylene oxide and Propylene oxide with a molecular weight of at least 6500 g / mol.
  • the at least one adjuvant is added both in step a1), optionally also in step a2), and in step b). It has been found that comminution of the graphite-containing suspension in a step a2), wherein at least one additive and / or at least one adjuvant may already be present in the suspension, is of advantage for the following
  • Crushing step b) may be.
  • the comminution in step a2) can be carried out with a lower energy input compared to the comminution step b).
  • the comminution step b) of the method according to the invention is not a dispersion of graphene platelets or a mixing process of
  • Graphene platelets in a medium In the comminution step b), cleavage takes place in graphene platelets, whereby monolayer graphene platelets can also be produced during the cleavage, preferably produced directly from commercially available graphite.
  • the commercially available graphite is first classified, then comminuted, optionally reclassified and, after providing a suspension, the inventive comminution step b) at least partially in the presence of at least one inventive additive to be used and at least one invention to be used Excipient performed.
  • the separation of the graphene layers takes place as a result of the action of forces, in particular shear forces.
  • Graphene layers in the process according to the invention mainly or completely on the exertion of forces on the interconnected graphene layers under the action of the at least one additive and the excipient.
  • consolidation is understood to mean that graphene platelets are delaminated from the graphite or the graphite particles
  • At least one additive and the at least one excipient are separated with energy input from the graphite or graphite particles graphene platelets.
  • the term "comminution” is understood to mean that an energy input of at least 252 kJ / kg of graphite per hour takes place by means of the process in question
  • Graphene platelet suspension made of graphite, wherein natural or synthetic graphite can be used.
  • Graphene platelets contained in graphene platelets have a
  • Graphite is understood to mean substances that have a large number of
  • ultrasound is used in step b) of the method according to the invention.
  • the use of ultrasound in the preparation of the graphite suspensions according to the invention has the advantage, for example, that this
  • ultrasound it is advantageously very easy to produce smaller quantities of product in a batch operation, which are made available flexibly for further testing.
  • the ultrasound method is therefore particularly suitable for purposes in which, for example, an exact matching of the at least one additive and the excipient to a further formulation is particularly important.
  • the comminution by means of ultrasound can be operated continuously and discontinuously.
  • Continuous ultrasonic comminution processes for example, use a flow cell in combination with an ultrasonic finger such as the UP50H (50 W, 30 kHz) from Hielscher.
  • ultrasonic fingers can also be used for stationary
  • Ultrasonic crushing is typically set to an amplitude of 20-80% and a cycle of 0.2 to 1.
  • the sonication period is for example 0.5 to 6 hours.
  • the graphite can be used for example in a concentration in the range of 0.5 to 20 g per liter.
  • a ball mill is used in step b) of the method according to the invention.
  • the milling of graphite in a ball mill can be done in a single step to make the manufacturing process as simple as possible and to minimize costs.
  • it is at
  • step b) Using a ball mill in step b) preferably, in the preparation of
  • the graphite suspension comprising solvent and at least one additive to be used according to the invention may be used at different grinding conditions, such as, for example, mill rotation speed, ball size, MahlSystem Stirllgrad, grinding time, grinding media material or density, such.
  • mill rotation speed e.g., mill rotation speed
  • ball size e.g., ball size
  • MahlSystem e.g., mill rotation speed
  • ball size e.g., ball size
  • MahlSystem e.g., a grinding time
  • grinding media material or density such as steel balls, ceramic balls, etc.
  • the milling product can be bottled, diluted or concentrated as desired.
  • the critical speed indicates the time at which the
  • the rotational speeds of a ball mill are preferably 25% to 68%, more preferably 28% to 60% and more preferably 30% to less than 50% and still more preferably 35% to 45% of the critical rotational speed n crit .
  • step b it has proved to be advantageous if, in the comminution process to be used according to the invention in step b), large shearing forces are exerted on the
  • Graphite particles are exercised.
  • an agitator ball mill is used in step b) of the process according to the invention.
