WO2020243345A1 - Nanocarbones monodispersés préparés à partir de nanopolymères polysulfonés - Google Patents

Nanocarbones monodispersés préparés à partir de nanopolymères polysulfonés Download PDF

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WO2020243345A1
WO2020243345A1 PCT/US2020/034976 US2020034976W WO2020243345A1 WO 2020243345 A1 WO2020243345 A1 WO 2020243345A1 US 2020034976 W US2020034976 W US 2020034976W WO 2020243345 A1 WO2020243345 A1 WO 2020243345A1
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spherical
carbon
nanopolymer
surfactant
nanospheres
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William R. Betz
Brittany A. SMITH
Michael Keeler
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Sigma Aldrich Co LLC
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Sigma Aldrich Co LLC
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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

Definitions

  • Carbon adsorbents have long been important in many diverse applications, ranging from bulk-scale solution process devices, to analytical devices, to energy storage.
  • carbon nanosphere particles These carbon nanosphere particles, or carbon nanospheres, preferably contain greater than 90% carbon by weight and have a diameter in the range from about 10 nm to 900 nm.
  • the carbon nanospheres are monodisperse, while in other embodiments the carbon nanospheres are polydisperse.
  • the carbon nanospheres include a plurality of pores, which may include micropores, mesopores, macropores or a combination of any two or three types of pores.
  • the carbon nanospheres may be nonporous.
  • the carbon nanospheres may include an external graphitic layer.
  • the carbon nanospheres may also include an adsorptive coating.
  • Also provided are methods for preparing spherical nanocarbons the method comprising the steps of forming a spherical nanopolymer through a miniemulsion process; polysulfonating the spherical nanopolymer to form a polysulfonated spherical nanopolymer; drying the polysulfonated spherical nanopolymer; pyrolyzing the polysulfonated spherical nanopolymer to yield a spherical nanocarbon, and optionally, activating the spherical nanocarbon.
  • the spherical nanocarbon is graphitized by thermally treating the spherical nanocarbon at a temperature of at least 2500°C.
  • the mini emulsion process includes preparing a dual phase mixture having an aqueous phase having an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and an organic phase having a vinylaromatic monomer, a co-stabilizer and, if forming porous nanocarbons, a porogen; applying sufficient shear to the dual phase mixture to form an emulsion; and heating the emulsion to about 70°C with shear mixing until the polymerization reaction is complete, yielding the spherical
  • nanopolymer [0010] Also provided are devices including the spherical nanoparticles disclosed herein.
  • Figure 1 provides a schematic of the miniemulsion process disclosed herein.
  • Figure 2 provides a mathematical example of a Gaussian distribution graph.
  • Figure 3 shows the particle size distribution for monodisperse carbon nanospheres prepared at 227 nm.
  • Figure 4 shows an exemplary particle size distribution curve for a
  • Figure 5 illustrates the pore structure of a porous carbon nanosphere as described herein.
  • Figure 6 shows Van Deemter Plots for carbon microspheres with various pore structures.
  • Figure 7 is a drawing illustrating velocity changes in pores.
  • Figure 8 is a plot of incremental pore volume (cc/g) versus pore diameter (A) for the starting polymer materials for two carbon microspheres made using a standard emulsion process compared with starting polymer materials for two carbon nanospheres made using the miniemulsion process described herein.
  • Figure 9 shows the pore structure of a spherical nanopolymer (before pyrolysis) and the resulting spherical nanocarbon (after pyrolysis).
  • Figure 10 is an SEM image of graphitized, spherical nanocarbon hybrid.
  • Figure 11 shows a DFT overlay plot for an uncoated spherical nanocarbon (solid) and for the same spherical nanocarbon after applying a polymer coating (dashed line).
  • the new methods provided herein not only allow production of spherical carbons with diameters in the nanometer range, and the ability to control porosity.
  • a miniemulsion technique is utilized for nanocarbons disclosed herein.
  • the miniemulsion process is illustrated schematically in Figure 1.
