WO2023097543A1 - 一种白炭黑的改性方法 - Google Patents

一种白炭黑的改性方法 Download PDF

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WO2023097543A1
WO2023097543A1 PCT/CN2021/134739 CN2021134739W WO2023097543A1 WO 2023097543 A1 WO2023097543 A1 WO 2023097543A1 CN 2021134739 W CN2021134739 W CN 2021134739W WO 2023097543 A1 WO2023097543 A1 WO 2023097543A1
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Prior art keywords
coupling agent
silane coupling
liquid
carbon black
white carbon
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PCT/CN2021/134739
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English (en)
French (fr)
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陈南飞
卢爱平
王明贺
陈辰
陈家树
史彤
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无锡恒诚硅业有限公司
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Priority to PCT/CN2021/134739 priority Critical patent/WO2023097543A1/zh
Priority to CN202180004230.3A priority patent/CN114302918B/zh
Publication of WO2023097543A1 publication Critical patent/WO2023097543A1/zh

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    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • 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
    • 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
    • C09C3/12—Treatment with organosilicon compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • This application relates to the field of white carbon black, in particular to a method for modifying white carbon black.
  • silica has gradually replaced carbon black in rubber products due to its excellent performance such as microstructure and surface properties.
  • modified white carbon black reinforced rubber tire material is made of solution polystyrene butadiene rubber, rare earth butadiene rubber, butadiene rubber, modified white carbon black It is prepared from carbon black, starch nanocrystals, cellulose acetate, calcium oxide, anti-slip agent, nano zinc oxide, stearic acid, anti-aging agent, accelerator, and vulcanizing agent, and the preparation of the modified white carbon black reinforced rubber tire material
  • the steps include: preparation of modified white carbon black, mixing of processing aids, mixing and kneading of rubber, mixing and heating of additives and rubber, and vulcanization molding.
  • the dispersion of silica in rubber is improved, and then the dispersion of silica is further enhanced by adding and mixing with processing aids in batches, reducing internal friction and fatigue heat generation Decrease, the ability to resist external mechanical force is enhanced, and the wear resistance and aging resistance are enhanced, thereby prolonging the service life of the rubber material.
  • CN113024913A discloses a rubber composition system for detecting the degree of reinforcement of white carbon black and its mixing method and application.
  • the rubber composition system includes the following components in parts by weight: 100 parts of solution-polymerized styrene-butadiene rubber, environmental protection oil 30-45 parts, 1.0-5.0 parts of zinc oxide, 1.0-3.0 parts of stearic acid, 2.0-5.0 parts of vulcanization accelerator, 0.5-2.0 parts of sulfur, 0-70 parts of white carbon black; rubber with different amounts of white carbon black
  • the added amount of white carbon black is increased from 0 parts, the increasing gradient is 10.0-30.0 parts, and the amount of silane coupling agent is appropriate.
  • the rubber composition system is used as a standard formula for testing the degree of reinforcement of silica in rubber. Its extremely simple formula composition and specific proportions of each component make it scientific and effective for evaluating the reinforcing performance.
  • the present application provides a method for modifying white carbon black, which solves the problem of poor loss performance and mechanical properties of the obtained rubber material when white carbon black is used as a reinforcing agent for rubber materials.
  • the application provides a modification method of white carbon black, the modification method comprising:
  • step (2) Reacting the first liquid obtained in step (1) with lignosulfonate under a protective atmosphere, and then obtaining modified white carbon black through solid-liquid separation.
  • the modification method provided by this application realizes the modification of white carbon black by using a specific modification reagent and a reasonable preparation process, so that the prepared white carbon black has good surface properties and dispersibility. At the same time, when it is used as a rubber reinforcing agent, it can significantly improve the loss performance and mechanical properties of the obtained rubber material.
  • the lignosulfonate may be one or a combination of at least two of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate or magnesium lignosulfonate.
  • the silica dispersion in step (1) is obtained by ultrasonically dispersing silica in an alcohol solution.
  • the alcohol liquid may be one or a combination of at least two of methanol, ethanol, ethylene glycol or glycerin.
  • the content of silica in the silica dispersion described in step (1) is 55-70%, for example, it can be 55%, 56%, 57%, 58%, 59%, 60% %, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, but not limited to the listed values, other unlisted combinations within this range are also Be applicable.
