WO2023097541A1 - 一种亲水白炭黑的制备方法及应用 - Google Patents

一种亲水白炭黑的制备方法及应用 Download PDF

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WO2023097541A1
WO2023097541A1 PCT/CN2021/134731 CN2021134731W WO2023097541A1 WO 2023097541 A1 WO2023097541 A1 WO 2023097541A1 CN 2021134731 W CN2021134731 W CN 2021134731W WO 2023097541 A1 WO2023097541 A1 WO 2023097541A1
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Prior art keywords
acid
solution
mixed
preparation
carbon black
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PCT/CN2021/134731
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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 CN202180004236.0A priority Critical patent/CN114286798B/zh
Priority to PCT/CN2021/134731 priority patent/WO2023097541A1/zh
Publication of WO2023097541A1 publication Critical patent/WO2023097541A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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 preparation method and application of hydrophilic white carbon black.
  • silica is widely used in various fields due to its unique properties.
  • Such as CN106046860A discloses a kind of preparation method of white carbon black/nano-calcium composite slurry coating wet process ultrafine calcium carbonate, high-quality calcium carbonate ore is through crushing, after adding grinding aid dry grinding, adding the first dispersant preparation Form a slurry with a solid content of 60-65%, and then grind at a high speed at a constant temperature to obtain a calcium carbonate slurry of 8,000 mesh, and add a slurry coating agent to the white carbon black/nano-calcium slurry with a solid content of 10-20% After coating in liquid phase, the surface is modified by compound modifier after drying, depolymerization and dispersion.
  • the wet-process superfine active calcium produced has a specific surface area of 25-30m 2 /g.
  • the activation degree of the product is greater than 97.5%, and the combination with the base resin is stronger.
  • three kinds of dispersants are added in the production process, and a compatibilizer and a liquid-phase coating agent are used at the same time, so that the three kinds of powders can be uniformly and stably coated together, and good dispersibility in the base material can be realized.
  • CN111690174A discloses a modified white carbon black, which includes 10-16 parts of fly ash; 28-45 parts of sodium carbonate; 31-48 parts of p-toluenesulfonic acid; dimethyldimethoxysilane 1.3-2.4 parts; 52-81 parts of n-octanol; 24-36 parts of ethanol; Dimethyldimethoxysilane and n-octanol are modified to obtain modified white carbon black.
  • a silicone rubber for rubber rollers containing modified white carbon black including 100 parts of methyl vinyl silicone rubber; 10-90 parts of modified white carbon black; the preparation method is: mixing methyl vinyl silicone rubber Add modified white carbon black into a kneader and mix into a ball.
  • the produced silicone rubber does not add structure control agent, which can significantly improve resilience and processing performance.
  • the present application provides a method for preparing hydrophilic white carbon black to solve the problems of poor hydrophilicity and small specific surface area of the currently prepared white carbon black.
  • the application provides a method for preparing hydrophilic silica, the preparation method comprising:
  • the preparation method of the present application realizes the preparation of high-performance silica by using various mixed solution systems and specific glycolic acid, so that the hydrophilicity and specific surface area of the prepared silica are significantly improved.
  • the number of hydroxyl groups on the surface of the white carbon black can be further increased.
  • the pH value of the maintained liquid phase is 9.5-12, such as 9.5, 10, 10.5, 11, 11.5 or 12, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable .
  • the adding of the glycolic acid solution to the pH value of the liquid phase is 5-7, such as 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8 or 7, etc., but not limited to the Listed values, other unlisted combinations within this range are also applicable.
  • the carbonate is a soluble carbonate, such as sodium carbonate, potassium carbonate and the like.
  • the bicarbonate is a soluble bicarbonate, such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and the like.
  • the mixed salt solution of sodium silicate and carbonate/bicarbonate is a mixed salt solution of sodium silicate and carbonate, or a mixed salt solution of sodium silicate and bicarbonate.