  • the comminution using a stirred ball mill is typically carried out in a continuous operation.
  • the grinding can be carried out using various grinding media, for example with respect to their material or their size, and grinding conditions, for example speed or duration of the
  • a homogenizer is used in step b) of the process according to the invention. Under a homogenizer are different
  • Homogenizers can be differentiated between rotor-stator-based homogenizers and pumping processes.
  • Rotor-stator homogenizers are mostly based primarily due to a strong turbulence due to the kinetic energy of the rotor.
  • the material to be homogenized can be set in motion by means of pumps and the achieved comminution effect can be based only to a small extent on turbulence. In between there are many different types of mixing.
  • additional blades may be attached to the rotor of a rotor-stator dispersing machine to achieve an intermediate stage of the aforementioned embodiments.
  • rotor-stator dispersing machine for example for laboratory use, are the ULTRA-TURRAX disperser from IKA and the L5 mixer from Silverson.
  • Homogenizing nozzle with a diameter of 0.3 to 0.7 mm lead to a
  • the aforesaid homogenizer is preferably operated in a circulatory system in order to achieve a uniform comminution of the particles.
  • the dispersion before the homogenizer through a Heat exchanger is performed to set a temperature of preferably 20 ° C to 70 ° C. Furthermore, it may be preferable in particular at high pressures, the
  • Dispersion after the homogenizer through a heat exchanger to allow rapid cooling of the dispersion and to avoid negative temperature effects.
  • a high pressure diaphragm pump is used to avoid contamination of the product with abrasion or lubricants.
  • the homogenizer nozzle can be made, for example, from a hard ceramic material pressed into a steel body.
  • a hard ceramic material for example, zirconia and
  • Silicon carbide can be used.
  • step b) is followed by a step c):
  • step c) isolating the graphene platelets obtained in step b) by centrifuging the suspension to obtain a mixture of graphene platelets, at least one additive and at least one adjuvant in the supernatant.
  • the energy is introduced into the suspension by means of agitator ball mill in step b).
  • the at least one additive is used in a concentration of at least 10% by weight, preferably at least 20% by weight, in each case based on the weight of the graphite.
  • the at least one adjuvant is used in a concentration of at least 30% by weight, preferably at least 70% by weight, in each case based on the weight of the graphite.
  • the present invention relates
  • Oxide content such graphene oxide platelets and products made therefrom do not have the outstanding properties of graphene platelets, such as electrical conductivity on.
  • the method according to the invention it is possible, in particular, to obtain stable suspensions which contain very large concentrations of graphene platelets.
  • the stability of the suspensions not only means their resistance to the settling of graphene platelets, but also that the suspensions according to the invention have a low tendency to agglomerate graphene platelets.
  • suspension may be preferred to disproportionately higher concentrations of additive and adjuvant to ensure a desired stability of the suspensions.
  • the combinations of at least one additive and at least one adjuvant to be used according to the invention have proven to be particularly advantageous for the preparation the high quality Graphenplattchen invention proved. This is naturally of great importance for products made therewith.
  • the suspensions of the invention show a high long-term stability. A high long-term stability ensures an uncomplicated incorporation of the graphene platelets with unchanged properties in a wide variety of products to achieve optimal
  • the present invention relates to a kit of at least one additive according to the invention and at least one excipient according to the invention.
  • the present invention relates to the use of a combination of at least one additive and at least one adjuvant in the production or handling of graphene sheets,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium Compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds; Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected, and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1),
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, unsubstituted C 2 -C 8
  • Phenyl groups and phenyl (C 1 -C 3 alkyl) groups may be unsubstituted or substituted with unsubstituted C 1 -C 3 alkyl groups or unsubstituted C 1 -C 3 vinyl groups.
  • the at least one additive is selected from the group consisting of N-alkylbetaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines.
  • the block copolymers of ethylene oxide (EO) and propylene oxide (PO) used as additive do not have triblock polymers with a
  • Composition of EO: PO: EO 20:70:20 with a deviation of up to 10% each, the respective ratios being molar ratios.