  • This method of polymerization has some similarities to emulsion polymerization.
  • the aqueous phase is usually made up of water, a water-soluble initiator and a surfactant.
  • the organic phase contains the monomer(s) and co-stabilizer and optionally porogens. These two immiscible phases are mixed together by shear through the use of a rotor stator or ultrasonication.
  • CMC critical micelle concentration
  • carbon nanospheres As used herein the terms carbon nanospheres, carbon nanosphere particles, carbon nanoparticles, spherical nanocarbons, and nanocarbons are used interchangeably to refer to approximately spherical particles composed primarily of carbon and having a diameter of less than 1 micron, or more specifically, a diameter in the range from about 1 nm up to 1 micron. In some embodiments described herein, the carbon nanospheres have a diameter in the range from about 10 nm to about 900 nm. In other embodiments, the carbon nanospheres have a diameter in the range from about 200 nm to about 800 nm.
  • the carbon nanospheres have a diameter in the range from about 150 nm to about 325 nm.
  • the carbon nanospheres may have a diameter of 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm or 900 nm.
  • the carbon nanospheres fall within a specified range.
  • other preferred ranges include, e.g., from about 250 nm to about 750 nm, from about 300 nm to about 700 nm, from about 350 nm to about 650 nm, from about 300 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, from about 200 nm to about 600 nm, from about 200 nm to about 700 nm, from about 200 nm to about 900 nm, from about 300 nm to about 400 nm, from about 300 nm to about 500 nm, from about 300 nm to about 600 nm, from about 300 nm to about 700 nm, from about 300 nm to about 800 nm, from about 300 nm to about 900 nm, from about 400 nm to about 500 nm, from about 400 nm to about 600 nm, from about 300
  • Dispersivity can be measured by a number of methods.
  • One exemplary method of measuring particle size is using a laser scattering instrument. Using this method, the mean particle size and standard deviation are calculated.
  • Particles are monodisperse when the standard deviation of particle size is below about 6%; preferably, the standard deviation of particle sizes is below 6.0%.
  • particle size distribution of a plurality of particles may be measured using an electrical zone sensing particle analyzer.
  • the mean particle size is determined, and standard deviation calculated. From Figure 2, Dio and D90 are ⁇ 2 standard deviations, respectively. Dispersivity is calculated as D (90/10), or the particle size value at D90 (+2 standard deviations) divided by Dio (-2 standard deviations). Using this method, D (90/10) values below about 1.2, preferably below about 1.17, are considered monodisperse.
  • the synthesis of the carbon nanospheres can be tailored to produce either monodisperse or polydisperse particles without the need for any particle size sorting.
  • Figure 3 shows a particle distribution graph for carbon nanospheres prepared at 227 nm, illustrating that the particles are monodisperse as prepared, even through the carbonization process.
  • a laser scatter instrument was used to measure the particle size distribution.
  • Figure 4 shows the particle size distribution for a carbon microsphere (2.5 pm diameter) prepared using a conventional emulsion process.
  • Figures 3 and 4 illustrate that both the inventive carbon nanospheres and the conventional carbon microspheres are monodisperse.
  • the carbon nanospheres described herein typically are about 99% carbon and about 1% hydrogen by weight. In some embodiments, however, the carbon nanospheres may contain about 80% carbon by weight. More preferably, the carbon nanospheres are at least about 90% carbon by weight. In some embodiments, the carbon nanospheres are at least about 95% carbon by weight. In other embodiments, the carbon nanospheres are at least about 97% carbon by weight.
  • the percentage of carbon, by weight is at the lower end of the preferred range, e.g. around 80% carbon by weight, the overall weight may be affected by, e.g., the addition of oxygen during preparation. For various applications, it may be desirable to have a higher or lower percentage of carbon by weight.
  • the carbon nanospheres may contain about 80%, about 82%, about 85%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, or about 99% carbon, by weight.
  • the carbon atoms of the carbon nanospheres described herein may be arranged in sheet-like complexes of interconnected 6-carbon rings, and each 6- carbon ring may include from one and three double bonds from adjacent carbon atoms.