  • the mass concentration of the sodium silicate solution 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 mass ratio of the sodium silicate solution and the mixed acid solution is 1:(0.6-0.8), such as 1:0.6, 1:0.61, 1:0.62, 1:0.63, 1:0.64, 1: 0.65, 1:0.66, 1:0.67, 1:0.68, 1:0.69, 1:0.7, 1:0.71, 1:0.72, 1:0.73, 1:0.74, 1:0.75, 1:0.76, 1:0.77, 1:0.78, 1:0.79 or 1:0.8, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mixed acid solution is a mixed solution of organic acid and inorganic acid.
  • the organic acid in the mixed acid solution includes monocarboxylic acid and/or dicarboxylic acid.
  • the monocarboxylic acid includes one or a combination of at least two of formic acid, acetic acid, propionic acid or butyric acid.
  • the dicarboxylic acid includes one or a combination of at least two of oxalic acid, glutamic acid, malic acid, or malonic acid.
  • the inorganic acid in the mixed acid solution includes one or a combination of at least two of hydrochloric acid, nitric acid or sulfuric acid.
  • the mass ratio of organic acid and inorganic acid in the mixed acid solution is 1:(3-5), for example, it can be 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1: 4.6, 1:4.7, 1:4.8, 1:4.9 or 1:5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mass ratio of sodium silicate and carbonate in the mixed salt solution is 1:(8-15), such as 1:8, 1:8.2, 1:8.4, 1: 8.6, 1:8.8, 1:9, 1:9.2, 1:9.4, 1:9.6, 1:9.8, 1:10, 1:10.2, 1:10.4, 1:10.6, 1:10.8, 1:11, 1:11.2, 1:11.4, 1:11.6, 1:11.8, 1:12, 1:12.2, 1:12.4, 1:12.6, 1:12.8, 1:13, 1:13.2, 1:13.4, 1:1: 13.6, 1:13.8, 1:14, 1:14.2, 1:14.6, 1:14.8 or 1:15, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
  • the mass concentration of the mixed salt solution is 10-15%, such as 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 values within this range are also applicable.
  • reaction is carried out under an ammonia atmosphere.
  • the reaction temperature is 110-150°C, for example, it can be 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C °C, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C or 150°C, etc., but not limited to Listed values, other unlisted combinations within this range are also applicable.
  • the reaction is carried out in a reactor or other airtight containers to ensure that the reaction temperature reaches the standard.
  • the reaction time is 1-2h, such as 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, etc., but not Limited to the listed values, other unlisted combinations within this range are also applicable.
  • the preparation method comprises:
  • the mass concentration of described sodium silicate solution is 20-30%;
  • the mass ratio of described sodium silicate solution and mixed acid solution is 1:(0.6-0.8);
  • Described mixed acid solution is the mixing of organic acid and inorganic acid solution; the organic acid in the mixed acid solution includes monocarboxylic acid and/or dicarboxylic acid; the inorganic acid in the mixed acid solution includes one or at least two combinations of hydrochloric acid, nitric acid or sulfuric acid;
  • the mass ratio of organic acid and inorganic acid in the mixed acid solution is 1:(3-5);
  • the mass ratio of sodium silicate and carbonate in the mixed salt solution is 1:(8-15); the mass concentration of the mixed salt solution is 10-15%; the reaction is carried out under an ammonia atmosphere; the The temperature of the reaction is 110-150°C; the time of the reaction is 1-2h.
  • the present application provides a method for preparing an adhesive, the preparation method comprising preparing an adhesive for epoxy resin using the white carbon black obtained by the preparation method described in the first aspect.
  • the scheme provided by the application improves the hydrophilic property of the obtained white carbon black by adopting a specific mixed salt solution and an ammonia gas atmosphere, further improves the specific surface area of the obtained white carbon black, and makes the white carbon black Adhesives used in epoxy resins to improve the adhesion and toughness of the adhesive.
  • the pre-nucleation of the crystal is realized by premixing the mixed acid and sodium silicate, and then the salt mixed solution is used to adjust the growth process of the crystal, regulate the specific surface area and hydrophilicity of the white carbon black, and finally introduce Specific glycolic acid is used to further improve the performance of the obtained silica.
  • the contact angle of the obtained white carbon black is ⁇ 7°
  • the BET specific surface area is ⁇ 162m 2 /g
  • the number of surface hydroxyl groups is ⁇ 5.18/nm 2 .