  • the at least one additive, the at least one adjuvant or their combination is selected according to one of the preceding embodiments.
  • the graphene platelets according to the invention and the suspensions according to the invention are suitable, for example, for use in and / or in the preparation of supercaps (supercapacitors), batteries, electrically conductive layers,
  • Composite material for achieving a mechanical reinforcement a preferred use according to the invention.
  • the use of the graphene platelets or of the suspensions according to the invention in the preparation of membranes for the industrial concentration of solutions by separation of water is a preferred embodiment of the invention.
  • the high electrical conductivity of the graphene platelets in combination with the high transparency makes it possible, for example, to use graphene platelets or a suspension thereof in or in the production of liquid crystal displays,
  • Antibody fragments occupied, for example, in diagnostic procedures or
  • the present invention relates Graphenplättchen and
  • the at least one additive selected from the group consisting of
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, lignin sulfonates and block copolymers of ethylene oxide and propylene oxide;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, preferably (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, and (alkyl) (polyalkylene oxide) ammonium compounds, to be selected; Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic aliphatic sulfates and C10-C25 alkyl sulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1),
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, and unsubstituted C 2 -C 8 alkynyl groups.
  • at least 3 R a1 are identical in the case of the at least one adjuvant according to formula (H1).
  • the at least one additive used according to the invention is preferably selected from the group consisting of
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, and unsubstituted C 2 -C 8 alkynyl groups.
  • the at least one additive used according to the invention is preferably selected from the group consisting of polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, lignin sulfonates and Block copolymers of ethylene oxide and propylene oxide; Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) - ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds and (C 1 -C 25 -alkyl ) (polyalkylene oxide) ammonium compounds; Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic aliphatic sulfates and C10-C25
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols and
  • the at least one excipient is selected from the group of excipients according to formula (H2),
  • R a2 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups
  • R b2 is selected from the group consisting of unsubstituted C 2 -C 4 alkenyl groups
  • at least 3 R a2 are identical in the case of the at least one adjuvant according to formula (H2).
  • the at least one additive is selected according to one of the aforementioned embodiments, wherein the abovementioned
  • Embodiment no acyclic, aliphatic sulfates, especially none
  • Alkyl sulfates Alkyl sulfates.
  • the at least one additive is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, lignin sulfonates, block copolymers of ethylene oxide and propylene oxide, (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C12-C25-alkyl) (trimethyl) ammonium compounds, C10-C25 acyclic aliphatic sulfates, C10-C25-alkyl sulfonates, ethoxylated (C1-C25-alkyl) phenols, ethoxylated C10-C25 acyclic aliphatic alcohols and ethoxylated C7-C25 acyclic aliphatic amines, more preferably from the group consisting of naphthalenesulfonic acid-formaldehyde
  • the present invention relates to a suspension comprising a water-miscible solvent, graphene platelets, at least one additive and at least one adjuvant,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 -alkyl) (dimethyl) (benzyl) ammonium compounds, and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids, wherein the fatty acids are independently from 10 to Ethoxylated C10 + acyclic aliphatic alcohols, in particular ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25, ethoxylated fatty acids, wherein the fatty acids independently have 10 to 25 carbon atoms acyclic aliphatic amines are selected, and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • Composition of EO: PO: EO 20:70:20 with a variation of up to 10% each, with ratios being in molar ratios.
  • the present invention relates to a suspension according to aspect 1, wherein the at least one additive is selected from polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth ) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and copolymers based on alkylamine monomers,
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth ) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and copolymers based on alkylamine monomers,
  • the polycationic compounds are selected from the group consisting of homopolymers and copolymers based on
  • Diallyldialkylammonium monomers homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof,
  • Homopolymers and copolymers based on allylamine monomers more preferably selected from the group consisting of homopolymers and copolymers based on Diallyldialkylammoniummonomeren and homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamidmonomeren and mixtures thereof.