  • the surface of the carbon nanospheres may include carbon atoms that possess predominantly sp 3 orbitals, likely due to the extensive double bonding from adjacent carbon atoms.
  • the surface of the carbon microspheres may be relatively hydrophobic as a result of this structure.
  • the carbon nanospheres described herein typically have a surface area in the range from about 1 m 2 /g to about 4000 m 2 /g of carbon nanosphere particles. In certain embodiments, the surface area of the carbon nanospheres is in the range from about 300 to about 3500 m 2 /g. In some embodiments, the surface area of the carbon nanospheres is in the range from about 1500 to about 2500 m 2 /g. In other embodiments, the surface area of the carbon nanospheres is in the range from about 2000 to about 3500 m 2 /g. In some particularly preferred embodiments, the surface area of the carbon nanospheres is in the range from about 500 m 2 /g to about 1000 m 2 /g.
  • Some exemplary surface area ranges include, e.g., from about 1 m 2 /g to about 100 m 2 /g, from about 1 m 2 /g to about 200 m 2 /g, from about 1 m 2 /g to about 300 m 2 /g, from about 1 m 2 /g to about 400 m 2 /g, from about 100 m 2 /g to about 4000 m 2 /g, from about 500 m 2 /g to about 4000 m 2 /g, from about 1000 m 2 /g to about 4000 m 2 /g, from about 2000 m 2 /g to about 4000 m 2 /g, from about 300 m 2 /g to about 3000 m 2 /g, from about 500 m 2 /g to about 3000 m 2 /g, from about 1000 m 2 /g to about 3000 m 2 /g, and from about 2000 m 2 /g to
  • the carbon nanospheres described herein are porous, i.e., there is a defined pore structure in the particle.
  • the carbon nanospheres may be non-porous.
  • the presence or absence of pores, and the pore structure itself, can be modified in accordance with the methods described herein.
  • a pore can be defined as any cavity present on a solid surface with a depth:width ratio of approximately 10: 1.
  • the carbon nanospheres described herein may have open pores, i.e., pores open to the particle surface and are accessible to an external fluid. Open pores may be open at both ends or only one end, e.g., blind or dead end. Alternately, in other embodiments, the carbon nanospheres may include pores that are not accessible from the surface because they are only in the interior (not available to external fluids but affect, e.g., density, mechanical strength, etc.)
  • the carbon nanospheres described herein can have open pore structures, closed pore structures, or a combination of open pore structures and closed pore structures.
  • Pores in particulate materials are typically categorized by diameter.
  • Macropores have a >500 A (50 nm) diameter, mesopores have a 20-500 A (2- 50 nm) diameter, and micropores have a ⁇ 20 A (2 nm) diameter.
  • Figure 5 provides an illustration of macropores, mesopores, and micropores in a spherical carbon particle.
  • the pores are selected from micropores, mesopores, macropores, and combinations thereof.
  • the carbon nanospheres have primarily micropores. In other embodiments, the carbon nanospheres have primarily mesopores. In still other embodiments, the carbon nanospheres have primarily macropores.
  • the carbon nanospheres may have a latticework that forms a plurality of interconnected pores.
  • the carbon nanospheres may include micropores having mean pore diameters greater than about 10 A located predominantly near the exposed exterior surface of the carbon nanosphere.
  • Ultramicropores having mean internal diameters less than about 7 A may be located within the walls of the interconnected micropores in the interior of the carbon nanosphere. Aspects of the fabrication process, such as those described below, may control the distribution of pore sizes.
  • the carbon nanospheres include a combination of micropores, mesopores and macropores. Moreover, because the methods described herein allow for production of carbon nanoparticles with greatly varying pore structures, from non-porous to fully porous with varying pore sizes, the potential ratios of micropore:mesopore:macropore are (100:0:0) to (0:100:0) to (0:0: 100). In some embodiments, the pore structures further contain ultramicropores.