  • the present embodiment provides a kind of preparation method of hydrophilic white carbon black, and described preparation method comprises:
  • the mass concentration of described sodium silicate solution is 25%;
  • the mass ratio of described sodium silicate solution and mixed acid solution is 1:0.7;
  • Described mixed acid solution is the mixed solution of organic acid and inorganic acid; Said mixed acid
  • the organic acid in the solution is acetic acid;
  • the inorganic acid in the mixed acid solution is hydrochloric acid;
  • the mass ratio of the organic acid and the inorganic acid in the mixed acid solution is 1:4;
  • the mass ratio of sodium silicate and carbonate in the mixed salt solution is 1:11; the mass concentration of the mixed salt solution is 12%; the reaction is carried out under an ammonia atmosphere; the reaction temperature is 130 ° C; the reaction time is 1.5 h.
  • the present embodiment provides a kind of preparation method of hydrophilic white carbon black, and described preparation method comprises:
  • the mass concentration of described sodium silicate solution is 20%;
  • the mass ratio of described sodium silicate solution and mixed acid solution is 1:0.8;
  • Described mixed acid solution is the mixed solution of organic acid and inorganic acid; Said mixed acid
  • the organic acid in the solution is oxalic acid;
  • the inorganic acid in the mixed acid solution is sulfuric acid;
  • the mass ratio of the organic acid and the inorganic acid in the mixed acid solution is 1:3;
  • the mass ratio of sodium silicate and carbonate in the mixed salt solution is 1:15; the mass concentration of the mixed salt solution is 15%; the reaction is carried out under an ammonia atmosphere; the reaction temperature is 150 ° C; the reaction time is 1 h.
  • the present embodiment provides a kind of preparation method of hydrophilic white carbon black, and described preparation method comprises:
  • the mass concentration of described sodium silicate solution is 30%;
  • the mass ratio of described sodium silicate solution and mixed acid solution is 1:0.6;
  • Described mixed acid solution is the mixed solution of organic acid and inorganic acid; Said mixed acid
  • the organic acid in the solution is formic acid;
  • the inorganic acid in the mixed acid solution is nitric acid;
  • the mass ratio of the organic acid and the inorganic acid in the mixed acid solution is 1:5;
  • the mass ratio of sodium silicate and carbonate in the mixed salt solution is 1:8; the mass concentration of the mixed salt solution is 10%; the reaction is carried out under an ammonia atmosphere; the reaction temperature is 110 °C; the reaction time is 2h.
  • Example 1 The difference from Example 1 is only that the mixed acid is replaced by sulfuric acid of the same amount and concentration; the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the mixed acid is replaced by acetic acid of the same amount and concentration; the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the mixed salt solution is replaced by sodium silicate of the same amount and concentration; the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the mixed salt solution is replaced by sodium chloride of the same amount and concentration; the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the glycolic acid solution is replaced with acetic acid of equal amount and concentration; the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The only difference from Example 1 is that the glycolic acid solution is replaced by equal amounts and equal concentrations of ethanol and acetic acid (the mass ratio of ethanol and acetic acid is 1:1); the performance parameters of the obtained white carbon black are shown in Table 1.
  • Example 1 The only difference from Example 1 is that the glycolic acid solution is replaced by equal amounts and equal concentrations of ethanol and sulfuric acid (the mass ratio of ethanol and acetic acid is 1:1); the performance parameters of the obtained white carbon black are shown in Table 1.
  • the contact angle in the above-mentioned examples and comparative examples measures the angle at which the liquid touches the solid, and the size of the contact angle can reflect whether the solid can be wetted by the liquid.
  • the DSA25 contact angle measuring instrument is used for measurement.
  • the specific operation steps are as follows: put the silica sample into the mold, press it for 3-5 minutes under the pressure of 20Mpa, take out the silica that is pressed into a sheet and place it On the glass slide, and then use the instrument to measure the contact angle; the detection method of the BET specific surface area: according to GB/T 10722-2014 carbon black total surface area and the determination of the external area nitrogen adsorption method; modified white carbon black surface hydroxyl number
  • the detection method is as follows: Weigh 2.0g of white carbon black in a 200mL beaker, add 25mL of absolute ethanol, and then add 75mL of 20% NaCl solution.