  • the amount of glycolic acid added in step (1) is 7-15% of the mass of silica in the first liquid, for example, it can be 7%, 7.2%, 7.4%, 7.6% , 7.8%, 8%, 8.2%, 8.4%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11 %, 11.2%, 11.4%, 11.6%, 11.8%, 12%, 12.2%, 12.4%, 12.6%, 12.8%, 13%, 13.2%, 13.4%, 13.6%, 13.8%, 14%, 14.2%, 14.4%, 14.6%, 14.8% or 15%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mass concentration of glycolic acid in step (1) is 20-30%, such as 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the silane coupling agent in step (1) includes one or at least two of silane coupling agent KH-550, silane coupling agent KH-560 or silane coupling agent KH-570 The combination.
  • the amount of the silane coupling agent added in step (1) is 15-25% of the mass of silica in the first liquid, for example, it can be 15%, 15.5%, 16%, 16.5%, 17% , 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5% or 25%, etc., But not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mixing in step (1) is carried out under high temperature and high pressure.
  • the mixed pressure in step (1) is 40-80MPa, such as 40MPa, 42MPa, 44MPa, 46MPa, 48MPa, 50MPa, 52MPa, 54MPa, 56MPa, 58MPa, 60MPa, 62MPa, 64MPa, 66MPa, 68MPa, 70MPa, 72MPa, 74MPa, 76MPa, 78MPa or 80MPa, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • 40MPa, 42MPa, 44MPa, 46MPa, 48MPa, 50MPa, 52MPa, 54MPa, 56MPa, 58MPa, 60MPa, 62MPa, 64MPa, 66MPa, 68MPa, 70MPa, 72MPa, 74MPa, 76MPa, 78MPa or 80MPa, etc. but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mixing temperature in step (1) is 150-200°C, such as 150°C, 152°C, 154°C, 156°C, 158°C, 160°C, 162°C, 164°C, 166°C, 168°C , 170°C, 172°C, 174°C, 176°C, 178°C, 180°C, 182°C, 184°C, 186°C, 188°C, 190°C, 192°C, 194°C, 196°C, 198°C or 200°C, etc., But not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mixing time in step (1) is 0.5-6h, such as 0.5h, 0.6h, 0.7h, 0.8h, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h , 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8 h or 6h, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the addition amount of the lignosulfonate in step (2) is 1.5-2 times the mass of the silane coupling agent in the first liquid, for example, it can be 1.5 times, 1.52 times, 1.54 times. times, 1.56 times, 1.58 times, 1.6 times, 1.62 times, 1.64 times, 1.66 times, 1.68 times, 1.7 times, 1.72 times, 1.74 times, 1.76 times, 1.78 times, 1.8 times, 1.82 times, 1.84 times, 1.86 times, 1.88 times, 1.9 times, 1.92 times, 1.94 times, 1.96 times, 1.98 times or 2 times, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the protective atmosphere in step (2) includes nitrogen or inert gas.
  • the inert gas may be helium, neon or argon, etc.
  • reaction in step (2) is carried out under high shear treatment.
  • the rate of the high shear treatment is 100-200r/min, such as 100r/min, 105r/min, 110r/min, 115r/min, 120r/min, 125r/min, 130r/min, 135r /min, 140r/min, 145r/min, 150r/min, 155r/min, 160r/min, 165r/min, 170r/min, 175r/min, 180r/min, 185r/min, 190r/min, 195r/min Or 200r/min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the end point of the high shear treatment is a slurry temperature of 80-100°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, etc.
  • the listed combinations are also applicable.
  • the temperature of the slurry at the beginning of the reaction in step (2) is ⁇ 30°C, for example, it can be 30°C, 28°C, 26°C, 24°C, 22°C, 20°C, 18°C, 16°C °C, 14 °C, 12 °C, or 10 °C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the modification method includes:
  • the silica dispersion is obtained by ultrasonically dispersing silica in an alcohol solution; the silica dispersion
  • the content of white carbon black in the liquid is 55-70%; the addition of the glycolic acid is 7-15% of the mass of white carbon black in the first liquid;
  • the silane coupling agent includes silane coupling agent KH- 550.
  • step (2) react the first liquid that step (1) obtains with lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition amount of described lignosulfonate is the 1.5-2 times of the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere includes nitrogen or inert gas;
  • the reaction is carried out under high shear treatment; the speed of the high shear treatment is 100-200r/ min; the end point of the high shear treatment is a slurry temperature of 80-100°C; the temperature of the slurry at the beginning of the reaction is ⁇ 30°C.
  • the modification method provided by this application realizes the modification of white carbon black by using specific reagents such as silane coupling agent and lignin sulfonate in combination with a specific high-shear process, and at the same time improves the white carbon black. Surface area and dispersibility of carbon black.
  • modified white carbon black When used as a reinforcing material, it can significantly improve the mechanical properties and wear resistance of rubber materials.