  • the polycationic compounds of homopolymers and copolymers based on Diallyldialkylammoniummonomeren such as
  • Polydilallyldi (C1 -C3) alkylammonium select Preferably, in the copolymers of the polycationic compounds, at least 60% by weight, more preferably at least 75% by weight, of the monomers are selected from the group of specified monomers. In particular, it is preferred that the corresponding copolymers consist essentially or completely of the specified monomers.
  • the present invention relates to a suspension comprising a water-miscible solvent, graphene platelets, at least one additive and at least one adjuvant,
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, lignosulfonates and block copolymers of ethylene oxide (EO) and Propylene oxide (PO) can be selected;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 -alkyl) (dimethyl) (benzyl) ammonium compounds, and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids, wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids, wherein the fatty acids are independent from 10 to 25 carbon atoms, ethoxylated C10 + acyclic aliphatic alcohols, especially ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25 acyclic aliphatic amines are selected, and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the present invention relates to a suspension according to any of aspects 1 to 3, wherein the R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups and unsubstituted C 2 -C 8 alkynyl groups.
  • the present invention relates to a suspension according to any of aspects 1 to 5, wherein the R a1 are independently selected from the group consisting of unsubstituted C 1 -C 4 alkyl groups and unsubstituted C 2 -C 4 alkenyl groups.
  • the present invention relates to a suspension according to any one of aspects 1 to 6, wherein the R a1 are independently selected from the group consisting of unsubstituted C 1 -C 4 alkyl groups, unsubstituted C 2 -C 4 alkenyl groups, C 2 -C 4 alkynyl groups, vinyl-substituted phenyl groups and
  • the present invention relates to a suspension according to any of aspects 1 to 7, wherein the R a1 are independently selected from the group consisting of unsubstituted C 1 -C 4 alkyl groups.
  • the present invention relates to a suspension according to one of the aspects 1 to 8, wherein at least one adjuvant is selected from compounds according to formula (H2),
  • R a2 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups
  • R b2 is selected from the group consisting of unsubstituted C 2 -C 4 alkenyl groups and unsubstituted C 2 -C 4 alkynyl groups
  • x is 3 or 4.
  • the present invention relates to a suspension according to aspect 9, wherein the R a2 are independently selected from the group consisting of C 1 -C 4 alkyl groups.
  • the present invention relates to a suspension according to any one of aspects 9 to 10, wherein x is 4.
  • the present invention relates to a suspension according to any one of aspects 1 to 1 1, wherein the at least one additive is selected from the group consisting of polymeric surfactants selected from the group consisting of naphthalene-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, lignin - Sulfonates and block copolymers of ethylene oxide and propylene oxide, the no
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium Compounds, and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated fatty acids where the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols, especially ethoxylated C 10 -C 25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, especially ethoxylated C7-C25 acyclic aliphatic amines.
  • ethoxylated (C 1 -C 25 -alkyl) phenols ethoxylated fatty acids where the fatty acids independently have from 10 to 25 carbon atoms
  • ethoxylated C 10 + acyclic aliphatic alcohols especially ethoxylated C 10 -C 25 acyclic aliphatic alcohols
  • the present invention relates to a suspension according to any of aspects 1 to 12, wherein the at least one additive is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, lignosulfonates, block copolymers of ethylene oxide and propylene oxide which do not contain triblock polymers having a
  • Composition of EO: PO: EO 20:70:20 with a variation of up to 10%, with ratios being in molar ratios, (C12-C25 alkyl) (tri (C1-C3-alkyl) ) ammonium compounds, in particular (C12-C25-alkyl) (trimethyl) ammonium compounds, C10-C25 acyclic aliphatic sulfates, C10-C25-alkyl sulfonates, ethoxylated (C1-C25-alkyl) phenols, ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines, more preferably from the group consisting of naphthalenesulfonic acid formaldehyde condensates, block copolymers of ethylene oxide and propylene oxide, (C12-C25-alkyl) (trimethyl) ammonium compounds, C10-C25
  • the present invention relates to a suspension according to any one of aspects 1 to 14, wherein the group for selecting the at least one additive comprises no alkyl sulfates, preferably no acyclic aliphatic sulfates.