  • V the volume (mL) of NaOH standard solution consumed to increase the pH value from 4 to 9;
  • N A Avogadro's constant.
  • the present application illustrates the detailed structural features of the present application through the above-mentioned embodiments, but the present application is not limited to the above-mentioned detailed structural features, that is, it does not mean that the application must rely on the above-mentioned detailed structural features to be implemented.
  • Those skilled in the art should understand that any improvement to the application, equivalent replacement of the components selected in the application, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

本申请涉及一种亲水白炭黑的制备方法及应用，所述制备方法包括：将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5-12，然后加入羟基乙酸溶液至液相pH值为5-7，经固液分离得到所述白炭黑。本申请的制备方法，通过采用多种混合溶液体系，并采用特定的羟基乙酸实现了高性能白炭黑的制备，使得制备得到的白炭黑的亲水性和比表面积显著提升。同时通过引入碳酸盐/碳酸氢盐和羟基乙酸配合，实现白炭黑表面羟基数量的进一步提升。

Description

一种亲水白炭黑的制备方法及应用 技术领域
本申请涉及白炭黑领域，具体涉及一种亲水白炭黑的制备方法及应用。
背景技术
目前，白炭黑由于其自身的独特性能，广泛用于各个领域。
如CN106046860A公开了一种白炭黑/纳米钙复合浆料包覆湿法超细碳酸钙的制备方法，将优质碳酸钙原矿经破碎、添加助磨剂干法研磨后，添加第一分散剂配制成固含量为60-65％的浆料，再经高速搅拌恒温研磨，得8000目的碳酸钙浆料，与10-20％固含量的白炭黑/纳米钙浆料通过添加浆料包覆剂后液相包覆，再经干燥、解聚打散后经复合改性剂表面改性。生产的湿法超细活性钙，其比表面积达25-30m 2/g。采用复合改性工艺，产品活化度大于97.5％，与基材树脂的结合性更强。该发明在生产工艺中添加了三种分散剂，同时采用相容剂和液相包覆剂，可以实现三种粉体均匀稳定的包覆在一起，实现在基料中良好的分散性。
CN111690174A公开了一种改性白炭黑，该改性白炭黑包括粉煤灰10-16份；碳酸钠28-45份；对甲苯磺酸31-48份；二甲基二甲氧基硅烷1.3-2.4份；正辛醇52-81份；乙醇24-36份；水58-74份；其制备方法为：将粉煤灰与碳酸钠反应，随后加对甲苯磺酸进行酸浸；加入二甲基二甲氧基硅烷和正辛醇改性，即得改性白炭黑。还公开了一种含有改性白炭黑的胶辊用硅橡胶，包括甲基乙烯基硅橡胶100份；改性白炭黑10-90份；其制备方法为：将甲基乙烯基硅橡胶和改性白炭黑加入捏合机混合成团。生产的硅橡胶不添加结构控制剂，可以显著提高回弹性和加工性能。
然而，目前针对亲水性白炭黑的制备中，仍存在亲水性差，比表面积较小的问题。
发明内容
本申请提供了一种亲水白炭黑的制备方法，以解决目前制备所得白炭黑存在的亲水性差，比表面积较小问题。
第一方面，本申请提供了一种亲水白炭黑的制备方法，所述制备方法包括：
将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5-12，然后加入羟基乙酸溶液至液相pH值为5-7，经固液分离得到所述白炭黑。
本申请的制备方法，通过采用多种混合溶液体系，并采用特定的羟基乙酸实现了高性能白炭黑的制备，使得制备得到的白炭黑的亲水性和比表面积显著提升。同时通过引入碳酸盐/碳酸氢盐和羟基乙酸配合，实现白炭黑表面羟基数量的进一步提升。
本申请中，所述保持液相pH值为9.5-12，例如可以是9.5、10、10.5、11、11.5或12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。
本申请中，所述加入羟基乙酸溶液至液相pH值为5-7，例如可以是5、5.2、5.4、5.6、5.8、6、6.2、6.4、6.6、6.8或7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。
