WO2015016639A1 - 분산제, 이의 제조 방법 및 이를 포함하는 탄소계 소재의 분산 조성물 - Google Patents
분산제, 이의 제조 방법 및 이를 포함하는 탄소계 소재의 분산 조성물 Download PDFInfo
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- WO2015016639A1 WO2015016639A1 PCT/KR2014/007064 KR2014007064W WO2015016639A1 WO 2015016639 A1 WO2015016639 A1 WO 2015016639A1 KR 2014007064 W KR2014007064 W KR 2014007064W WO 2015016639 A1 WO2015016639 A1 WO 2015016639A1
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- dispersant
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 124
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 239000006185 dispersion Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 66
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 229910021389 graphene Inorganic materials 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 11
- 229910003472 fullerene Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- PCCNIENXBRUYFK-UHFFFAOYSA-O azanium;cerium(4+);pentanitrate Chemical compound [NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PCCNIENXBRUYFK-UHFFFAOYSA-O 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000002803 fossil fuel Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000921 elemental analysis Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 claims description 4
- 125000001174 sulfone group Chemical group 0.000 claims description 4
- NPYWBTRFOVOZNK-UHFFFAOYSA-L [O-]S([O-])(=O)=O.N.[Ce+4] Chemical compound [O-]S([O-])(=O)=O.N.[Ce+4] NPYWBTRFOVOZNK-UHFFFAOYSA-L 0.000 claims description 3
- 229910019617 (NH4)4Ce(SO4)4 Inorganic materials 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 239000003125 aqueous solvent Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012776 electronic material Substances 0.000 description 6
- 238000000527 sonication Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000012769 display material Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004482 13C cross polarization magic angle spinning Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- -1 solar cells Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001196 time-of-flight mass spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
-
- 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
- C01B32/152—Fullerenes
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- 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
- C01B32/194—After-treatment
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Definitions
- Dispersant, preparation method thereof and dispersion composition of carbon-based material comprising the same
- the present invention relates to a novel dispersing agent capable of uniformly dispersing various carbon-based materials in various media including a receiving medium, a method for preparing the same, and a dispersion composition of a carbon-based material including the same.
- thermoplastic resin compositions secondary batteries, solar cells, display materials, or electronic materials.
- carbon nanotubes or derivatives thereof has been examined and attempted, and the characteristics of various semiconductor devices or display devices have been further investigated.
- carbon-based nanomaterials such as graphene (graphene) or derivatives thereof have been attempted.
- thermoplastic resin composition the use of various carbon-type materials is tried for the purpose of improving the mechanical characteristic, adding a novel characteristic, such as electrical conductivity, etc. '
- the carbon-based material such as the carbon nanotube, graphene, carbon black, fullerene-based material or derivatives thereof in various fields, desired physical properties
- a conductive material including carbon nanotubes it is necessary to uniformly disperse such carbon-based material in a medium such as an aqueous solvent at high concentration.
- dispersants that have been known or studied before are not able to sufficiently disperse the carbon-based material depending on the type of medium, or in many cases, the use of an excessive amount of the dispersant is required to effectively disperse the carbon-based material.
- previously known dispersants have disadvantages such that the raw material itself is expensive or requires a complicated manufacturing process, resulting in a very high manufacturing cost.
- various carbon-based materials such as carbon nanotubes, graphene or fullerene-based materials can be uniformly dispersed at high concentrations in various media, for example, environmentally friendly solvents. Simplified manufacturing process and low cost of new dispersants Development continues to be required.
- the present invention provides a novel dispersant and a method for producing the same, which can uniformly disperse various carbon-based materials in various media including a solvent.
- the present invention provides a dispersion composition of a carbon-based material comprising such a novel dispersant and a carbon-based material uniformly dispersed thereby.
- the present invention provides a dispersant comprising a mixture of a plurality of polyaromatic hydrocarbon oxides, the mixture comprising a polyaromatic hydrocarbon oxide having a molecular weight of 300 to 1000 in an amount of 60% by weight or more.
- the oxygen content may be 12 to 50 weight 0 / ° of the total element content of the entire mixture.
