WO2012156442A1 - Procédé de préparation de charges de carbone présentant des groupes amino à liaison covalente - Google Patents

Procédé de préparation de charges de carbone présentant des groupes amino à liaison covalente Download PDF

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WO2012156442A1
WO2012156442A1 PCT/EP2012/059113 EP2012059113W WO2012156442A1 WO 2012156442 A1 WO2012156442 A1 WO 2012156442A1 EP 2012059113 W EP2012059113 W EP 2012059113W WO 2012156442 A1 WO2012156442 A1 WO 2012156442A1
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Prior art keywords
carbon
reaction
fillers
carbon fillers
amino groups
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PCT/EP2012/059113
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German (de)
English (en)
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Christof W. Wigbers
Marion Kristina BRINKS
Johann-Peter Melder
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Basf Se
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Priority to CN201280030927.9A priority Critical patent/CN103619964A/zh
Priority to CA2836399A priority patent/CA2836399A1/fr
Priority to KR1020137030312A priority patent/KR20140037844A/ko
Priority to EA201391704A priority patent/EA201391704A1/ru
Priority to MX2013013311A priority patent/MX2013013311A/es
Priority to JP2014510791A priority patent/JP2014523926A/ja
Application filed by Basf Se filed Critical Basf Se
Priority to AU2012258241A priority patent/AU2012258241A1/en
Priority to EP12723430.0A priority patent/EP2710077A1/fr
Priority to BR112013029652A priority patent/BR112013029652A2/pt
Publication of WO2012156442A1 publication Critical patent/WO2012156442A1/fr
Priority to IL229311A priority patent/IL229311A0/en
Priority to ZA2013/09441A priority patent/ZA201309441B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • 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
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    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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    • 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
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C01P2004/133—Multiwall nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • the invention relates to a process for the preparation of carbon-containing covalently bound amino groups.
  • Carbon fillers have long been used, in particular in plastic molding compositions as a filler. Examples of such carbon fillers are (conductivity) carbon black, graphite, carbon nanotubes or graphene. Activated carbon or carbon fibers can also be used. The use is not limited to common filler applications, but also applications, for example in the field of electronics and storage media, such as electrical conductors and transistors, electrode materials, storage media, etc. imaginable.
  • CNTs carbon nanotubes
  • CNTs are understood in the prior art mainly cylindrical carbon tubes having a diameter of about 3 to 100 nm and a length which is a multiple of the diameter.
  • These tubes consist of one or more layers of ordered carbon atoms and have a different nucleus in morphology.
  • they are also referred to as “carbon fibrils” or “hollow carbon fibers” and are available in various forms (eg bamboo or onion shape).
  • Typical structures of these carbon nanotubes are of the cylinder type.
  • cylindrical structures a distinction is made between single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled cylindrical carbon nanotubes (Multi Wall Carbon Nano Tubes, (MWCNT)).
  • SWCNTs single-walled carbon nanotubes
  • DWCNTs double-walled carbon nanotubes
  • MWCNT multi-walled cylindrical carbon nanotubes
  • Common methods for their preparation are for. Arc discharge, laser ablation, chemical vapor deposition (CVD), and chemical vapor deposition (CCVD process).
  • Carbon nanotubes are lightweight, tensile and conduct electricity. They have hitherto been used mainly as additives for polymers.
  • CNTs are prone to strong agglomeration and are poorly soluble in polar or non-polar solvents.
  • One way to compensate for this disadvantage is the application of functional groups, eg. As amino groups, on the outer surface of the CNTs.
  • functional groups eg. As amino groups
  • amino groups-containing CNTs for example, K. Karousis, N. Tagmatarchis, D. Tasis, Chem. Rev. 2010. 1 10, pages 5366 to 5397).
  • the CNT must be pretreated prior to the application of amino groups.
  • the pretreatment may be a chemical reaction leading to a functional group such as As a carboxyl group leads. Only in one or more further chemical steps, this functional group is converted into an amino group.
  • the pretreatment can also be in a physical action such. As a temperature, plasma or ultrasonic treatment or mechanical treatment by crushing the carbon compound exist.
  • CN-A-101774573 a process for the amination of carbon nanotubes is described in which carbon nanotubes are first pretreated by heat, acids and / or ultrasound treatment and subsequently with ammonia or ethylenediamine at a temperature of 340 to 350 ° C and be implemented at a pressure of 6 to 1 1 MPa.
  • the pretreatment makes the process very expensive.