  • the carbon nanospheres include a combination of micropores and macropores.
  • the ratio of micropores to macropores is in the range from about 1% to about 99%.
  • the pore structures further contain ultramicropores.
  • Controlling pore composition is important as it determines the adsorption and desorption characteristics of the particle. Different pore structures are desirable for different applications. A highly microporous carbon which possesses mesopores and/or macropores is kinetically improved compared to a microporous-only carbon. A mesoporous-only carbon is best for large- biomolecule adsorption and chromatographic processes.
  • Figure 6 shows Van Deemter plots for carbon microspheres; this is illustrative for the carbon nanospheres described herein which can be produced with similar pore structures.
  • Figure 7 provides a graphical illustration of the velocity changes in pores.
  • vi is the interparticle velocity as well as the macropore velocity.
  • V2 is the mesopore velocity, approximately 0.1 vi.
  • V3 is the micropore velocity, approximately 0.01-0.001 vi. Velocity and diffusion are synonymous here.
  • Figure 8 shows a plot of incremental pore volume (cc/g) versus pore diameter (A) for the starting polymer materials for two carbon microspheres made using a standard emulsion process compared with starting polymer materials for two carbon nanospheres made using the miniemulsion process described herein.
  • Figure 9 illustrates the pores present in the mesopore and macropore ranges are maintained through the polysulfonation process. It is typical to observe some coalescing of these larger pores to produce micropores during the carbonization once the skeletal framework is stabilized by the polysulfonation process.
  • the carbon yield is approximately 90-95%.
  • the carbon yield is approximately 5%, and no porosity is maintained.
  • the carbon nanospheres include an external layer of graphitic carbon. Carbonization, by heating the pyrolyzed or
  • the graphitic/amorphous hybrid carbon is stable at high pressure of approximately 10,000 psi and does not fracture during vibration.
  • Figure 10 is a low-resolution SEM image of a graphitized, spherical polymer carbon.
  • the carbon nanospheres may include an absorptive coating bonded to the surface of the carbon nanospheres.
  • the absorptive coating may be an HLB polymeric coating, such as that disclosed in International Patent Publication No. WO2019040868, incorporated herein by reference.
  • the polymeric coating may be polyethylene glycol, or any non-polar to polar polymeric stationary phase used for gas chromatography (GC) or solid phase extraction (SPE) applications.
  • a first method for producing porous spherical nanocarbon includes the steps of first forming a porous spherical nanopolymer through a miniemulsion process; polysulfonating the porous spherical nanopolymer to form a polysulfonated porous spherical nanopolymer; drying the polysulfonated porous spherical nanopolymer; pyrolyzing the polysulfonated porous spherical nanopolymer to yield a porous spherical nanocarbon, and optionally, activating the porous spherical nanocarbon.
  • the miniemulsion polymerization involves the combination of a
  • the continuous phase (aqueous phase) is made up of an aqueous solvent, water-soluble initiator, and surfactant.
  • the dispersed phase (organic phase) contains the monomer, costabilizer and, optionally, porogens.
  • the two phases are mixed together via homogenization while stirring with an overhead stirrer. Once sufficiently mixed, the mixture is heated to 70°C with stirring for a time sufficient to form polymer nanospheres.
  • the water-soluble initiator may be a thermal initiator or a redox initiator.
  • Some exemplary thermal initiators selected from ammonium persulfate, potassium persulfate, lauroyl peroxide, benzoyl peroxide, 2,2- azobisisobutyronitrile and combinations thereof.
  • Some exemplary redox initiators include ammonium persulfate/sodium sulfite, ammonium
  • the surfactant used in the miniemulsion process may be an anionic surfactant, a cationic surfactant, or a nonionic surfactant.
  • anionic surfactants for use in the methods described herein include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium oleate and combinations thereof.
  • cetyltrimethylammonium bromide cetyltrimethylammonium chloride, octadecyl pyridium bromide and combinations thereof.
