WO2022205580A1 - Noir de carbone en bloc solide ultrafin instantanément soluble, procédé pour sa préparation et applications correspondante - Google Patents

Noir de carbone en bloc solide ultrafin instantanément soluble, procédé pour sa préparation et applications correspondante Download PDF

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Publication number
WO2022205580A1
WO2022205580A1 PCT/CN2021/094466 CN2021094466W WO2022205580A1 WO 2022205580 A1 WO2022205580 A1 WO 2022205580A1 CN 2021094466 W CN2021094466 W CN 2021094466W WO 2022205580 A1 WO2022205580 A1 WO 2022205580A1
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Prior art keywords
carbon black
instant
solid block
emulsion
water
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PCT/CN2021/094466
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English (en)
Chinese (zh)
Inventor
石瑜博
艾丽
候礼文
朱亚伟
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苏州大学
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Publication of WO2022205580A1 publication Critical patent/WO2022205580A1/fr

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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
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • 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
    • C09C1/58—Agglomerating, pelleting, or the like by wet methods
    • 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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • 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
    • C09C3/10—Treatment with macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes

Definitions

  • the invention relates to a preparation technology of a carbon-based material, in particular to the preparation of an environment-friendly solid block carbon black, so as to solve the dust pollution of the existing powdery carbon black.
  • Carbon black is an amorphous carbon, a light, loose, and extremely fine black powder with a very large surface area. Carbon black has the advantages of low price and wide range of raw material sources. However, carbon black has serious carbon black dust pollution in the process of production, processing, packaging and transportation, which not only deteriorates the production environment, but also seriously affects the health of production workers. In the application process of carbon black powder, there are also problems of carbon black dust pollution and deterioration of the production environment, and according to the application requirements, powder carbon black needs to be emulsified and dispersed, which is extremely inconvenient to use.
  • a carbon black compressor and a block carbon black processing device are used to make block carbon black by mechanical compression (ZL200520033701.1) or extrusion (ZL201820897798.8) to solve the existing problems.
  • ZL200520033701.1 mechanical compression
  • ZL201820897798.8 extrusion
  • there are still shortcomings such as the need to emulsify and disperse powder carbon black.
  • the purpose of the present invention is to provide a kind of instant ultrafine solid block carbon black, which can directly use the carbon black conveniently, avoid the emulsification and dispersion when the carbon black is used, and reduce the environmental pollution caused by the carbon black dust.
  • An instant type ultrafine solid block carbon black comprising the following steps: mixing powdery carbon black, an auxiliary agent and water and grinding to obtain a carbon black emulsion; after drying the carbon black emulsion, an instant type carbon black emulsion is obtained Ultrafine solid block carbon black.
  • the invention discloses an ultra-fine carbon black instant solution, and a preparation method thereof comprises the following steps: mixing powdery carbon black, auxiliary agents and water, and then grinding to obtain a carbon black emulsion; and drying the carbon black emulsion to obtain an instant solution type ultrafine solid block carbon black; mixing instant ultrafine solid block carbon black with water to obtain a superfine carbon black instant solution.
  • the invention discloses a conductive fabric.
  • the preparation method comprises the following steps: mixing powdery carbon black, auxiliary agents and water and then grinding to obtain a carbon black emulsion; and drying the carbon black emulsion to obtain an instant ultrafine solid block carbon black; mixing instant ultrafine solid block carbon black with water to obtain a superfine carbon black quick solution; padding the fabric with the superfine carbon black quick solution and drying to obtain a conductive fabric.
  • powdery carbon black is a conventional product, which is one or a mixture of pigment carbon black, conductive carbon black and rubber carbon black.