  • US Pat. No. 7,794,683 likewise describes the preparation of aminated carbon nanotubes, in which first carboxylic acid groups are introduced by acid treatment with sulfuric acid and nitric acid, which groups are then converted into acylazides by reaction with diphenylphosphoryl azide. The further reaction leads via isocyanate groups by hydrolysis to the formation of amino-functionalized carbon nanotubes.
  • a disadvantage of the process is the large number of reaction steps, which also sometimes require high-priced reagents.
  • Lithium amide is prepared from n-butyllithium and propylamine in dry THF. The reaction takes place at room temperature. After the reaction, oxygen is passed through the reaction mixture, thereby obtaining carbon nanotubes substituted by groups of the structure -NH-CH 2 -CH 2 -CH 3 -.
  • WO 2005/090233 describes the reductive functionalization of carbon nanotubes.
  • carbon nanotubes are introduced into liquid ammonia, into which lithium is also introduced as metal.
  • alkyl halide or aryl halide which leads to an alkylation of the outer surfaces of the carbon nanotubes, see Figure 1 and Example 1.
  • the reaction is carried out under cooling with the aid of acetone / T rockeneis, being heated to room temperature at the end of the reaction. Aminated carbon nanotubes are not described.
  • the invention of the above-described methods requires the chemical and / or physical pretreatment of the carbon nanotubes prior to functionalization.
  • the disadvantage of such pretreatment is that the structure of the carbon compounds can be damaged by the pretreatment. For example, damage may occur by sonicating the carbon nanotubes, as described in WO 2005/090233 in paragraph [0009].
  • the surface of the carbon nanotubes is attacked by the oxidizing agents, which leads to defects on the surface.
  • the object of the present invention is to provide a process for the preparation of carbon-containing covalently bound amino groups, such as carbon nanotubes, in which pretreatment of the carbon fillers can be dispensed with, damage to the carbon fillers, such as carbon nanotubes, is avoided, and the functionalization can be carried out in a reaction step with inexpensive reagents.
  • the functionalization should preferably not reduce the electrical conductivity of carbon nanotubes or reduce them only to a small extent.
  • the object is achieved by a process for the preparation of covalently bound amino groups having carbon fillers, by reacting a mixture containing carbon fillers and alkali and / or alkaline earth metals and / or their amides in liquid anhydrous ammonia, optionally together with an inert Solvent at temperatures of 35 to 500 ° C and a pressure of 30 to 250 bar.
  • carbon fillers can be functionalized by reaction with liquid ammonia containing alkali metals and / or alkaline earth metals or their amides with covalently bound amino groups.
  • WO 2005/090233 disclosed only alkylation by reaction with alkyl halides in the presence of lithium in liquid ammonia.
  • carbon filler refers to a particulate solid carbon material that is wholly or predominantly composed of carbon as a single element, examples of such materials being carbon nanotubes, graphene, carbon black, graphite, activated carbon These may be superficially modified, thereby introducing further chemical elements, yet their character is largely attributed to a carbon-only backbone, meaning that the term “carbon filler” does not imply a particular application in the present invention but rather the structure and state of matter of the particulate carbon material.
  • particulate carbon materials in addition to filler applications, are also conceivable and encompassed in electronics and storage media applications such as electrical conductors and transistors, electrode materials, storage media, etc.
  • modified Leitruß serves to provide thermoplastic molding compositions electrically conductive.
  • the use of the functionalized carbon fillers is not restricted to fillers. All advantageous applications are included.
  • the term “carbon filler” the term “particulate carbon material” may be used.
  • the carbon fillers are not pretreated.
  • reaction is preferably carried out in the absence of halogen-containing compounds, in particular organic halides, such as alkyl or aryl halides.
  • ammonia is preferably removed from the mixture, then excess alkali and / or alkaline earth metals or their amides are reacted with alcohols and / or water, and the carbon-containing covalently bound carbon atoms are separated from the reaction mixture.
  • the excess alkali and / or alkaline earth metals or their amides are preferential as implemented with Ci -4 -alkanols.
  • the carbon fillers used in the process are preferably selected from single- or multi-walled carbon nanotubes, graphenes, carbon black, graphite, activated carbon, carbon fibers or mixtures thereof.
  • the carbon fillers used in the process according to the invention may be selected from any suitable carbon fillers.
  • the fillers contain essentially only carbon as a chemical element, apart from possible impurities.
  • the carbon fillers have in particular a graphitic surface structure.