  • Some exemplary nonionic surfactants polyethylene oxide derivatives, and nonylphenol polyethoxylate with an average of 40 ethylene oxide units. Other suitable surfactants may also be used.
  • the surfactant is always added at a concentration below the critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • the dispersed phase contains the monomer, costabilizer and porogens.
  • the monomer is a vinylaromatic monomer.
  • Suitable vinylaromatic monomer include, but are not limited to, divinylbenzene, styrene, alpha-methylstyrene, vinyltoluene, p-methyl styrene, ethyl-vinylbenzene, vinylnaphthalene, trivinylbenzene,
  • vinylisopropenylbenzene diisopropypenylbenzene and combinations thereof.
  • the vinylaromatic monomer is selected from divinylbenzene, styrene and combinations thereof.
  • the mini -emulsion process also includes the addition of a co-stabilizer in the dispersed (organic phase).
  • the use of the co-stabilizer is another contrast to suspension polymerization processes, such as those used to make carbon microparticles.
  • the co-stabilizer is added to prevent Ostwald ripening or coalescence of smaller particles that merge together to create larger particles.
  • the co-stabilizer may be selected from Cio - C22 alkyl, C10 - C22 aliphatic alcohol, non-“ surface-active” polymers, and combinations thereof.
  • the co-stabilizer is selected from Cio - Ci8 alkyl, Cio - Ci8 aliphatic alcohol and combinations thereof.
  • the co-stabilizer is selected from the group consisting of hexadecane, cetyl alcohol and combinations thereof.
  • Porogens are solvents that are added to polymerization to affect the properties of the polymer being formed. Porogens can affect many properties of a polymer, including, but not limited to surface area, pore volume, pore size, porosity, and hydrophobic-hydrophilic properties. Particular porogens, or combinations of porogens are preferably added to tune the properties of the resulting polymer.
  • Suitable porogens may be selected from solvating porogens, i.e., porogens miscible in the polymer and monomer, non-solvating porogens, i.e., those with poor miscibility with the polymer, in particular, and combinations thereof.
  • Some exemplary porogens include toluene, xylenes, benzene, hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane, isooctane, dichloromethane, chloroform, carbon tetrachloride, benzyl alcohol, butanol, pentanol, hexanol, heptanol, 4-methyl -2-pentanol, isoamyl alcohol, dodecanol, ethyl acetate, 2-ethylhexanol, cyclohexanol, and combinations thereof.
  • One skilled in the art would also be able to choose additional porogens to tune the properties of the resulting polymers.
  • a combination of o-xylene and 4-methyl-2-pentanol are used for porogens.
  • the mini-emulsion is usually agitated through means such as ultracentrifugation or homogenization.
  • means such as ultracentrifugation or homogenization.
  • the inventors were able to obtain nanometer-sized particles using lower agitation with an overhead stirrer at 500 rpm. Accordingly, a homogenizer or stir paddle system may be used during the mini-emulsion process described herein.
  • the porous spherical nanopolymer is then polysulfonated.
  • Polysulfonation of the polymer nanospheres may be achieved by contacting the polymer nanospheres resulting from the processes described above with an amount of fuming sulfuric acid for a period ranging from about five hours to about 72 hours at a temperature ranging from about 150°C up to the polymer degradation temperature of the polymer nanospheres.
  • the amount of fuming sulfuric acid may range from about 100% and about 2000% of the total weight of the polymer nanosphere particles.
  • Fuming sulfuric acid refers to a solution of sulfur trioxide in sulfuric acid.
  • both sulfonate and sulfone groups may covalently bind to available carbons in the polymer nanospheres.
  • sulfone crosslinks may form from non- crosslinked carbons in the polymer nanospheres.
  • the methods described herein employ a higher temperature for this step.
  • the polysulfonization process described herein is carried out at 150°C.
  • the polysulfonization step may also be carried out at temperatures above 150°C, provided the temperature is below the polymer degradation temperature.
  • the higher temperature helps to stabilize the sulfur complex on the polymer ring structures when neutralizing with water.