- the polyaromatic hydrocarbon oxide may have a structure in which at least one oxygen-containing functional group is bonded to an aromatic hydrocarbon including 5 to 30 benzene rings. More specifically, the aromatic hydrocarbon may have 7 to 20 benzene rings in the structure, and the oxygen-containing functional group may be at least one selected from the group consisting of hydroxy group, epoxy group, carboxyl group, nitro group and sulfone group.
- the above-mentioned dispersant may be used for dispersion in the solvent of the carbon-based material. More specific examples of the carbon-based material that the dispersant may be used for dispersion include graphene, carbon nanotubes, graphite, carbon black and fullerene-based materials, and derivatives thereof. Species and the like, and various other carbon-based materials.
- the present invention also provides a method for preparing the dispersant comprising the step of oxidizing a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 in the presence of an oxidizing agent.
- the oxidizing agent is nitric acid (HN0 3 ), sulfuric acid (H 2 S0 4 ), hydrogen peroxide (H 2 0 2 ), ammonium cerium (IV) sulfate; (NH 4 ) 4 Ce (S0 4 ) 4 ) and ammonium cerium (IV) nitrate (Ammonium cerium (IV) nitrate; (NH 4 ) 2 Ce (N0 3 ) 6 ).
- the mixture including polyaromatic hydrocarbons having a molecular weight of 200 to 1500 may include a plurality of aromatic hydrocarbons containing 5 to 50 benzene rings.
- the oxidation step may be performed for 10 to 9 hours (0.5 to 20 hours under a reaction temperature of rc) in the solvent.
- the mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 as a starting material of the production method may be derived from a pitch obtained from a fossil fuel or a product thereof.
- the production method after the oxidation step, to purify the resultant It may further comprise the step of obtaining a mixture of a plurality of polyaromatic hydrocarbon oxides, this purification step may proceed including the step of centrifuging the result of the oxidation step.
- the present invention also carbon-based material; And it provides a dispersion composition of a carbon-based material comprising the dispersant described above.
- the carbon-based material may be at least one selected from the group consisting of graphene, carbon nano-leave, graphite, carbon black, fullerene-based material, and derivatives thereof.
- Such a dispersion composition is a dispersion of a high concentration of carbon-based material in a higher concentration and uniformly in a medium such as an aqueous solvent by the action of the above-described dispersant, carbon-based for a variety of products such as secondary batteries, solar cells, display materials or electronic materials It can be very preferably applied for improving the physical properties using the material.
- a novel dispersant and a method for producing the same which can uniformly disperse various carbon-based materials in various media such as aqueous solvents.
- a dispersant can be obtained through a very simplified manufacturing process using a low-cost raw material such as pitch obtained from the residue of fossil fuel, and thus exhibits excellent dispersibility for the carbon-based material and has a very low manufacturing cost.
- 1A and 1B (enlarged view of the molecular weight 400 to 500 region) is a diagram showing the molecular weight distribution of the pitch analyzed by MALDI-T F mass spectrum.
- 2A and 2B (enlarged view of the molecular weight 400 to 500 region) is a diagram showing the molecular weight distribution of the dispersant obtained in Example 1 analyzed by MALDI-TOF mass spectrum.
- Example 3 is a diagram showing a result of analyzing the pitch and the dispersant of Example 1 by 13C CPMAS NMR, respectively.
- 5 is a diagram showing the molecular weight distribution of the dispersant obtained in Examples 2 to 4 by MALDI-TOF mass spectrum, and comparing the analysis results.
- FIG. 7 shows various examples in the case of using the dispersant of Example in Test Example 2. Visual observation photograph showing the dispersibility of a carbon-based material (graphene flake) to a solvent.
- dispenser refers to any component for uniformly dispersing other components, for example, carbon-based materials such as graphene or carbon nanotubes, in a solvent, an organic solvent, or a liquid medium. can do.
- a composition in which other components to be dispersed, such as a "dispersant” and a carbon-based material, is dispersed in a liquid medium may be referred to as a "dispersion composition", and such a “dispersion composition” may be in solution, slurry, or paste form. Can exist in multiple states.