  • the present invention relates to a suspension according to any one of aspects 1 to 15, wherein the oxide content of the graphene platelets is below 1, 5 wt .-%, based on the total weight of the graphene platelets contained in the suspension. The oxide content of the graphene platelets is preferably less than 1.2% by weight.
  • the present invention relates to a suspension according to any one of aspects 1 to 16, wherein the graphene platelets in the Raman spectrum
  • the graphene sheets further have a half width of the 2D peak in a range of 35 to 65 cm -1
  • Graphene platelets in the Raman spectrum have an intensity ratio of the 2D peak to the G peak in a range of 0.5 to 2 and a half width of the 2D peak in a range of 35 to 65 cm “1 .
  • the present invention relates to a suspension according to any one of aspects 1 to 17, wherein the at least one additive according to formula (I) a
  • the present invention relates to a suspension according to one of the aspects 1 to 18, wherein the suspension contains the at least one additive in one
  • the present invention relates to a suspension according to any one of aspects 1 to 19, wherein the graphene platelets have an average thickness of a range of 0.5 and 5 nm, preferably from 0.6 to 3 nm.
  • the present invention relates to a suspension according to any one of aspects 1 to 20, wherein the graphene platelets in the suspension in a
  • the present invention relates to a suspension according to any one of aspects 1 to 21, wherein the suspension comprises at least two adjuvants according to formula (H1), wherein the at least two adjuvants are different from each other.
  • the present invention relates to a suspension according to one of aspects 1 to 22, wherein the water miscible solvent to at least 90% by weight 30 Cm consists of a solvent having a dipole moment of at least 3.5 x 10 ".
  • the present invention relates to a process for the preparation of a suspension according to any one of the preceding aspects, the process comprising the following steps:
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, in particular poly ((4-vinylbenzyl) (trimethyl) ammonium) compounds, lignin sulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO);
  • EO ethylene oxide
  • PO propylene oxide
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates, Polyethylene polyamine dicyandiamide polycondensates and cationically modified starches and celluloses;
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 alkyl) (dimethyl)) (benzyl) ammonium compounds, and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols, especially ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25 acyclic aliphatic amines, are selected, and selected
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups and unsubstituted C 2 -C 8 alkynyl groups.
  • the block copolymers of ethylene oxide and propylene oxide used as additive are none
  • the aforementioned block copolymers of ethylene oxide and propylene oxide have a molecular weight of at most 5000 g / mol, more preferably greater than 120 to 4500 g / mol, or at least 6500 g / mol.
  • the present invention relates to a process according to aspect 24, wherein the additive is selected from polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers , (Meth) acrylamide monomers and mixtures thereof, Homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and copolymers based on alkylamine monomers,
  • the present invention relates to a process for the preparation of a suspension according to one of the preceding aspects, the process comprising the following steps:
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, in particular poly ((4-vinylbenzyl) (trimethyl) ammonium) compounds, lignin sulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO);
  • EO ethylene oxide
  • PO propylene oxide
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 alkyl) (dimethyl)) (benzyl) ammonium compounds, and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids, wherein the fatty acids are independently from 10 to 25 C atoms, ethoxylated fatty acids, wherein the fatty acids independently 10 to 25 carbon atoms, ethoxylated C10 + acyclic aliphatic alcohols, especially ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25 acyclic aliphatic amines, are selected, and
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups and unsubstituted C 2 -C 8 alkynyl groups.
  • the block copolymers of ethylene oxide and propylene oxide used as additive are none
  • the aforementioned block copolymers of ethylene oxide and propylene oxide have a molecular weight of at most 5000 g / mol, more preferably greater than 120 to 4500 g / mol, or at least 6500 g / mol.