  • Polysulfonating at 150°C improves the stability of the sulfur-carbon bonds during neutralization.
  • the theoretical bonding level of 1.6 sulfur groups per benzene ring structure is ensured, and the resultant carbon pore structure was found to be effective and repeatable.
  • polysulfonization is carried out by (a) cautiously adding sulfuric acid to the porous spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer; (b) heating the combination from the above step to a temperature of just below the melting point of the porous spherical nanopolymer and (c) maintaining the reaction at the temperature of just below the melting point of the porous spherical nanopolymer for a time sufficient to complete the polysulfonization.
  • the sulfuric acid is added at a ratio of at least 1.6 S: 1 ring structure of the porous spherical nanopolymer.
  • a ratio of greater than 1.6 S: 1 ring structure i.e., 2 S: 1 ring structure, or even greater is used.
  • the reaction temperature is maintained to at least 150°C, or potentially higher if the polymer degradation temperature allows.
  • polysulfonization is carried out by cautiously adding sulfuric acid to the porous spherical nanopolymer, wherein the sulfuric acid is added at a ratio of 1 : 10 sulfuric acid:porous spherical polymer (wt.:wt.); heating the combination from the above step to about 150°C; and maintaining the reaction at 150°C for a time sufficient to complete the polysulfonization.
  • the polymer nanospheres may be neutralized by rinsing the particles in deionized water, while maintaining the temperature of the mixture of water and particles below about 100°C.
  • nanospheres are subjected to pyrolysis to produce the inventive carbon nanospheres.
  • Pyrolysis is carried out by heating the the polysulfonated porous polymer nanospheres at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete to yield the carbon nanospheres.
  • pyrolysis is performed for a period ranging from about 15 minutes to about two hours.
  • a fluidized bed treatment may be used for the pyrolysis; in that
  • heated nitrogen is passed upward through a bed of polysulfonated polymer nanospheres.
  • the gas serves to agitate as well as to heat the particles.
  • a static bed may be used for pyrolysis.
  • the polysulfonated polymer nanospheres may be loaded into quartz trays and loaded into a thermal furnace and heated to a temperature of about 1100° C for about two hours under inert gas sweep.
  • the resulting carbonaceous nanospheres may be removed from the thermal furnace after cooling the oven to room temperature.
  • the resulting carbon nanospheres may be activated through an activation step.
  • the activation step involves contacting the porous spherical nanocarbons with a physical activation gas a temperature in the range from about 300°C to about 1200°C.
  • the physical activation gas may be selected from steam, oxygen, carbon dioxide or a combination thereof.
  • Steam activation may widen the micropores within the porous spherical nanocarbons by a process in which the water vapor dissociates and reacts with the porous spherical nanocarbons.
  • the oxygen component of the dissociated steam may react with carbon in the framework of the carbonaceous particles to form CO2 and/or CO, which outgases from the particles.
  • the steam activation process may create new pores by the removal of carbon from the porous spherical nanocarbons and may also reopen pores closed by the initial pyrolysis process described above. Any adsorbed compounds trapped within the pores of the porous spherical nanocarbons may be solubilized and removed from the particles during the activation processes.
  • the steam activation process is performed by placing porous spherical nanocarbons in a Lindberg vertical furnace and attaching a source of steam to the inlet line of the furnace.
  • the steam activation process may be performed for a period of time sufficient to ensure that the maximum number of pores has opened up in the carbon nanospheres, and to ensure that the desired pore diameter is achieved.
  • the size of the pores within the carbon nanospheres may be manipulated to predetermined values by specifying the duration and temperature at which the steam activation is performed. Longer durations and higher activation temperatures may be associated with larger and more numerous pores in the carbon nanospheres.
  • the steam activation of the carbon nanospheres may be conducted at a temperature ranging from about 600°C and about 1,000°C. In some embodiments, steam activation is carried out in the range from about 700°C to about 900°C. In an additional embodiment, the steam activation of the carbon nanospheres may be conducted at a temperature of about 850°C.