- such a "dispersion composition” includes a conductive material composition of a secondary battery; Electrodes or conductive compositions applied in the manufacturing process of various batteries, displays or devices; Active material compositions such as secondary batteries; Compositions for producing various polymers or resin composites; Or manufacture of various electronic materials or devices It can be used for various uses such as an ink or paste composition applied in the process, and the use thereof is not particularly limited, and as long as the "dispersant" and the component to be dispersed are included together in the liquid medium, the " And "dispersion composition”.
- polyaromatic hydrocarbon may refer to an aromatic hydrocarbon compound in which at least two, or at least five, benzene rings are bonded and included in a single compound structure.
- polyaromatic hydrocarbon oxide may refer to any compound in which the "polyaromatic hydrocarbon” described above reacts with an oxidant such that at least one oxygen containing functional group is bonded in its chemical structure.
- the oxygen-containing functional group which can be introduced into the "polyaromatic hydrocarbon" by the reaction with the oxidizing agent may be bonded to an aromatic ring such as a hydroxyl group, an epoxy group, a carboxyl group, a nitro group or a sulfone group and includes one or more oxygen in the functional group. It can be any functional group.
- carbon-based material refers to any material mainly containing carbon-carbon bonds, for example, graphene, carbon nanotubes, graphite, carbon black, and C60. Fullerene and other similar fullerene materials or derivatives thereof may be collectively referred to. However, it can be interpreted that "polyaromatic hydrocarbon” or an oxide thereof, which is a main component or main raw material of "dispersant” in the present invention, does not belong to this category of "carbon-based material”.
- a dispersant including a mixture containing a polyaromatic hydrocarbon oxide having a molecular weight of about 300 to 1000 in an amount of about 60% by weight or more is provided. . .
- Pitch discharged from wastes during the refining of fossil fuels such as petroleum or coal is a by-product used for asphalt production, etc., and has a viscous complex form containing a plurality of polyaromatic hydrocarbons having a plurality of aromatic rings. I can stand.
- Specific types, structures, and distributions of the polyaromatic hydrocarbon oxides contained in such a mixture are determined by the pitch of the raw material. The type, its origin, and black may vary depending on the type of oxidant.
- the mixture of polyaromatic hydrocarbon oxides included in the dispersant of the above embodiment has a structure in which at least one oxygen-containing functional group is introduced into the polyaromatic hydrocarbon containing 5 to 30 or 7 to 20 benzene rings, respectively. It includes a plurality of polyaromatic hydrocarbon oxide having, the polyaromatic hydrocarbon oxide in such a mixture has a molecular weight distribution described above, that is, an oxide having a molecular weight of about 300 to 1000, or about 300 to 700 to about 60% by weight or more of the total mixture It has molecular weight distribution which becomes.
- the type of the oxygen-containing functional group may vary depending on the type of oxidant used in the oxidation process such as pitch, etc., for example, at least one selected from the group consisting of hydroxy group, epoxy group, carboxyl group, nitro group and sulfone group. Can be.
- Polyaromatic hydrocarbon oxides satisfying the above-described structural characteristics, molecular weight distribution, and the like, and a mixture thereof, may simultaneously have a hydrophobic ⁇ -domain where aromatic rings are collected and a hydrophilic region by oxygen-containing functional groups bonded to the aromatic ring.
- the hydrophobic ⁇ -domain can interact with the surface of a carbon-based material on which carbon-carbon bonds are formed, such as graphene or carbon nanotubes, and the hydrophilic region is a single graphene or carbon nano. The repulsive force between the tubes can be expressed.
- the dispersing agent of the embodiment including the mixture of the polyaromatic hydrocarbon oxides may be formed of a carbon-based material such as graphene or carbon nanotubes in a liquid medium such as a solvent. It can be present between molecules to uniformly disperse these carbon-based materials. Therefore, it was confirmed that the dispersing agent of one embodiment may exhibit excellent dispersing force to uniformly disperse the carbonaceous material at a higher concentration even when a relatively small amount is used.