  • the loss factor at 0°C is ⁇ 0.81.
  • This embodiment provides a modification method of white carbon black, the modification method comprising:
  • silica dispersion, glycolic acid (mass concentration is 25%), silane coupling agent (silane coupling agent KH-550) are mixed to obtain the first liquid;
  • the silica dispersion is white carbon Black is obtained by ultrasonic dispersion in ethanol;
  • the content of silica in the silica dispersion is 62%;
  • the addition of the glycolic acid is 11% of the mass of silica in the first liquid;
  • the addition of the silane coupling agent is 20% of the mass of silica in the first liquid;
  • the mixing is carried out under high temperature and high pressure; the mixing pressure is 60MPa; the mixing temperature is 170°C;
  • the mixing time is 2h;
  • step (2) react the first liquid that step (1) obtains with sodium lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition amount of described sodium lignosulfonate is 1.7 times of the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere is nitrogen;
  • the reaction is carried out under high shear treatment;
  • the speed of the high shear treatment is 125r/min;
  • the end point of the treatment was a slurry temperature of 95°C; the temperature of the slurry at the beginning of the reaction was 30°C.
  • This embodiment provides a modification method of white carbon black, the modification method comprising:
  • silica dispersion, glycolic acid (mass concentration is 20%), silane coupling agent (silane coupling agent KH-560) are mixed to obtain the first liquid;
  • the silica dispersion is white carbon Black is obtained by ultrasonic dispersion in methanol;
  • the content of silica in the silica dispersion is 55%;
  • the addition of the glycolic acid is 15% of the mass of silica in the first liquid;
  • the addition of the silane coupling agent is 15% of the mass of silica in the first liquid;
  • the mixing is carried out under high temperature and high pressure; the mixing pressure is 40MPa;
  • the mixing temperature is 200°C;
  • the mixing time is 0.5h;
  • step (2) react the first liquid that step (1) obtains with potassium lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition amount of described potassium lignosulfonate is 1.5 times of the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere is helium;
  • the reaction is carried out under high shear treatment;
  • the speed of the high shear treatment is 200r/min;
  • the end point of the cutting treatment was a slurry temperature of 80°C; the temperature of the slurry was 20°C at the beginning of the reaction.
  • This embodiment provides a modification method of white carbon black, the modification method comprising:
  • silica dispersion, glycolic acid (mass concentration is 30%), silane coupling agent (silane coupling agent KH-570) are mixed to obtain the first liquid;
  • the silica dispersion is white carbon Black is obtained by ultrasonic dispersion in ethanol;
  • the content of silica in the silica dispersion is 70%;
  • the addition of the glycolic acid is 7% of the mass of silica in the first liquid;
  • the addition of the silane coupling agent is 25% of the mass of silica in the first liquid;
  • the mixing is carried out under high temperature and high pressure; the mixing pressure is 80MPa;
  • the mixing temperature is 150°C;
  • the mixing time is 1h;
  • step (2) react the first liquid that step (1) obtains with sodium lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition amount of described sodium lignosulfonate is 2 times the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere is nitrogen;
  • the reaction is carried out under high shear treatment;
  • the speed of the high shear treatment is 100r/min;
  • the high shear The end point of the treatment was a slurry temperature of 100°C; the temperature of the slurry at the beginning of the reaction was 25°C.
  • This embodiment provides a modification method of white carbon black, the modification method comprising:
  • silica dispersion, glycolic acid (mass concentration is 27%), silane coupling agent (alkane coupling agent KH-570) are mixed to obtain the first liquid;
  • the silica dispersion is white carbon Black is obtained by ultrasonic dispersion in glycerol; the content of silica in the silica dispersion is 67%; the amount of glycolic acid added is 10% of the mass of silica in the first liquid;
  • the addition amount of the silane coupling agent is 22% of the mass of the silica in the first liquid;
  • the mixing is carried out under high temperature and high pressure; the mixing pressure is 67MPa; the mixing temperature is 177°C;
  • the mixing time is 0.8h;
  • step (2) react the first liquid that step (1) obtains with calcium lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition of described calcium lignosulfonate is 1.6 times of the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere is helium;
  • the reaction is carried out under high shear treatment;
  • the speed of the high shear treatment is 168r/min;
  • the end point of the cutting process was a slurry temperature of 86°C; the temperature of the slurry at the beginning of the reaction was 22°C.