  • the adjuvant includes a surfactant and a surfactant, wherein the surfactant is an anionic surfactant, a nonionic surfactant; preferably, the adjuvant is an anionic surfactant, a nonionic surfactant, a Active agent composition, more preferably, the auxiliary agent is composed of anionic surfactant, nonionic surfactant and surfactant with a mass ratio of 1:(0.5-0.8):(0.02-0.1).
  • the anionic surfactant is a mixture of formaldehyde condensate of sodium methylnaphthalene sulfonate and sodium lignosulfonate;
  • the nonionic surfactant is aliphatic amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether , a mixture of polyether polyols;
  • the surfactant is an amphiphilic surfactant.
  • the forces between carbon black particles include van der Waals force, electrostatic attraction and steric resistance. The van der Waals force between particles increases with the increase of particle size and decreases with the increase of the distance between particles.
  • the electrostatic attraction between carbon black particles can be reduced by adding a dispersant, and the stable dispersion of carbon black in an aqueous system can be promoted by using an effective dispersion method.
  • the key technology is to select an appropriate dispersant.
  • the additive defined in the present invention increases the distance between carbon black particles, thereby preventing the aggregation of carbon black particles, changing the surface charge of the carbon black particles, and preventing the aggregation of carbon black particles through electrostatic repulsion.
  • the anchoring group is adsorbed to the surface of carbon black particles, forming a large number of shells or enhancing the charge on the surface of carbon black, effectively preventing the flocculation and coagulation of the carbon black dispersion system.
  • grinding is carried out in a conventional zirconia ball milling device, the specific operation of grinding is the prior art, and the grinding time is preferably 2 to 4 hours to obtain a carbon black emulsion with a carbon black particle size not higher than 200 nm.
  • drying the carbon black emulsion is a conventional technique, and the carbon black emulsion can be placed in a container and dried to obtain solid block carbon black.
  • the container is a conventional product, which can store the carbon black emulsion; drying is a conventional drying method, such as placing the carbon black liquid in a conventional container and drying it at 100-120 ° C for 1-4 hours to obtain solid lump carbon black.
  • the instant ultra-fine solid block carbon black is mixed with water, and stirred at 700-800 rpm for 2-8 minutes to obtain the ultra-fine carbon black quick solution, which is the creativity of the present invention.
  • the powdery carbon black of the existing product is ground and then dried to obtain the lumpy carbon black, which solves the problem of powder pollution in the transportation and application of the powdery carbon black in the prior art.
  • the lumpy carbon black of the present invention Black can be instantly dissolved in water, and in the formed instant solution, the particle size of carbon black particles is small, and there is no agglomeration phenomenon, which is a technical effect that cannot be achieved by the existing technology, and significantly improves the environment in the application field of carbon black and reduces dust pollution. .
  • the fabric can be polyester spandex fabric; the rolling ratio of padding is 85%; the specific padding and drying are conventional techniques.
  • the method for preparing instant ultrafine solid block carbon black in the present invention is as follows.
  • the carbon black solution is continuously ground in a zirconia grinding device to obtain a carbon black emulsion.
  • the mass sum of powdered carbon black, additives and water is 100%, wherein 10-40% of powdered carbon black, 3-15% of additives, and water are the balance;
  • the ratio is 1:(0.5 ⁇ 0.8):(0.02 ⁇ 0.1) of anionic surfactant, nonionic surfactant and surfactant.
  • the instant ultra-fine solid block carbon black disclosed in the invention has ultra-fine self-dispersion performance, and the solid block carbon black is mixed with water to prepare an ultra-fine self-dispersing carbon black liquid with a carbon black particle size not higher than 200 nm. Then, it is applied to the surface of the material by conventional methods such as padding and coating, and then dried to obtain a carbon black modified material. Therefore, the present invention discloses the application of the above-mentioned instant ultrafine solid block carbon black in the preparation of carbon black modified materials.