- the dispersant of one embodiment may exhibit water solubility in itself due to the presence of the hydrophilic region described above, the dispersing agent may uniformly disperse the carbonaceous material even in an environmentally friendly solvent.
- the dispersant is not only an environmentally friendly solvent, but also acetone,
- the dispersant of one embodiment may be prepared from a raw material such as a low-cost pitch through a simplified oxidation process, the manufacturing cost of the dispersant of the carbon-based material may be greatly lowered and the manufacturing process may be further simplified.
- the dispersing agent of one embodiment overcomes the limitations of the existing dispersing agents, and can uniformly disperse various carbon-based materials in various liquid media at high manufacturing costs at low manufacturing costs. It can be very preferably applied for improving physical properties using carbon-based materials for various products such as display materials or electronic materials.
- the dispersant includes a plurality of types of poly-aromatic hydrocarbons when elemental analysis of the oxide, the oxygen content contained in the entire common compound total element content of from about 12 to 50 increased 0/0, or from about 15 to in it contains 45 weight can be 0 /.
- the oxygen content reflects the degree to which oxygen-containing functional groups are introduced by the oxidation process in the polyaromatic hydrocarbon oxide, and the hydrophilic region described above may be included to an appropriate degree according to the layer of oxygen content.
- the dispersant of one embodiment can be used to uniformly disperse various carbon-based materials in higher concentrations in the solvent.
- the oxygen content may be calculated by elemental analysis of a plurality of polyaromatic hydrocarbon oxides contained in the above-described mixture. That is, when the mixture sample (for example, about 1 mg) is heated to a high temperature of about 90C C, for example, on a thin foil, the temperature rises to about 1500 to 1800 ° C while the foil melts instantly. By such high temperature, gas may be generated from the mixture sample, and the collection and element content may be measured and analyzed. As a result of this elemental analysis, the total elemental content of carbon, oxygen, hydrogen and nitrogen contained in the plurality of polyaromatic hydrocarbon oxides can be measured and analyzed, and the oxygen content with respect to the total elemental content can be obtained.
- Dispersant of one embodiment described above ⁇ can be used for dispersion in a solvent of various carbon-based materials, suitably the high carbon-based material in the solvent It can be used to uniformly disperse the concentration.
- the type of carbon-based material that can be used to improve the dispersibility by using such a dispersant is not particularly limited, for example, graphene, carbon nanotubes, graphite, carbon black, fullerene Materials, derivatives thereof, and the like.
- the dispersant of one embodiment may be suitably used to disperse other various carbon-based materials.
- the process for preparing such a dispersant may comprise oxidizing a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 in the presence of an oxidant.
- the pitch discharged from the residue of the fossil fuel may include a plurality of polyaromatic hydrocarbons, and may have a viscous or powdery complex state.
- the specific type, structure, composition ratio or molecular weight distribution of the polyaromatic hydrocarbon may vary depending on the raw material or the origin of the pitch, the pitch may include, for example, 5 to 50 aromatic rings, for example, a benzene ring. It may include a plurality of polyaromatic hydrocarbons included in the structure, and may include polyaromatic hydrocarbons having a molecular weight of 200 to 1500.
- common compounds including poly aromatic hydrocarbon having a molecular weight of 200 to 1,500 is used as starting material in other implementations the manufacturing method (for example, pitch) is a poly-aromatic hydrocarbons such molecular weight of from about 80 weight 0/0 or more Or about 90 It may be included in a content of weight 0 /.
- pitch is a poly-aromatic hydrocarbons such molecular weight of from about 80 weight 0/0 or more Or about 90 It may be included in a content of weight 0 /.
- polyaromatic hydrocarbons having an excessively large molecular weight are decomposed in the polyaromatic hydrocarbons included in the pitch, and a relatively narrow molecular weight distribution is obtained.
- Mixtures of polyaromatic hydrocarbons having can be obtained.
- polyaromatic hydrocarbons having molecular weights in excess of about 1000, or about 700 can be broken down to small molecular weights.