  • single- or multi-walled carbon nanotubes are single-walled, double-walled or multi-walled carbon nanotubes (SWCNT, DWCNT, MWNT), as described above, for example.
  • Suitable carbon nanotubes and graphenes are known to those skilled in the art.
  • suitable carbon nanotubes CNT
  • suitable carbon nanotubes are described in WO 2006/026691, paragraphs [0069] to [0074].
  • overall Suitable carbon nanotubes are also described in WO 2009/000408, page 2, lines 28 to page 3, line 11.
  • carbon nanotubes are understood as meaning carbon-containing macromolecules in which the carbon has (mainly) graphite structure and the individual graphite layers are arranged in a tubular manner.
  • Nanotubes and their synthesis are already known in the literature (for example J. Hu et al., Acc. Chem. Res. 32 (1999), 435-445). In principle, any type of nanotube can be used in the context of the present invention.
  • the diameter of the individual tubular graphite layers is preferably from 0.3 to 100 nm, in particular from 0.3 to 30 nm.
  • Nanotubes can be divided into so-called single-walled nanotubes (SWCNTs) and multi-waved nanotubes (MWCNTs) ; "Multi-faceted” nanotubes). In the MWCNTs several graphite tubes are thus placed one above the other.
  • the outer shape of the tubes may vary, this may have uniform diameter inside and outside, but there are also knot-shaped tubes and worm-like structures (vermicular) produced.
  • the aspect ratio (length of the respective graphite tube to its diameter) is at least> 10, preferably> 5.
  • the nanotubes have a length of at least 10 nm.
  • MWCNTs are preferred as component B).
  • the MWCNTs have an aspect ratio of about 500: 1 and an average length in the range of 1 to 500 ⁇ m.
  • the BET specific surface area is usually from 50 to 2000 m 2 / g, preferably from 130 to 1200 m 2 / g.
  • the impurities (eg metal oxides) produced during the catalytic preparation are generally from 0.1 to 12%, preferably from 0.2 to 10%, according to HRTEM.
  • Suitable nanotubes can be obtained under the name "multiwall” from Hyperion Catalytic Int., Cambridge MA (USA) (see also EP 205 556, EP 969 128, EP 270 666, US Pat. No. 6,844,061), as well as from Bayer Material Science, Nanocyl, Arkema and FutureCarbon.
  • Suitable graphenes are described, for example, in Macromolecules 2010, 43, pages 6515 to 6530.
  • (conductivity) carbon black, graphite or mixtures thereof are used.
  • Suitable carbon blacks and graphites are known to those skilled in the art.
  • the carbon black is in particular a Leitruß or conductivity soot, z. B. acetylene carbon.
  • Leitruß any common form of carbon black can be used, suitable, for example, the commercial product Ketjenblack 300 Akzo.
  • Conductivity can also be used for conductivity modification. Due to graphitic layers embedded in amorphous carbon, carbon black conducts electrons (F. Camona, Ann. Chim., Fr., 13, 395 (1988)). The power line takes place within the aggregates of soot particles and between the aggregates, if the distances between the aggregates are small enough. In order to achieve conductivity with the lowest possible dosage, preference is given to using carbon blacks with anisotropic structure (G. Wehner, Advances in Plastics Technology, APT 2005, Paper 1, Katowice 2005). In such Russians, the primary particles combine to form anisotropic structures, so that the distances required to achieve the conductivity of the carbon black particles in compounds are achieved even at comparatively low loading (C. Van Bellingen, N. Probst, E. Grivei, Advances in Plastics Technology , APT 2005, Paper 13, Katowice 2005).
  • Suitable carbon black types have, for example, an oil absorption (measured according to ASTM D 2414-01) of at least 60 ml / 100 g, preferably more than 90 ml / 100 g.
  • the BET surface area of suitable products is more than 50, preferably more than 60 m 2 g (measured according to ASTM D 3037-89).
  • the Leitrusse can be prepared by various methods (G. Wehner, Advances in Plastics Technology, APT 2005, Paper 1 1, Katowice 2005).
  • graphite can also be used as a filler.
  • Graphite is a modification of the carbon as described, for example, in AF Hollemann, E.
  • Graphite consists of planar carbon layers arranged one above the other Graphite can be comminuted by milling
  • the particle size is in the range from 0.01 ⁇ m to 1 mm, preferably in the range from 1 to 250 ⁇ m.