  • This embodiment provides a modification method of white carbon black, the modification method comprising:
  • silica dispersion, glycolic acid (mass concentration is 23%), silane coupling agent (silane coupling agent KH-550) are mixed to obtain the first liquid;
  • the silica dispersion is white carbon Black is obtained by ultrasonic dispersion in ethylene glycol; the content of silica in the silica dispersion is 58%; the amount of glycolic acid added is 9% of the mass of silica in the first liquid;
  • the addition amount of the silane coupling agent is 17% of the mass of the silica in the first liquid;
  • the mixing is carried out under high temperature and high pressure; the mixing pressure is 44MPa; the mixing temperature is 158°C;
  • the mixing time is 1.2h;
  • step (2) react the first liquid that step (1) obtains with magnesium lignosulfonate under protective atmosphere, obtain modified white carbon black through solid-liquid separation afterwards;
  • the addition amount of described magnesium lignosulfonate is 1.9 times of the quality of the silane coupling agent in the first liquid;
  • the protective atmosphere is argon;
  • the reaction is carried out under high shear treatment;
  • the speed of the high shear treatment is 126r/min;
  • the end point of the cutting process was a slurry temperature of 92°C; the temperature of the slurry at the beginning of the reaction was 25°C.
  • Example 1 The difference from Example 1 is only that glycolic acid is replaced by an equivalent amount of sulfuric acid.
  • Example 1 The difference from Example 1 is only that the mixing is carried out at normal temperature and pressure.
  • Example 1 The difference from Example 1 is only that lignosulfonate is replaced by sodium dodecylbenzenesulfonate.
  • Example 1 The difference from Example 1 is only that the high-shear treatment is replaced by isothermal and constant-rate stirring.
  • Example 1 The difference from Example 1 is only that the addition positions of the silane coupling agent and sodium lignosulfonate are exchanged, that is, the sodium lignosulfonate is added first, and then the silane coupling agent is added in sequence.
  • the nitrogen adsorption method is used to determine the specific surface area of white carbon black; Oil absorption value of carbon black; rubber mixing according to HGT 2404-2020 "Identification of Precipitated Hydrated Silica in Rubber Compounding Agent in SBR”; according to GB/T528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber "Test the stress-strain characteristics; test the Mooney viscosity according to GB/T1232.1 "Determination of Unvulcanized Rubber with a Disc Shear Viscometer Part One: Determination of Mooney Viscosity".