- At least one oxygen-containing functional group is introduced into the aromatic ring of each polyaromatic hydrocarbon, a mixture containing a plurality of polyaromatic hydrocarbon oxides, that is, a dispersant of one embodiment can be prepared very simply.
- oxidizing agents are not particularly limited, and any oxidizing agent can be used without any limitation as long as it can cause oxidation reaction to introduce oxygen-containing functional groups to aromatic hydrocarbons.
- oxidants include nitric acid (HN0 3 ), sulfuric acid (H 2 S0 4 ), hydrogen peroxide (H 2 O 2 ), ammonium cerium (IV) sulfate; (NH 4 ) 4 Ce ( SO 4 ) 4 ) or ammonium cerium (IV) nitrate (Ammonium cerium (IV) nitrate; (NH 4 ) 2 Ce (N0 3 ) 6 ) and the like, and two or more kinds of mixtures selected from them may be used.
- this oxidation step can be carried out in the solvent, for about 0.5 to 20 hours under a reaction temperature of about 10 to 90 ° C.
- a solution phase oxidant such as sulfuric acid and / or nitric acid
- the ply aromatic A certain amount of the mixture including the hydrocarbons can be added and the oxidation step can be carried out at room temperature, for example about 20 ° C. black or 80 ° C. for about 1 to 12 hours.
- the mixture including polyaromatic hydrocarbons having a molecular weight of 200 to 1500 as a starting material of the production method may be derived from a pitch obtained from a fossil fuel or a product thereof.
- the type, structure or molecular weight distribution of the polyaromatic hydrocarbons may be different from each other.
- a dispersant of one embodiment, which exhibits excellent dispersibility for a carbon-based material may be simply prepared.
- the above-described manufacturing method after the oxidation step may further comprise the step of purifying the resultant to obtain a mixture of a plurality of polyaromatic hydrocarbon oxides, the purification step is a step of centrifuging the result of the oxidation step It may proceed to include.
- a purification step a mixture of polyaromatic hydrocarbon oxides stratifying molecular weight distribution and the like of one embodiment can be obtained more highly and appropriately, and a carbon-based material can be obtained in a liquid medium such as an aqueous solvent by using a dispersant containing the same. It can disperse suitably.
- the carbon-based material according to another embodiment of the invention, the carbon-based material; And it provides a dispersion composition of a carbon-based material comprising a dispersant of one embodiment described above.
- the carbon-based material may be at least one selected from the group consisting of graphene, carbon nanotubes, graphite, carbon black, fullerene-based materials, and derivatives thereof.
- Such a dispersing composition may be in a state in which a high concentration of carbon-based material is dispersed in a liquid medium such as an aqueous solvent more uniformly at a higher concentration by the action of the above-described dispersant.
- the dispersion composition may be used in various applications such as a conductive material composition, an electrode composition, or an active material composition of a secondary battery, depending on the kind of the carbon-based material, the use of other additional components, or the specific composition.
- the state may also be in various states such as solution, slurry, or paste, depending on the kind of carbon-based material, the specific composition, and the like.
- dispersion composition of these various uses, types or states can be obtained by applying the compositions and methods commonly known to those skilled in the art except for using the dispersing agent of the above embodiment, further description thereof will be omitted.
- the above-described dispersion composition may be a liquid composition in which a higher concentration of carbon-based material is uniformly dispersed due to the use of the dispersant of one embodiment. Therefore, the dispersion composition may be very preferably applied for improving physical properties using a carbon-based material for various products such as solar cells, display materials, or electronic materials.
- the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.
- the dispersant of Example 1 was prepared by performing the following oxidation process and purification process on pitch, a petroleum by-product obtained from POSCO. First, 5 to 1.5 g of pitch was added to 75 ml of a mixed solution of sulfuric acid / nitric acid (volume ratio 3: 1), and oxidation reaction was performed at 70 ° C. for about 3.5 hours. Thereafter, the pitch reaction solution subjected to the oxidation reaction was incinerated to room temperature, diluted with about 53 ⁇ 4 B of distilled water, and then centrifuged at about 3500 rpm for 30 minutes. Subsequently, the supernatant was removed, the same amount of distilled water was added and redispersed, followed by centrifugation again under the same conditions to finally recover the precipitate and dried. Through this, the dispersant of Example 1 was prepared.