  • Carbon black and graphite are described, for example, in Donnet, J.B. et al., Carbon Black Science and Technology, Second Edition, Marcel Dekker, Inc., New York 1993. Conductivity soot based on highly ordered carbon black can also be used. This is described, for example, in DE-A-102 43 592, in particular [0028] to [0030], in EP-A-2 049 597, in particular page 17, lines 1 to 23, in DE-A-102 59 498 , in particular in paragraphs [0136] to [0140], as well as in EP-A-1 999 201, in particular page 3, lines 10 to 17.
  • the particle size is dependent on the respective carbon material and is preferably in the range from 1 nm to 1 mm, particularly preferably from 2 nm to 250 ⁇ m.
  • Carbon fibers preferably have a diameter in the range from 1 to 20 ⁇ m, particularly preferably from 5 to 10 ⁇ m.
  • the fibers may also be in the form of fiber bundles.
  • the reaction is carried out in the presence of alkali and / or alkaline earth metals or their amides.
  • Alkaline earth metals are preferably Ca or Mg.
  • Alkali metals are preferably selected from Li, Na, K and mixtures thereof. Particular preference is given to using Li or Na, in particular Na.
  • the alkali and alkaline earth metals it is also possible to use the corresponding amides, which are prepared in an independent reaction step.
  • preferred are Li, Na, K, Ca, Mg amide, Li, Na, Ca amide, more preferably Li and Na amide, most preferably Na amide.
  • the alkali metal and alkaline earth metal amides can be prepared by reacting the metals in liquid ammonia, if appropriate in the presence of catalysts.
  • Sodium amide is technically synthesized by passing gaseous ammonia over molten sodium (Ullmanns Encyclopedia of Technical Chemistry, 5th Ed., A 2, pages 151-161).
  • Ammonia is used as anhydrous liquid ammonia.
  • anhydrous is meant a water content of less than 1000 ppm.
  • the reaction can be carried out in liquid anhydrous ammonia.
  • a solvent or diluent which is inert under the reaction conditions may additionally be used.
  • ethers such as tetrahydrofuran, dioxane, methyl tert-butyl ether, and aliphatic, cycloaliphatic, aromatic hydrocarbons such as hexanes, cyclohexane and toluene, dimethylformamide or mixtures of these solvents in question.
  • the amount of said solvents is 0 to 20,000 wt .-%, in particular 0 to 2000 wt .-%, based on the carbon compound used.
  • the carbon fillers can be suspended in the said solvents are introduced into the reactor. After the amination they can be obtained after separation of ammonia suspended or dissolved in the solvents. Due to the use of solvents dusts occur only to a very small extent. This allows safe working.
  • the weight ratio of carbon fillers to ammonia is preferably 1 to 200, more preferably 1 to 20 to 1 to 90.
  • the molar ratio of alkali metal and alkaline earth metal or alkali metal amide and alkaline earth metal amide to ammonia is preferably 1 to 1000, more preferably 1 to 50 to 1 to 400.
  • the amination of the carbon compounds is carried out at temperatures of 35 to 500 ° C, preferably 50 to 250 ° C, particularly preferably 80 to 180 ° C. Work is carried out at total pressures, under which the ammonia is present in liquid form. The pressures are 30 to 250 MPa (bar), in particular 70 to 150 MPa (bar).
  • the reaction can be carried out in any suitable reactor which can withstand said pressure and temperatures. Preferably, in the reaction, the reaction mixture is mixed or stirred in the reactor.
  • the reaction mixture is preferably stirred vigorously under the reaction conditions mentioned in a reactor.
  • the stirrer speeds are 50 to 1000 rpm, in particular 250 to 350 rpm.
  • the reactor is preferably purged with an inert gas, for example nitrogen or argon, before use.
  • the reaction according to the invention is preferably carried out for 2 to 24 hours, more preferably 4 to 8 hours, preferably batchwise or else continuously.
  • reaction mixture is preferably expanded and cooled to 20 to 40 ° C. During the expansion of the ammonia can be evaporated and recovered by cooling back. It is also possible to separate the ammonia in a distillation column.
  • Unreacted alkali metals, alkaline earth metals or corresponding amides contained in the reaction effluent are preferably converted into safely separable compounds.
  • Alcohols or water preferably linear or branched alkyl alcohols having one to four carbon atoms, particularly preferably methanol or ethanol, very particularly preferably methanol suitable.
  • the alcoholates formed as reaction products can be separated from the aminated carbon compounds together with the corresponding excess alcohols and, if appropriate, solvents. This is preferably done by aspirating the carbon compounds on a suction filter, z. B. a glass filter.