  • the present invention relates to a method for producing a graphene suspension, the method comprising the following steps:
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 -alkyl) (dimethyl) (benzyl) ammonium compounds, and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols, especially ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25 acyclic aliphatic amines, are selected and added
  • step b) at least one adjuvant according to formula (H 1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups, unsubstituted C 2 -C 8 alkynyl groups, phenyl groups and phenyl (C 1 -C 3 -alkyl) groups, where the phenyl groups and phenyl (C 1 -C 3 -alkyl) groups may be unsubstituted or substituted by unsubstituted C 1 -C 3 alkyl groups or unsubstituted C 1 -C 3 vinyl groups ,
  • the aforesaid block copolymers of ethylene oxide and propylene oxide have a molecular weight of at most 5000 g / mol, more preferably greater than 120 to 4500 g / mol, or of at least 6500 g / mol.
  • the present invention relates to a method according to aspect 27, wherein the at least one additive is selected from polycationic
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • the present invention relates to a method for producing a graphene suspension, the method comprising the following steps:
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds, especially (C 10 -C 20 -alkyl) (dimethyl) (benzyl) ammonium compounds, and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols, especially ethoxylated C10-C25 acyclic aliphatic alcohols, and ethoxylated C7 + acyclic aliphatic amines, in particular ethoxylated C7-C25 acyclic aliphatic amines, are selected and added
  • step b) at least one adjuvant according to formula (H 1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the aforesaid block copolymers of ethylene oxide and propylene oxide have a molecular weight of at most 5000 g / mol, more preferably from more than 120 to 4500 g / mol, or of at least 6500 g / mol.
  • the present invention relates to a method according to one of the aspects 24 to 29, wherein step b) is followed by a step c):
  • step c) isolating the graphene platelets obtained in step b) by centrifuging the suspension to obtain a mixture of graphene platelets, at least one additive and at least one adjuvant in the supernatant.
  • the present invention relates to a method according to any of aspects 24 and 26 to 30, wherein the at least one additive is selected from the group consisting of polymeric surfactants selected from the group consisting of
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 alkyl) (trimethyl) ammonium compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C10-C25 acyclic aliphatic sulfates and C10-C25 alkyl sulfonates; and ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 alkyl) phenols, ethoxylated fatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated C 10 + acyclic aliphatic alcohols, and ethoxylated
  • the present invention relates to a process according to one of the aspects 24 and 26 to 31, wherein the at least one additive is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, lignosulfonates, block copolymers of ethylene oxide and propylene oxide, (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) - ammonium compounds, in particular (C 12 -C 25 -alkyl) (trimethyl) ammonium compounds, C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 -alkyl sulfonates, ethoxylated (C 1 -C 25 -alkyl) phenols , ethoxylated C10 + acyclic aliphatic Alcohols and ethoxylated C7 + acyclic aliphatic amines, more
  • the at least one additive is selected from the
  • ethoxylated C7 + acyclic aliphatic amines especially ethoxylated C7-C25 acyclic aliphatic amines.
  • it is in the aforementioned
  • the present invention relates to a process according to any of aspects 24 and 26 to 32, wherein the at least one additive is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensates, block copolymers of ethylene oxide and propylene oxide, C 10 -C 25 acyclic aliphatic sulfates and C10-C25-alkylsulfonates.
  • the present invention relates to a method according to any one of aspects 24 to 33, wherein the group for selecting the at least one additive comprises no alkyl sulfates, preferably no acyclic aliphatic sulfates.
  • the present invention relates to a method according to one of the aspects 24 to 34, wherein in step b) the energy in the suspension means
  • the present invention relates to a method according to any of aspects 24 to 35, wherein the at least one adjuvant is used in a concentration of at least 30% by weight, preferably at least 70% by weight, based on the weight of the graphite becomes.
  • the present invention relates to graphene sheets wherein the graphene sheets were produced by a method according to any one of aspects 24 to 36.
  • the present invention relates to a suspension wherein the suspension has been prepared according to any one of aspects 24 to 36.