  • the modification method provided by the application realizes the modification of white carbon black by using a specific modification reagent and a reasonable preparation process, so that the prepared white carbon black Has good surface properties and dispersibility. At the same time, when it is used as a rubber reinforcing agent, it can significantly improve the loss performance and mechanical properties of the obtained rubber material.

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Abstract

一种白炭黑的改性方法，所述改性方法包括：(1)将白炭黑分散液、羟基乙酸、硅烷偶联剂进行混合得到第一液；(2)将步骤(1)得到的第一液与木质素磺酸盐在保护气氛下进行反应，之后经固液分离得到改性白炭黑。该改性方法通过采用特定的改性试剂和合理的制备过程相配合，实现了白炭黑的改性，使得制备得到的白炭黑具有良好的表面性能和分散性。同时其作为橡胶补强剂使用时可以显著提升所得橡胶材料的损耗性能和力学性能。

Description

一种白炭黑的改性方法 技术领域
本申请涉及白炭黑领域，具体涉及一种白炭黑的改性方法。
背景技术
目前，白炭黑由于其优异的使用性能如微观结构和表面性能等，已逐渐取代炭黑在橡胶制品进行使用。
如CN111171410A公开了一种改性白炭黑增强橡胶轮胎材料及其制备方法，所述改性白炭黑增强橡胶轮胎材料由溶聚丁苯胶、稀土丁二橡胶、顺丁橡胶、改性白炭黑、淀粉纳米晶、醋酸纤维素、氧化钙、防滑剂、纳米氧化锌、硬脂酸、防老剂、促进剂、硫化剂制备而成，所述改性白炭黑增强橡胶轮胎材料的制备步骤包括：改性白炭黑的制备、加工助剂的混合、橡胶的混合开炼、助剂与橡胶的混合加热成型、硫化成型。通过加入改性的白炭黑，提高了白炭黑在橡胶中的分散性，之后通过与加工助剂分批添加混合的方式进一步增强了白炭黑的分散性，内摩擦减少，疲劳生热下降，抵抗外界机械力的能力增强，耐磨性、抗老化性增强，从而延长了橡胶材料的使用寿命。
CN113024913A公开了一种白炭黑补强程度检测的橡胶组合物体系及其混炼方法和应用，该橡胶组合物体系包括如下重量份数的各组分：溶聚丁苯橡胶100份，环保油30-45份，氧化锌1.0-5.0份，硬脂酸1.0-3.0份，硫化促进剂2.0-5.0份，硫磺0.5-2.0份，白炭黑0-70份；不同白炭黑添加量的橡胶组合物体系，白炭黑的加入量从0份递增，递增梯度为10.0-30.0份，硅烷偶联剂适量。该橡胶组合物体系作为白炭黑在橡胶中补强程度测试使用的标准配方，其极简的配方构成、特定的各组份比例使其具有科学有效的补强性能评估作用。
然而，当前白炭黑在作为橡胶补强材料使用时仍存在补强性能差，效果提升不明显的问题。
发明内容
本申请提供了一种白炭黑的改性方法，解决了目前白炭黑作为橡胶材料的补强剂使用时，所得橡胶材料的损耗性能和力学性能较差的问题。
本申请提供了一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸、硅烷偶联剂进行混合得到第一液；
(2)将步骤(1)得到的第一液与木质素磺酸盐在保护气氛下进行反应，之后经固液分离得到改性白炭黑。
本申请提供的改性方法，通过采用特定的改性试剂和合理的制备过程相配合，实现了白炭黑的改性，使得制备得到的白炭黑具有良好的表面性能和分散性。同时其作为橡胶补强剂使用时可以显著提升所得橡胶材料的损耗性能和力学性能。
本申请中，所述木质素磺酸盐可以是木质素磺酸钠、木质素磺酸钾、木质素磺酸钙或木质素磺酸镁中的1种或至少2种的组合。
作为本申请优选的技术方案，步骤(1)所述白炭黑分散液为白炭黑在醇液中进行超声分散得到。所述醇液可以是甲醇、乙醇、乙二醇或丙三醇等的1种或至少2种的组合。
作为本申请优选的技术方案，步骤(1)所述白炭黑分散液中白炭黑的含量为55-70％，例如可以是55％、56％、57％、58％、59％、60％、61％、62％、63％、64％、65％、66％、67％、68％、69％或70％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，步骤(1)所述羟基乙酸的添加量为所述第一液中白炭黑质量的7-15％，例如可以是7％、7.2％、7.4％、7.6％、7.8％、8％、8.2％、8.4％、8.6％、8.8％、9％、9.2％、9.4％、9.6％、9.8％、10％、10.2％、10.4％、10.6％、10.8％、11％、11.2％、11.4％、11.6％、11.8％、12％、12.2％、12.4％、12.6％、12.8％、13％、13.2％、13.4％、13.6％、13.8％、14％、14.2％、14.4％、14.6％、14.8％或15％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
优选地，步骤(1)所述羟基乙酸的质量浓度为20-30％，例如可以是20％、21％、22％、23％、24％、25％、26％、27％、28％、29％或30％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，步骤(1)所述硅烷偶联剂包括硅烷偶联剂KH-550、硅烷偶联剂KH-560或硅烷偶联剂KH-570中的1种或至少2种的组合。
优选地，步骤(1)所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的 15-25％，例如可以是15％、15.5％、16％、16.5％、17％、17.5％、18％、18.5％、19％、19.5％、20％、20.5％、21％、21.5％、22％、22.5％、23％、23.5％、24％、24.5％或25％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，步骤(1)所述混合在高温高压下进行。