  • the pore size of the filter is preferably 10 to 16 ⁇ .
  • the carbon fillers can be washed with an alcohol until the filtrate is no longer alkaline.
  • a dry carbon compound may, for. B. at 50 to 100 ° C in vacuo to constant weight.
  • the resulting aminated carbon fillers were tested after preparation by XPS analysis to determine the nitrogen content.
  • Functionalization is determined from detail spectra (measuring range ⁇ 5 - 10 eV from the peak maximum, 0.1 eV energy resolution, pass energy 20 - 30 eV) by comparison of the peak maxima of the carbon and the heteroatoms with known comparative data (eg Beamson G., Briggs D. High Resolution XPS of Organic Polymers: the Scienta ESCA300 Database (1992).).
  • the carbon line shape of the educt is determined under identical measuring conditions on the same spectrometer as for the product. (Details spectrum, Shirley background print)
  • the peak maximum of the carbon is corrected to 284.5 eV (aromatic carbon) and the change in the functionalization is determined by the fit of the line form of the starting material and various reference peaks in the measured spectrum of the product. example 1
  • the reaction was carried out in a stirred autoclave (3.5 l reaction volume with disk stirrer).
  • the autoclave was purged with argon.
  • 30 g MWCNT Baytubes ® C 150 P (with 140 ml of tetrahydrofuran moistened) and 8 g of sodium were charged.
  • 1200 ml (720 g) of ammonia were added in liquid form.
  • the autoclave was heated to 120 ° C. It set a pressure of 84 bar.
  • the autoclave was cooled to 40 ° C.
  • 0.5 l of methanol were pumped in to react with any remaining sodium and sodium amide.
  • the autoclave was slowly decompressed and held at 40 ° C for one hour for outgassing. After renewed pumping of 0.5 l of methanol, the autoclave was emptied via a riser.
  • the reaction product was filtered off with suction through a glass suction filter (10-16 ⁇ m) and washed with one liter of methanol. After transferring the CNTs into an 11 Erlenmeyer flask, they were stirred with one liter of methanol for 15 minutes and sucked off again. This process was repeated three times. Subsequently, the CNTs were dried at 70 ° C in vacuo to constant weight.
  • the detailed spectra of nitrogen from the XPS analysis show amine at 400.6 eV. The nitrogen content was determined to be 0.6 at% (average of 3 measuring points).
  • the autoclave was cooled to 40 ° C.
  • the aminated graphene was rinsed with methanol from the autoclave and aspirated through a 0.5 micron Teflon membrane. Then the graphene was suspended in 100 ml of methanol, stirred for 30 minutes and sucked off again.
  • the pressing on of nitrogen is not absolutely necessary.
  • Example 4 Analogously to Example 2 were reacted liquid ammonia in the presence of 10 ml of tetrahydrofuran, 250 mg of sodium amide and 120 ml of 500 mg MWCNT Baytubes ® C 150 P. After the workup and drying described in Example 2, the XPS analysis was performed. The detailed spectra of nitrogen from the XPS analysis show amine at 400.4 eV and imine at 398.9 eV. The amine nitrogen content was determined to be 1, 1 at% and the imine nitrogen content to 0.9 at% (for each average of 5 measurement points).
  • Example 4 Example 4:
  • Example 5 Analogously to Example 1, 10 g of MWCNT Nanocyl 7000 were reacted in the presence of 140 ml of tetrahydrofuran, 5 g of sodium and 1200 ml (720 g) of ammonia. The work-up and drying was carried out as described in Example 1. The detailed spectra of nitrogen from the XPS analysis show amine at 400.7 eV. The nitrogen content was determined to be 1, 1 at% (average of 3 measuring points).
  • Example 5 Example 5:
  • Example 2 Analogously to Example 1, 30 g of MWCNT Arkema C100 were reacted in the presence of 140 ml of tetrahydrofuran, 15 g of sodium and 1200 ml (720 g) of ammonia. The work-up and drying was carried out as described in Example 1.
  • Example 2 Analogously to Example 2, 500 mg of acetylene carbon (ABCR - 50% compressed, average particle size: 0.042 ⁇ , density: 0.100 g / cm 3 , surface area: 80 m 2 / g) in the presence of 10 ml of tetrahydrofuran, 500 mg of sodium and 120 ml (72 g) of liquid ammonia and reacted after pressing 30 bar of nitrogen. The work-up and drying was carried out as described in Example 2.