- the molecular weight distribution of the pitch used as a raw material during the preparation of such a dispersant was analyzed by MALDI-TOF mass spectrum and shown in FIGS. 1A and 1B (an enlarged view of the molecular weight 400 to 500 region), and the dispersant of Example 1
- the molecular weight distribution of was analyzed in the same manner and shown in FIGS. 2A and 2B (an enlarged view of the molecular weight 400 to 500 region).
- This analysis was performed using a MALCM-TOF mass spectrum instrument (Ultraflex II, Bruker), where the pitch or dispersant was added to the matrix. After mixing, drying was performed.
- the pitch was found to include polyaromatic hydrocarbons having a molecular weight of 200 to 1500, especially a large peak at 14Da interval in the enlarged view of FIG. From the detection, it was confirmed that a plurality of polyaromatic hydrocarbons having different numbers of aromatic rings (benzene rings) were connected by aliphatic hydrocarbons. In contrast, referring to FIGS. 1A and 1B (enlarged view), the pitch was found to include polyaromatic hydrocarbons having a molecular weight of 200 to 1500, especially a large peak at 14Da interval in the enlarged view of FIG. From the detection, it was confirmed that a plurality of polyaromatic hydrocarbons having different numbers of aromatic rings (benzene rings) were connected by aliphatic hydrocarbons. In contrast, referring to FIGS.
- the large peaks in the dispersant of Example 1 are present in the polyaromatic hydrocarbons at intervals of 44 Da and 16 D, respectively, which is represented by -COOH or Proof of the presence of oxygen-containing functional groups such as -OH in the form of a mixture of introduced polyaromatic hydrocarbon oxides, oxides having a molecular weight of about 300 to 1000, black to about 300 to 700 is contained in more than 60 weight 0 /. This was confirmed.
- the pitch (top) used as a raw material and the dispersant (bottom) of Example 1 were analyzed by 13C CPMAS NMR (Varian 400MHz S is id-State NMR), respectively, and the results of the analysis were compared with FIG. 3.
- the carbon-derived peak of the aromatic hydrocarbon and the carbon-derived peak of some aliphatic hydrocarbon were confirmed, but the presence of the oxygen-containing functional group was not confirmed.
- NMR analysis of the dispersant of Example 1 confirmed the peak of the oxygen-containing functional group.
- oxygen-containing functional groups were found to be epoxy groups, hydroxyl groups, carboxyl groups, and the like.
- Example 2 which is a petroleum by-product obtained from POSCO, except using a pitch of a sample different from Example 1, and the reaction reaction time was 1 hour (Example 2), 3.5 hours (Example 3) and 7
- the dispersing agents of Examples 2 to 4 were prepared in the same manner as in Example 1, except that the time of Example 4 was changed.
- This dispersant was analyzed by MALDI-TOF mass spectrum in the same manner as in Example 1, and compared with FIG. Referring to FIG. 5, as the oxidation time is increased, the content of the component (polyaromatic hydrocarbon oxide) of about 1000 and black is greater than about 700 in the dispersant, so that the molecular weight is about 300 to 1000 and black is about 300 to 700. It was found that a dispersant in the form of a mixture containing a higher content of polyaromatic hydrocarbon oxides was obtained. Comparative Examples 1 and 2: Dispersant
- Example 4 40.0 1.5 7.8 39.2
- the oxygen content was about 12-50 weight 0 / ⁇ , or about It was confirmed that it was 30-40 weight 0 /.
- Test Example 2 Evaluation of Dispersant of Dispersant in Carbon-Based Materials
- dispersants of Examples 2 to 4 were subjected to peeling and dispersion into grapheme flakes using a high speed homogenizer, tip sonication, and the like for graphite as a carbon-based material, and the dispersing force of the dispersant to the graphene flakes was measured. It evaluated in the same manner as 1.