优选地，步骤(1)所述混合的压强为40-80MPa，例如可以是40MPa、42MPa、44MPa、46MPa、48MPa、50MPa、52MPa、54MPa、56MPa、58MPa、60MPa、62MPa、64MPa、66MPa、68MPa、70MPa、72MPa、74MPa、76MPa、78MPa或80MPa等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
优选地，步骤(1)所述混合的温度为150-200℃，例如可以是150℃、152℃、154℃、156℃、158℃、160℃、162℃、164℃、166℃、168℃、170℃、172℃、174℃、176℃、178℃、180℃、182℃、184℃、186℃、188℃、190℃、192℃、194℃、196℃、198℃或200℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
优选地，步骤(1)所述混合的时间为0.5-6h，例如可以是0.5h、0.6h、0.7h、0.8h、1h、1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h、4h、4.2h、4.4h、4.6h、4.8h、5h、5.2h、5.4h、5.6h、5.8h或6h等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，步骤(2)所述木质素磺酸盐的添加量为所述第一液中硅烷偶联剂质量的1.5-2倍，例如可以是1.5倍、1.52倍、1.54倍、1.56倍、1.58倍、1.6倍、1.62倍、1.64倍、1.66倍、1.68倍、1.7倍、1.72倍、1.74倍、1.76倍、1.78倍、1.8倍、1.82倍、1.84倍、1.86倍、1.88倍、1.9倍、1.92倍、1.94倍、1.96倍、1.98倍或2倍等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
优选地，步骤(2)所述保护气氛包括氮气或惰性气体。
本申请中，所述惰性气体可以是氦气、氖气或氩气等。
作为本申请优选的技术方案，步骤(2)所述反应在高剪切处理下进行。
优选地，所述高剪切处理的速率为100-200r/min，例如可以是100r/min、105r/min、110r/min、115r/min、120r/min、125r/min、130r/min、135r/min、140r/min、145r/min、150r/min、155r/min、160r/min、165r/min、170r/min、 175r/min、180r/min、185r/min、190r/min、195r/min或200r/min等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
优选地，所述高剪切处理的终点为浆料温度80-100℃，例如可以是80℃、81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃、90℃、91℃、92℃、93℃、94℃、95℃、96℃、97℃、98℃、99℃或100℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，步骤(2)所述反应开始时浆料的温度≤30℃，例如可以是30℃、28℃、26℃、24℃、22℃、20℃、18℃、16℃、14℃、12℃或10℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。
作为本申请优选的技术方案，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸、硅烷偶联剂进行混合得到第一液；所述白炭黑分散液为白炭黑在醇液中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为55-70％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的7-15％；所述硅烷偶联剂包括硅烷偶联剂KH-550、硅烷偶联剂KH-560或硅烷偶联剂KH-570中的1种或至少2种的组合；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的15-25％；所述混合在高温高压下进行；所述混合的压强为40-80MPa；所述混合的温度为150-200℃；所述混合的时间为0.5-6h；
(2)将步骤(1)得到的第一液与木质素磺酸盐在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸盐的添加量为所述第一液中硅烷偶联剂质量的1.5-2倍；所述保护气氛包括氮气或惰性气体；所述反应在高剪切处理下进行；所述高剪切处理的速率为100-200r/min；所述高剪切处理的终点为浆料温度80-100℃；所述反应开始时浆料的温度≤30℃。
与现有技术方案相比，本申请至少具有以下有益效果：
(1)本申请提供的改性方法，通过采用特定的试剂如硅烷偶联剂和木质素磺酸盐与特定的高剪切过程相配合，实现了白炭黑的改性，同时提升了白炭黑的表面积和分散性。
(2)改性后的白炭黑作为补强材料使用时，可以明显提升橡胶材料的力学性能和耐磨损性能。0℃的损耗因子≥0.81。
具体实施方式
为更好地说明本申请，便于理解本申请的技术方案，本申请的典型但非限制性的实施例如下：
实施例1
本实施例提供一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸(质量浓度为25％)、硅烷偶联剂(硅烷偶联剂KH-550)进行混合得到第一液；所述白炭黑分散液为白炭黑在乙醇中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为62％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的11％；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的20％；所述混合在高温高压下进行；所述混合的压强为60MPa；所述混合的温度为170℃；所述混合的时间为2h；