  • the present invention relates to the use of a
  • the at least one additive is selected from the group consisting of
  • N-alkyl betaines Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, in particular poly ((4-vinylbenzyl) (trimethyl) ammonium) compounds, lignin sulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO);
  • EO ethylene oxide
  • PO propylene oxide
  • polycationic compounds selected from the group consisting of homopolymers and copolymers based on diallyldialkylammonium monomers, homopolymers and copolymers based on (meth) acrylate monomers, (meth) acrylamide monomers and mixtures thereof, homopolymers and copolymers based on quaternary vinylpyridines, homopolymers and Copolymers based on
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium compounds and (C 1 -C 25 -alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids, wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids, wherein the fatty acids are independent from 10 to 25 carbon atoms, ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected, and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the block copolymers of ethylene oxide and propylene oxide are none
  • the present invention relates to the use according to aspect 39, wherein the at least one additive is selected from polycationic
  • Allylamine monomers allylamine hydrochloride-diallylamine hydrochloride copolymers, N-vinylacrylamidine hydrochloride-acrylamide copolymers, dialkylamine-epichlorohydrin copolymers, polyamide-polyamine-epichlorohydrin copolymers, dicyandiamide-formaldehyde polycondensates, urea-formaldehyde polycondensates,
  • the present invention relates to the use of a
  • the at least one additive is selected from the group consisting of N-alkyl betaines; Sorbitan trifatty acids wherein the fatty acids independently have 10 to 25 C atoms;
  • polymeric surfactants selected from the group consisting of naphthalenesulfonic acid-formaldehyde condensates, cellulose ethers, polyvinyl alcohols, poly ((4-vinylbenzyl) (tri (C 1 -C 3 -alkyl)) ammonium) compounds, in particular poly ((4-vinylbenzyl) (trimethyl) ammonium) compounds, lignin sulfonates and block copolymers of ethylene oxide (EO) and propylene oxide (PO);
  • EO ethylene oxide
  • PO propylene oxide
  • Ammonium compounds selected from the group consisting of (C 12 -C 25 -alkyl) (tri (C 1 -C 3 -alkyl)) ammonium compounds, (C 10 -C 20 -alkyl) (di (C 1 -C 3 -alkyl)) (benzyl) ammonium Compounds and (C 1 -C 25 alkyl) (polyalkylene oxide) ammonium compounds;
  • Sulfonic acid derivatives selected from the group consisting of C 10 -C 25 acyclic aliphatic sulfates, C 10 -C 25 alkyl sulfonates and (C 10 -C 25 alkyl) benzenesulfonates; and
  • Ethoxylates selected from the group consisting of ethoxylated (C 1 -C 25 -alkyl) phenols, ethoxylated sorbitan trifatty acids wherein the fatty acids independently have from 10 to 25 carbon atoms, ethoxylated fatty acids wherein the fatty acids independently have 10 to 25 carbon atoms , ethoxylated C10 + acyclic aliphatic alcohols and ethoxylated C7 + acyclic aliphatic amines are selected, and
  • the at least one adjuvant is selected from the group of adjuvants according to formula (H1)
  • R a1 are independently selected from the group consisting of unsubstituted C 1 -C 8 alkyl groups, unsubstituted C 2 -C 8 alkenyl groups,
  • the block copolymers of ethylene oxide and propylene oxide are none
  • the present invention relates to a use of
  • Examples 1 -1 to 1 -3 and Comparative Examples 1 -7 to 1 -10 200 mg of graphite flakes (SGL Carbon) in 40 ml of a solution of additive and
  • TAA Tetraethylammonium hydroxide
  • TSA Tetraethylammonium hydroxide
  • the stability of the suspensions is determined by determining the concentration of graphene contained in the suspension after 1 months of service life.
  • the shelf life was determined by storing 4 ml of graphene platelet suspension in a sealed 14 mm diameter tube vertically at a temperature of 25 ° C without shaking.
  • the amount of dispersed material was determined by UVA is spectroscopy.
  • the optical density of the centrifuged material was determined at 660 nm and the concentration of graphene with the known from the literature extinction coefficient of 2460 L g "1 m " 1 determined for exfoliated graphite.