  • the activated carbon nanospheres may be subjected to a second pyrolysis treatment to reduce the overall size of the pores within the particles and which may also provide a more hydrophobic carbon surface.
  • the desired overall size of the pores within the particles may be selected to impart specificity for the adsorption of particular compounds based on the internal diameter of ultramicropores.
  • the resulting internal diameters of the pores within the carbon nanospheres after post-activation pyrolysis may depend upon the temperature and duration at which the pyrolysis is conducted.
  • the post-activation pyrolysis is conducted at a temperature ranging from about 560°C and about 1300°C. In another embodiment, the post-activation pyrolysis is conducted at a temperature in the range from about 800°C and about 1200°C. In another embodiment, the post activation pyrolysis is conducted at a temperature of about 1150°C.
  • the carbon nanospheres are graphitized.
  • Graphitization, or carbonization may be carried out on the pyrolyzed or pyrolyzed/activated carbon nanospheres by heating to a temperature of at least 2500°C, results in a graphitized, spherical polymer carbon.
  • This carbon possesses an external layering of graphitic carbon with an amorphous internal carbon structure. This layer is typically about 2% of the total carbon mass.
  • the graphitic/amorphous hybrid carbon is stable at high pressure of approximately 10,000 psi and does not fracture during vibration.
  • Figure 10 is a low-resolution SEM image of a graphitized, spherical polymer carbon.
  • the graphitic carbon on the carbon nanospheres is about 1% to about 40% of the carbon by weight. In a preferred embodiment, the graphitic carbon is about 1% to about 3% of the carbon by weight.
  • the carbon nanospheres may further include an adsorptive coating, such as a coating suitable for GC, SPE, or other adsorptive process.
  • an adsorptive coating such as a coating suitable for GC, SPE, or other adsorptive process.
  • such devices may include, for example, filtration devices, electrical devices, chromatography columns, solid phase extraction cartridges, solid phase microextraction fibers, thermal desorption tubes, bulk preparation devices, batteries, electrodes and drug delivery devices.
  • the spherical nanocarbons described herein may be used in place of, or in addition to, conventional carbons, such as carbon microspheres such as the Carboxen® carbons available from Supelco Inc., or other conventional particles.
  • Carbon nanospheres comprising at least 99% carbon by weight and having a diameter in the range from about 10 nm to 900 nm.
  • nanospheres are monodisperse.
  • nanospheres comprise a combination of micropores, mesopores and macropores.
  • a method for preparing a porous spherical nanocarbon comprising the steps of forming a porous spherical nanopolymer through a miniemulsion process; polysulfonating the porous spherical nanopolymer to form a
  • polysulfonated porous spherical nanopolymer drying the polysulfonated porous spherical nanopolymer; pyrolyzing the polysulfonated porous spherical nanopolymer to yield a porous spherical nanocarbon, and optionally, activating the porous spherical nanocarbon.
  • miniemulsion process comprises the steps of providing a dual phase mixture having an aqueous phase and an organic phase, wherein the aqueous phase comprises an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer, a co stabilizer and a porogen; applying sufficient shear to the dual phase mixture to form an emulsion; and heating the emulsion to 70°C with shear mixing until the polymerization reaction is complete, yielding the porous spherical nanopolymer.
  • the initiator comprises a thermal initiator selected from the group consisting of ammonium persulfate, potassium persulfate, lauroyl peroxide, benzoyl peroxide, 2,2-azobisisobutyronitrile and combinations thereof.
  • the initiator comprises a redox initiator selected from the group consisting of ammonium persulfate/sodium sulfite, ammonium persulfate/tetramethyl ethylene diamine, hydrogen peroxide/sodium formaldehyde sulfoxylate and combinations thereof.
  • cetyltrimethylammonium chloride cetyltrimethylammonium chloride, octadecyl pyridium bromide and
  • step of polysulfonating the porous spherical nanopolymer comprises the steps of cautiously adding sulfuric acid to the porous spherical nanopolymer, wherein the sulfuric acid is added at a ratio of 1 : 10 sulfuric acid:porous spherical polymer (wt.:wt.); heating the combination from the above step to about 150°C; and maintaining the reaction at 150°C for a time sufficient to complete the polysulfonization.