(2)将步骤(1)得到的第一液与木质素磺酸钠在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸钠的添加量为所述第一液中硅烷偶联剂质量的1.7倍；所述保护气氛为氮气；所述反应在高剪切处理下进行；所述高剪切处理的速率为125r/min；所述高剪切处理的终点为浆料温度95℃；所述反应开始时浆料的温度为30℃。
实施例2
本实施例提供一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸(质量浓度为20％)、硅烷偶联剂(硅烷偶联剂KH-560)进行混合得到第一液；所述白炭黑分散液为白炭黑在甲醇中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为55％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的15％；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的15％；所述混合在高温高压下进行；所述混合的压强为40MPa；所述混合的温度为200℃；所述混合的时间为0.5h；
(2)将步骤(1)得到的第一液与木质素磺酸钾在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸钾的添加量为所述第一液中硅烷偶联剂质量的1.5倍；所述保护气氛为氦气；所述反应在高剪切处理下进行；所述高剪切处理的速率为200r/min；所述高剪切处理的终点为浆料温度80℃；所述反应开始时浆料的温度为20℃。
实施例3
本实施例提供一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸(质量浓度为30％)、硅烷偶联剂(硅烷偶联剂KH-570)进行混合得到第一液；所述白炭黑分散液为白炭黑在乙醇中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为70％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的7％；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的25％；所述混合在高温高压下进行；所述混合的压强为80MPa；所述混合的温度为150℃；所述混合的时间为1h；
(2)将步骤(1)得到的第一液与木质素磺酸钠在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸钠的添加量为所述第一液中硅烷偶联剂质量的2倍；所述保护气氛为氮气；所述反应在高剪切处理下进行；所述高剪切处理的速率为100r/min；所述高剪切处理的终点为浆料温度100℃；所述反应开始时浆料的温度为25℃。
实施例4
本实施例提供一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸(质量浓度为27％)、硅烷偶联剂(烷偶联剂KH-570)进行混合得到第一液；所述白炭黑分散液为白炭黑在丙三醇中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为67％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的10％；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的22％；所述混合在高温高压下进行；所述混合的压强为67MPa；所述混合的温度为177℃；所述混合的时间为0.8h；
(2)将步骤(1)得到的第一液与木质素磺酸钙在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸钙的添加量为所述第一液中硅烷偶联剂质量的1.6倍；所述保护气氛为氦气；所述反应在高剪切处理下进行；所述高剪切处理的速率为168r/min；所述高剪切处理的终点为浆料温度86℃；所述反应开始时浆料的温度为22℃。
实施例5
本实施例提供一种白炭黑的改性方法，所述改性方法包括：
(1)将白炭黑分散液、羟基乙酸(质量浓度为23％)、硅烷偶联剂(硅烷偶联剂KH-550)进行混合得到第一液；所述白炭黑分散液为白炭黑在乙二醇中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为58％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的9％；所述硅烷偶联剂的添加量为所述第 一液中白炭黑质量的17％；所述混合在高温高压下进行；所述混合的压强为44MPa；所述混合的温度为158℃；所述混合的时间为1.2h；
(2)将步骤(1)得到的第一液与木质素磺酸镁在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸镁的添加量为所述第一液中硅烷偶联剂质量的1.9倍；所述保护气氛为氩气；所述反应在高剪切处理下进行；所述高剪切处理的速率为126r/min；所述高剪切处理的终点为浆料温度92℃；所述反应开始时浆料的温度为25℃。
对比例1
与实施例1的区别仅在于将羟基乙酸替换为等量的硫酸。
对比例2
与实施例1的区别仅在于所述混合在常温常压下进行。
对比例3
与实施例1的区别仅在于将木质素磺酸盐替换为十二烷基苯磺酸钠。
对比例4
与实施例1的区别仅在于将所述高剪切处理替换为等温等速率的搅拌。
对比例5
与实施例1的区别仅在于将硅烷偶联剂和木质素磺酸钠的添加位置进行调换，即先加木质素磺酸钠，之后按顺序加入硅烷偶联剂。
对上述实施例和对比例所得白炭黑进行性能检测，具体结果详见表1。上述实施例和对比例中所用白炭黑为市售白炭黑，具体参数详见表1。
其中，按照GB/T 10722-2014炭黑总表面积和外表面积的测定氮吸附法测定白炭黑的比表面积；按照HGT 3072-2019《橡胶配合剂沉淀水合二氧化硅吸油值的测定》测定白炭黑的吸油值；按照HGT 2404-2020《橡胶配合剂沉淀水合二氧化硅在丁苯胶中的鉴定》进行炼胶；按照GB/T528-2009《硫化橡胶或热塑性橡胶拉伸应力应变性能的测定》测试应力-应变特性；按照GB/T1232.1《未硫化橡胶用圆盘剪切粘度计进行测定第一部分：门尼粘度的测定》测试门尼粘度。
表1
Figure PCTCN2021134739-appb-000001
Figure PCTCN2021134739-appb-000002