- CNT or carbon black which is another carbon-based material
- CNT or carbon black which is another carbon-based material
- 10ml of distilled water by weight of the CNT or the carbon black were dissolved in the dispersing agent of Example 1 in 5 to 30 parts by weight 0/0, insert a carbon-based material or carbon black 0.1g of the CNT, batch-type sonication And dispersed.
- the content of the dispersant or the experimental conditions of the equipment used for the dispersion may vary depending on the type of carbon-based material.
- FIGS. 6 (d) to 6 (f) show the results of SEM analysis after dispersing the carbonaceous material in water without using a dispersant
- FIGS. 6 (g) to 6 (i) show the SEM after dispersing using a dispersant.
- MWCNT graphite and carbon nanotubes
- the graphene flake acted as a carbon-based material to evaluate the dispersing power of the dispersant of Example 1.
- the dispersion power was evaluated using various solvents of water, acetone, THF, ethanol and NMP, and the evaluation results are shown in FIG. Shown.
- the precipitate obtained by dispersing and exfoliating Graphite in water using the dispersant of Example 1 above was centrifuged at 1500 rpm to remove the unexfoliated chunks, and the supernatant was recovered by centrifugation at 8000 rpm for 30 minutes. Was dried at 55 ° C. Thereafter, 10 mg of each dried powder was put in 10 ml of various solvents of water, acetone, THF, ethanol or NMP, and sonicated for 1 hour by batch-type sonication to remove the graphite. Dispersed in. Referring to Figure 7, it was confirmed that the carbon-based material of the graphene flakes can be dispersed very uniformly in various solvents when using the dispersant of the embodiment.
- Example 1 the dispersing agent of Example 1 and Comparative Examples 1 and 2 was respectively Was used to compare and evaluate the dispersibility for the carbon-based material in the following manner,
- Example 1 1.0 g of the dispersant of Comparative Examples 1 and 2, 50 ml of distilled water, and 2.5 g of Graphene flake (hereinafter, peeled from Graphite) as a carbonaceous material were mixed, and batch-type sonication The graphene flakes obtained by sonication for 1 hour with the graphite were peeled off.
- This dispersion result is shown in comparison with FIG. Referring to FIG. 9, when the dispersants of Comparative Example 1 (PNE) and Comparative Example 2 (PNS) were used, the graphene flakes did not disperse properly, but existed in the state of being simply floating in water while being stuck to the walls of vias. Was confirmed.
Abstract
Description
Claims
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US14/903,121 US10569243B2 (en) | 2013-08-01 | 2014-07-31 | Dispersing agent, its preparation method and dispersed composition of carbon-based material comprising the same |
EP14833087.1A EP3002313B1 (en) | 2013-08-01 | 2014-07-31 | Dispersant, preparation method therefor, and dispersion composition of carbon-based materials, containing same |
JP2016523676A JP6106339B2 (ja) | 2013-08-01 | 2014-07-31 | 分散剤、その製造方法およびこれを含む炭素系素材の分散組成物 |
CN201480043649.XA CN105452360B (zh) | 2013-08-01 | 2014-07-31 | 分散剂、其制备方法以及包含该分散剂的碳类材料分散组合物 |
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CN105452360B (zh) | 2017-11-17 |
KR20170015443A (ko) | 2017-02-08 |
TWI542643B (zh) | 2016-07-21 |
KR101858719B1 (ko) | 2018-05-16 |
EP3002313A4 (en) | 2017-03-29 |
EP3002313A1 (en) | 2016-04-06 |
KR20150016123A (ko) | 2015-02-11 |
JP2016525589A (ja) | 2016-08-25 |
TW201522519A (zh) | 2015-06-16 |
US10569243B2 (en) | 2020-02-25 |
US20170001161A1 (en) | 2017-01-05 |
EP3002313B1 (en) | 2019-07-31 |
CN105452360A (zh) | 2016-03-30 |
JP6106339B2 (ja) | 2017-03-29 |
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