  • the method of item (23) wherein the pyrolyzing step comprises heating the polysulfonated porous spherical nanopolymer at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete.
  • aqueous phase comprises an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer and a co stabilizer;
  • step (ii) heating the combination from step (b)(i) to a temperature of about 150°C and
  • Homogenization was started after addition of the aqueous phase. Once the organic phase was added, the homogenization rate was increased. The solution turned from a 2-layer clear liquid to a white continuous phase. Heating was started immediately to 70°C. The reaction was carried out for about 3 hours.
  • the polymer was filtered and washed using a filtering centrifuge.
  • the contents of the flask were poured into a funnel which would feed into the basket.
  • a polypropylene bag particles were separated from the liquid.
  • a line was connected for the outlet feed which emptied into a waste bucket.
  • the contents were washed with copious amounts of methanol. After removal of the methanol, the contents were left to spin for about 15 minutes before shutting down the centrifuge.
  • a polysulfonation reaction setup was assembled which included a 4-neck 5000mL round bottom flask, reflux condenser, addition funnel and temperature probe. The previously synthesized polymer was added to the flask. Stirring commenced while 2000 mL H2SO4 was cautiously added dropwise through the addition funnel. Addition of H2SO4 was temporarily stopped when the temperature reached 70°C. Stirring was stopped and done manually until the contents became fluid. Once the reactor had cooled to about 45°C, addition of acid was resumed. This process was repeated until the temperature started to drop even with acid addition. The remaining acid was then added through the addition funnel. Heat was applied and set to 150°C. Once 150°C was reached, heating continued for 4 hours.
  • Nitrogen gas was passed through the combustion tube at a flow rate of 50 - 500 mL/minute. The effluent was trapped in an impinger, and subsequently vented to an appropriate scrubber and hood.
  • Activation was performed using a quartz combustion tube, positioned in a horizontal tube furnace.
  • the thermal profile followed in summarized in the table below:
  • Oxygen (compressed air) activation was accomplished by passing 100% air at 100 mL/minute, using a similar profile.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne des nanoparticules de carbone sphériques ayant des diamètres dans la plage d'environ 200 à environ 900 nm et leurs procédés de fabrication. Selon les procédés de l'invention, des nanopolymères sphériques sont formés par un procédé de mini-émulsion, les nanopolymères sphériques sont ensuite polysulfonés puis pyrolysés pour former des nanoparticules de carbone sphériques. Les surfaces peuvent être en outre modifiées avec, par exemple, divers adsorbants pour modifier davantage les propriétés. Le procédé de formation permet la production de diverses structures de pores, de non poreuses à entièrement poreuses, l'accordabilité de la structure des pores permettant des micropores, des mésopores, des macropores et des combinaisons quelconques de ceux-ci, permettant une large gamme de surfaces rendant ces nanocarbones appropriés pour de nombreuses applications, y compris la préparation, la purification et l'analyse d'échantillons et de vrac, et des applications d'administration de médicament.
PCT/US2020/034976 2019-05-31 2020-05-28 Nanocarbones monodispersés préparés à partir de nanopolymères polysulfonés Ceased WO2020243345A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021004906A1 (de) 2021-09-29 2023-03-30 Smart Material Printing B.V. Schwermetallfreie topische Medizinprodukte und Kosmetika, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102021004907A1 (de) 2021-09-29 2023-03-30 Smart Material Printing B.V. Mechanochemisch vorbehandelte, schwermetallfreie Aktivkohlepartikel A zur Verwendung in der Medizin
WO2025015417A1 (fr) * 2023-07-14 2025-01-23 UNIVERSITé LAVAL Procédé de production de feuilles de graphène et de nanostructures de carbone creuses ainsi que graphène bicouche/à quelques couches torsadé ainsi produit

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