  • Example example according to the invention
  • Examples 2-1 to 2-2 and Comparative Examples 2-3 to 2-5 4 g of graphite flakes (SGL Carbon) were dispersed in 800 ml of a solution of tetraethylammonium hydroxide (TEA) (Sigma Aldrich) in water. After stirring for 10 h by means of a magnetic stirrer at RT, the suspension was exposed for 2 h in a M-1 10P homogenizer from Microfluidics (pressure: 1200 bar). Subsequently, the supernatant was discarded and the sediment redispersed in 800 ml of an additive solution. Subsequently, the suspension for 8 h in a homogenizer M-1 10P Fa. Microfluidics (pressure: 1200 bar) claimed. In all experiments, the temperature of the suspension was adjusted to 20 ° C by means of flow cooling. The resulting product was 20 min at
  • the concentrations of graphene were determined after 1 month of service life.
  • 4 ml Graphenplättchensuspension were stored in a sealed tube with a diameter of 14 mm vertically at a temperature of 25 ° C without shaking.
  • the amount of dispersed material was determined by UVA is spectroscopy.
  • the optical density of the centrifuged material was determined at 660 nm and the concentration of graphene with the known from the literature extinction coefficient of 2460 L g "1 m " 1 determined for exfoliated graphite.

Abstract

L'invention concerne un procédé perfectionné de fabrication de suspensions de feuillets de graphène comprenant l'utilisation de combinaisons de composés spécifiques, les suspensions de feuillets de graphène obtenues par ce procédé, comprenant un solvant miscible avec l'eau, au moins un additif et au moins un adjuvant, ainsi que leur utilisation lors de la fabrication et de la manipulation de feuillets de graphène.
PCT/EP2014/064984 2013-07-12 2014-07-11 Suspension contenant du graphène, procédé de préparation de cette suspension, feuillets de graphène et leur utilisation WO2015004283A1 (fr)

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CN109437152A (zh) * 2018-12-12 2019-03-08 西北大学 一种钴氮共掺杂介孔碳材料的制备方法
CN110358035A (zh) * 2019-07-31 2019-10-22 西安工业大学 氨基化石墨烯改性脲醛树脂制备环保型胶粘剂的方法
CN110564481A (zh) * 2019-09-17 2019-12-13 南方科技大学 一种包含石墨烯的油溶性浆料及其制备方法和应用
WO2022206927A1 (fr) * 2021-04-01 2022-10-06 浙江正泰电器股份有限公司 Dispersant composite et procédé de préparation, ainsi que solution d'électrodéposition mixte et procédé de préparation

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WO2017105208A1 (fr) * 2015-12-16 2017-06-22 Centro De Investigación En Química Aplicada Procédé de préparation de concentrés de nanoplaquettes de graphène par broyage de graphite et d'exfoliants
CN106587034A (zh) * 2017-02-24 2017-04-26 安徽桑瑞斯环保新材料有限公司 一种生产薄层石墨烯的方法
CN109437152A (zh) * 2018-12-12 2019-03-08 西北大学 一种钴氮共掺杂介孔碳材料的制备方法
CN110358035A (zh) * 2019-07-31 2019-10-22 西安工业大学 氨基化石墨烯改性脲醛树脂制备环保型胶粘剂的方法
CN110358035B (zh) * 2019-07-31 2022-03-08 西安工业大学 氨基化石墨烯改性脲醛树脂制备环保型胶粘剂的方法
CN110564481A (zh) * 2019-09-17 2019-12-13 南方科技大学 一种包含石墨烯的油溶性浆料及其制备方法和应用
CN110564481B (zh) * 2019-09-17 2022-03-25 南方科技大学 一种包含石墨烯的油溶性浆料及其制备方法和应用
WO2022206927A1 (fr) * 2021-04-01 2022-10-06 浙江正泰电器股份有限公司 Dispersant composite et procédé de préparation, ainsi que solution d'électrodéposition mixte et procédé de préparation

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