  • the invention provides a preparation technology of ultra-fine solid block carbon black, which integrates "no dust pollution, no waste water discharge, rapid dissolution, and ultra-fine nano-particles", and solves the problems of carbon black dust pollution and easy agglomeration of water-based carbon black.
  • powdered carbon black can be added with additives and ground into a certain concentration of nano-carbon black emulsion, and then dried to prepare solid block carbon black, and solid block carbon black has the characteristics of rapid dissolution, which can be easily applied to carbon black Modification of other materials to obtain excellent antistatic properties and electrical conductivity.
  • the present invention has the following advantages compared with the prior art.
  • the prepared block carbon black can be blended with other materials to obtain excellent application performance.
  • Fig. 1 is the particle size test result of the carbon black emulsion prepared in Example 1.
  • Figure 2 is the particle size test result of the carbon black emulsion prepared in Example 2.
  • Example 4 is the particle size test result of the carbon black emulsion prepared in Example 4.
  • Example 5 is the particle size test result of the carbon black emulsion prepared in Example 5.
  • FIG. 6 is the particle size test result of the carbon black emulsion prepared in Example 6.
  • Example 8 is the particle size test result of the instant carbon black liquid prepared in Example 8.
  • Example 10 is the particle size test result of the instant carbon black liquid prepared in Example 10.
  • Example 11 is the particle size test result of the instant carbon black liquid prepared in Example 11.
  • Example 13 is the morphology of carbon black in the carbon black emulsion prepared in Example 4 (transmission electron microscope, 500 nm).
  • Example 14 is the morphology of carbon black in the carbon black emulsion prepared in Example 4 (transmission electron microscope, 200 nm).
  • Figure 15 is a photo of the solid block carbon black prepared in Example 4.
  • All raw materials in the embodiment are commercially available products, such as commercially available carbon black 15F (Anhui Heiyu Pigment New Materials Co., Ltd.), commercially available dispersant MF, commercially available sodium lignosulfonate-N, commercially available octadecylamine Polyoxyethylene ether (EO is 15, 20, 30 respectively), commercially available peregal O (EO is 15, 20, 30 respectively), commercially available polyether polyol HSH-210, commercially available dispersant AKN-2290, Foshan City Qianyou Chemical Co., Ltd., commercially available dispersant RQT-FS, and Henan Richite Chemical Co., Ltd. are all industrial grades.
  • the drying of the bulk carbon black prepared from the carbon black liquid is a conventional method.
  • the carbon black liquid is placed in a suitable container and dried at 100 to 120 ° C for 1 to 4 hours. In the following example, 110 ° C is selected to be dried for 2 hours to obtain Solid lump carbon black.
  • the drying of the prepared conductive fabric is a conventional method, such as padding the instant carbon black liquid on the fabric and drying at 140° C. for 5 minutes.
  • composition (g) of the raw materials is as follows.
  • the carbon black solution was prepared by premixing 1 g of polyether polyol HSH-210, 14 g of dispersant RQT-FS and 8700 g of water. The carbon black solution was continuously ground in a zirconia grinding device for 2.5 hours to obtain a carbon black emulsion. The above nanometer carbon black emulsion is placed in a container and dried to obtain solid block carbon black.
  • the carbon black solution was prepared by pre-mixing gram of polyether polyol HSH, 30 grams of dispersant RQT-FS and 6000 grams of water, with a total of 1000 grams of abrasive.
  • the carbon black solution was continuously ground in a zirconia grinding device for 3 hours to obtain a carbon black emulsion.
  • the above carbon black emulsion is placed in a container and dried to obtain solid block carbon black.
  • the above-mentioned carbon black emulsion was placed in a container, and the solid block carbon black was obtained by drying, and 15 grams of solid block carbon black (prepared in Example 4) was mixed with 85 grams of water, and stirred with a stirrer at 800 rpm. After 5 minutes, there were particles visible to the naked eye, and the mixture was stirred for another 15 minutes to obtain a carbon black liquid. Trace particles were also seen, and the measured particle size was 286.88 nm.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Polyester spandex fabric (gram weight: 304 g/square meter) was pad-rolled with the carbon black solution, the rolling ratio was controlled to be 85%, and dried to obtain a conductive polyester spandex fabric.