  • acetylene carbon ABCR - 50% compressed, average particle size: 0.042 ⁇ , density: 0.100 g / cm 3 , surface area: 80 m 2 / g
  • the detailed spectra of nitrogen from the XPS analysis show amine at 399.7 eV.
  • the nitrogen content was determined to be 1, 1 at% (average of 5 measuring points).
  • Example 2 Analogously to Example 2, 500 mg SWCNT, z. B. available from nanocyl in the presence of 10 ml of tetrahydrofuran, 500 mg of sodium and 120 ml (72 g) of liquid ammonia and after pressing of 30 bar of nitrogen. The work-up and drying was carried out as described in Example 2.
  • the detailed spectra of nitrogen from the XPS analysis show amine at 399.7 eV.
  • the nitrogen content was determined to be 0.9 at% (average of 5 measuring points).

Abstract

L'invention concerne un procédé de préparation de charges de carbone présentant des groupes amino à liaison covalente par mise en réaction d'un mélange contenant des charges de carbone et des métaux alcalins et/ou alcalinoterreux et/ou leurs amides dans de l'ammoniac anhydre liquide, éventuellement avec un solvant inerte, à des températures de 35 à 500 °C et à une pression de 30 à 250 bars.
PCT/EP2012/059113 2011-05-18 2012-05-16 Procédé de préparation de charges de carbone présentant des groupes amino à liaison covalente WO2012156442A1 (fr)

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CA2836399A CA2836399A1 (fr) 2011-05-18 2012-05-16 Procede de preparation de charges de carbone presentant des groupes amino a liaison covalente
KR1020137030312A KR20140037844A (ko) 2011-05-18 2012-05-16 공유 결합된 아미노기를 갖는 탄소 충전제의 제조 방법
EA201391704A EA201391704A1 (ru) 2011-05-18 2012-05-16 Способ получения углеродных наполнителей, обнаруживающих соединенные ковалентной связью аминогруппы
MX2013013311A MX2013013311A (es) 2011-05-18 2012-05-16 Proceso para producir cargas de carbono que tienen grupos amino covalentes enlazados.
JP2014510791A JP2014523926A (ja) 2011-05-18 2012-05-16 共有結合したアミノ基を有する炭素充填剤の製造法
CN201280030927.9A CN103619964A (zh) 2011-05-18 2012-05-16 制备具有共价结合的氨基的碳质填料的方法
AU2012258241A AU2012258241A1 (en) 2011-05-18 2012-05-16 Method for producing carbon fillers having covalently bonded amino groups
EP12723430.0A EP2710077A1 (fr) 2011-05-18 2012-05-16 Procédé de préparation de charges de carbone présentant des groupes amino à liaison covalente
BR112013029652A BR112013029652A2 (pt) 2011-05-18 2012-05-16 "processo para a produção de materiais de enchimento de carbono"
IL229311A IL229311A0 (en) 2011-05-18 2013-11-07 A process for producing carbon fillers having covalently bonded amino groups
ZA2013/09441A ZA201309441B (en) 2011-05-18 2013-12-13 Method for producing carbon fillers having covalently bonded amino groups

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CN114450249A (zh) * 2019-07-10 2022-05-06 弗劳恩霍夫应用研究促进协会 含碳材料的处理和纯化
CN115466482A (zh) * 2022-06-01 2022-12-13 湖南碳导新材料科技有限公司 一种高温下力学性能优异的轻质型复合材料及其制备方法

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WO2015071441A3 (fr) * 2013-11-14 2015-07-23 Imperial Innovations Limited Préparation de matériaux fonctionnalisés
CN114450249A (zh) * 2019-07-10 2022-05-06 弗劳恩霍夫应用研究促进协会 含碳材料的处理和纯化
CN115466482A (zh) * 2022-06-01 2022-12-13 湖南碳导新材料科技有限公司 一种高温下力学性能优异的轻质型复合材料及其制备方法
CN115466482B (zh) * 2022-06-01 2023-11-24 湖南碳导新材料科技有限公司 一种高温下力学性能优异的轻质型复合材料及其制备方法

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CA2836399A1 (fr) 2012-11-22
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ZA201309441B (en) 2016-02-24
IL229311A0 (en) 2014-01-30
BR112013029652A2 (pt) 2019-09-24
MX2013013311A (es) 2014-02-20
AU2012258241A1 (en) 2013-12-19
EA201391704A1 (ru) 2014-05-30
EP2710077A1 (fr) 2014-03-26
KR20140037844A (ko) 2014-03-27

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