通过上述实施例和对比例的结果可知，本申请提供的改性方法，通过采用特定的改性试剂和合理的制备过程相配合，实现了白炭黑的改性，使得制备得到的白炭黑具有良好的表面性能和分散性。同时其作为橡胶补强剂使用时可以显著提升所得橡胶材料的损耗性能和力学性能。
申请人声明，本申请通过上述实施例来说明本申请的详细结构特征，但本申请并不局限于上述详细结构特征，即不意味着本申请必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落 在本申请的保护范围和公开范围之内。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (10)

  1. 一种白炭黑的改性方法，其包括：
    (1)将白炭黑分散液、羟基乙酸、硅烷偶联剂进行混合得到第一液；
    (2)将步骤(1)得到的第一液与木质素磺酸盐在保护气氛下进行反应，之后经固液分离得到改性白炭黑。
  2. 如权利要求1所述的改性方法，其中，步骤(1)所述白炭黑分散液为白炭黑在醇液中进行超声分散得到。
  3. 如权利要求1或2所述的改性方法，其中，步骤(1)所述白炭黑分散液中白炭黑的含量为55-70％。
  4. 如权利要求1-3任一项所述的改性方法，其中，步骤(1)所述羟基乙酸的添加量为所述第一液中白炭黑质量的7-15％；
    任选地，步骤(1)所述羟基乙酸的质量浓度为20-30％。
  5. 如权利要求1-4任一项所述的改性方法，其中，步骤(1)所述硅烷偶联剂包括硅烷偶联剂KH-550、硅烷偶联剂KH-560或硅烷偶联剂KH-570中的1种或至少2种的组合；
    任选地，步骤(1)所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的15-25％。
  6. 如权利要求1-5任一项所述的改性方法，其中，步骤(1)所述混合在高温高压下进行；
    任选地，步骤(1)所述混合的压强为40-80MPa；
    任选地，步骤(1)所述混合的温度为150-200℃；
    任选地，步骤(1)所述混合的时间为0.5-6h。
  7. 如权利要求1-6任一项所述的改性方法，其中，步骤(2)所述木质素磺酸盐的添加量为所述第一液中硅烷偶联剂质量的1.5-2倍；
    任选地，步骤(2)所述保护气氛包括氮气或惰性气体。
  8. 如权利要求1-7任一项所述的改性方法，其中，步骤(2)所述反应在高剪切处理下进行；
    任选地，所述高剪切处理的速率为100-200r/min；
    任选地，所述高剪切处理的终点为浆料温度80-100℃。
  9. 如权利要求1-8任一项所述的改性方法，其中，步骤(2)所述反应开始时浆料的温度≤30℃。
  10. 如权利要求1-9任一项所述的改性方法，其中，所述改性方法包括：
    (1)将白炭黑分散液、羟基乙酸、硅烷偶联剂进行混合得到第一液；所述白炭黑分散液为白炭黑在醇液中进行超声分散得到；所述白炭黑分散液中白炭黑的含量为55-70％；所述羟基乙酸的添加量为所述第一液中白炭黑质量的7-15％；所述硅烷偶联剂包括硅烷偶联剂KH-550、硅烷偶联剂KH-560或硅烷偶联剂KH-570中的1种或至少2种的组合；所述硅烷偶联剂的添加量为所述第一液中白炭黑质量的15-25％；所述混合在高温高压下进行；所述混合的压强为40-80MPa；所述混合的温度为150-200℃；所述混合的时间为0.5-6h；
    (2)将步骤(1)得到的第一液与木质素磺酸盐在保护气氛下进行反应，之后经固液分离得到改性白炭黑；所述木质素磺酸盐的添加量为所述第一液中硅烷偶联剂质量的1.5-2倍；所述保护气氛包括氮气或惰性气体；所述反应在高剪切处理下进行；所述高剪切处理的速率为100-200r/min；所述高剪切处理的终点为浆料温度80-100℃；所述反应开始时浆料的温度≤30℃。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012162937A1 (zh) * 2011-06-02 2012-12-06 北京化工大学 一种制备硅烷偶联剂改性白炭黑的方法
US20140080752A1 (en) * 2012-09-17 2014-03-20 Tocad America, Inc. White Carbon Black Formulations and Methods
CN108410041A (zh) * 2018-01-31 2018-08-17 中国科学院长春应用化学研究所 一种白炭黑湿法母炼胶的制备方法
CN109232983A (zh) * 2018-07-26 2019-01-18 安徽锦华氧化锌有限公司 一种丁苯胶复合材料用改性白炭黑
CN110734653A (zh) * 2019-10-23 2020-01-31 浙江新纳材料科技股份有限公司 一种化学包覆式疏水性白炭黑的制备方法
WO2021003814A1 (zh) * 2019-07-05 2021-01-14 北京化工大学 一种改性白炭黑及其制备方法和母炼胶

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012162937A1 (zh) * 2011-06-02 2012-12-06 北京化工大学 一种制备硅烷偶联剂改性白炭黑的方法
US20140080752A1 (en) * 2012-09-17 2014-03-20 Tocad America, Inc. White Carbon Black Formulations and Methods
CN108410041A (zh) * 2018-01-31 2018-08-17 中国科学院长春应用化学研究所 一种白炭黑湿法母炼胶的制备方法
CN109232983A (zh) * 2018-07-26 2019-01-18 安徽锦华氧化锌有限公司 一种丁苯胶复合材料用改性白炭黑
WO2021003814A1 (zh) * 2019-07-05 2021-01-14 北京化工大学 一种改性白炭黑及其制备方法和母炼胶
CN110734653A (zh) * 2019-10-23 2020-01-31 浙江新纳材料科技股份有限公司 一种化学包覆式疏水性白炭黑的制备方法

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