  • Particle size of instant carbon black liquid measured on a nanometer particle sizer, and D50 is used to represent the particle size, and the unit is nm.
  • Morphology of carbon black The morphology of instant carbon black liquid is tested by transmission electron microscope, and the morphology of spherical carbon black can be observed.
  • the sheet resistance of the fabric was tested on a digital four-point probe tester. The test conditions were temperature 20 °C, humidity 65%, and the sample was equilibrated for 24 h.
  • the test results of the particle size of the instant carbon black liquid are shown in Figures 1 to 12. It can be seen that the D50 particle sizes of the nano-carbon black emulsions of Examples 1 to 6 are 131.49, 111.30, 120.09, 141.10, 154.59 and 140.02 nm, respectively; the D50 particle sizes of the nano-carbon black liquids of Examples 7 to 12 are respectively are 151.63, 142.10, 166.29, 180.37, 184.59 and 164.86nm. This shows that the solid block carbon black prepared by the solution disclosed in the present technology can have excellent water solubility and instant solubility, and the particle size of the dissolved carbon black liquid is not higher than 200 nm.
  • the ground carbon black particles will aggregate, especially when they are dried and then dispersed, the particles aggregate obviously, resulting in a large particle size, exceeding the nanometer level.
  • the present invention effectively solves this problem, and the prepared block carbon black Black not only has strong instant solubility, but also in the dispersed carbon black liquid, the particle size of carbon black particles increases very little.
  • Figure 13 and Figure 14 are the carbon black morphology (transmission electron microscope) of the carbon black emulsion prepared in Example 4. It can be seen that the carbon black morphology in the prepared nano-carbon black emulsion is mostly nano-scale spherical structure (attached A) in Fig. 13, a small amount of nano-scale sheet-like structures can also be seen (B in Fig. 13), such nano-scale sheet-like structures can be clearly observed (Fig. 14); Fig. 15 shows the implementation The photo of the solid lump carbon black prepared in Example 4, compared with the powdery carbon black without grinding modification, has no dust pollution, and there is obvious orientation in the lump carbon black.
  • polyester spandex fabrics prepared from Examples 7 to 12 have been tested for electrical conductivity, and the sheet resistances of the polyester spandex fabrics are 0.0751, 0.0715, 0.0782, 0.0633, 0.0681 and 0.0565 M ⁇ , respectively, with excellent electrical conductivity.
  • the invention discloses a preparation method of instant ultra-fine solid block carbon black, which can not only prepare solid block carbon black without dust pollution, but also When used, it has the advantages of rapid dissolution and ultra-fine carbon black particle size, which significantly improves the environmental pollution caused by powder carbon black, has the effect of extremely simple use, and can meet the performance requirements of water-based carbon black applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un noir de carbone en bloc solide ultrafin instantanément soluble, un procédé pour sa préparation et des applications correspondantes. Du noir de carbone en poudre, un tensioactif anionique, un tensioactif non ionique, un tensioactif et de l'eau sont prémélangés et ensuite broyés avec de l'oxyde de zirconium pour produire une nano-émulsion de noir de carbone, la grosseur de particule du noir de carbone n'étant pas supérieure à 200 nm ; l'émulsion est cuite et moulée pour produire le noir de carbone en bloc solide. La solution technique décrite ci-dessus présente l'avantage d'être exempte de pollution de la poussière, peut être utilisée de manière pratique, peut être rapidement dissoute en noir de carbone en bloc, présente d'excellentes performances d'application, est appliquée à la surface d'un matériau à l'aide de procédés classiques tels que le garnissage et le revêtement et est ensuite cuite pour produire un matériau modifié par le noir de carbone.
PCT/CN2021/094466 2021-03-29 2021-05-18 Noir de carbone en bloc solide ultrafin instantanément soluble, procédé pour sa préparation et applications correspondante WO2022205580A1 (fr)

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CN202110336706.5A CN113122028B (zh) 2021-03-29 2021-03-29 一种速溶型超细固体块状炭黑及其制备方法和应用
CN202110336706.5 2021-03-29

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CN114686023A (zh) * 2022-05-07 2022-07-01 山东耐斯特炭黑有限公司 一种塑料母粒色浆用高色素炭黑的生产方法

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