本申请中，所述碳酸盐为可溶性碳酸盐，例如可以是碳酸钠、碳酸钾等。
本申请中，所述碳酸氢盐为可溶性碳酸氢盐，例如可以是碳酸氢钠、碳酸氢钾、碳酸氢铵等。
本申请中，所述硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液为硅酸钠和碳酸盐的混合盐溶液、或硅酸钠和碳酸氢盐的混合盐溶液。
作为本申请优选的技术方案，所述硅酸钠溶液的质量浓度为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。
优选地，所述硅酸钠溶液和混合酸溶液的质量比为1:(0.6-0.8)，例如可以是1:0.6、1:0.61、1:0.62、1:0.63、1:0.64、1:0.65、1:0.66、1:0.67、1:0.68、1:0.69、1:0.7、1:0.71、1:0.72、1:0.73、1:0.74、1:0.75、1:0.76、1:0.77、1:0.78、1:0.79或1:0.8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，所述混合酸溶液为有机酸和无机酸的混合溶液。
作为本申请优选的技术方案，所述混合酸溶液中的有机酸包括一元羧酸和/或二元羧酸。
本申请中，所述一元羧酸包括甲酸、乙酸、丙酸或丁酸中的1种或至少2 种的组合。
本申请中，所述二元羧酸包括乙二酸、谷氨酸、苹果酸或丙二酸等的1种或至少2种的组合。
优选地，所述混合酸溶液中的无机酸包括盐酸、硝酸或硫酸中的1种或至少2种的组合。
作为本申请优选的技术方案，所述混合酸溶液中有机酸和无机酸的质量比为1:(3-5)，例如可以是1:3、1:3.1、1:3.2、1:3.3、1:3.4、1:3.5、1:3.6、1:3.7、1:3.8、1:3.9、1:4、1:4.1、1:4.2、1:4.3、1:4.4、1:4.5、1:4.6、1:4.7、1:4.8、1:4.9或1:5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，所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:(8-15)，例如可以是1:8、1:8.2、1:8.4、1:8.6、1:8.8、1:9、1:9.2、1:9.4、1:9.6、1:9.8、1:10、1:10.2、1:10.4、1:10.6、1:10.8、1:11、1:11.2、1:11.4、1:11.6、1:11.8、1:12、1:12.2、1:12.4、1:12.6、1:12.8、1:13、1:13.2、1:13.4、1:13.6、1:13.8、1:14、1:14.2、1:14.6、1:14.8或1:15等，但不限于所列举的数值，该范围内其他未列举的数值同样适用。
优选地，所述混合盐溶液的质量浓度为10-15％，例如可以是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数值同样适用。
作为本申请优选的技术方案，所述反应在氨气氛围下进行。
作为本申请优选的技术方案，所述反应的温度为110-150℃，例如可以是110℃、111℃、112℃、113℃、114℃、115℃、116℃、117℃、118℃、119℃、120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃、140℃、141℃、142℃、143℃、144℃、145℃、146℃、147℃、148℃、149℃或150℃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。
本申请中，所述反应在反应釜或其他密闭容器中进行，以保证反应温度达标。
优选地，所述反应的时间为1-2h，例如可以是1h、1.1h、1.2h、1.3h、1.4 h、1.5h、1.6h、1.7h、1.8h、1.9h或2h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，所述制备方法包括：
将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5-12，然后加入羟基乙酸溶液至液相pH值为5-7，经固液分离得到所述白炭黑；
所述硅酸钠溶液的质量浓度为20-30％；所述硅酸钠溶液和混合酸溶液的质量比为1:(0.6-0.8)；所述混合酸溶液为有机酸和无机酸的混合溶液；所述混合酸溶液中的有机酸包括一元羧酸和/或二元羧酸；所述混合酸溶液中的无机酸包括盐酸、硝酸或硫酸中的1种或至少2种的组合；所述混合酸溶液中有机酸和无机酸的质量比为1:(3-5)；
所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:(8-15)；所述混合盐溶液的质量浓度为10-15％；所述反应在氨气氛围下进行；所述反应的温度为110-150℃；所述反应的时间为1-2h。
第二方面，本申请提供了一种胶黏剂的制备方法，所述制备方法包括采用由第一方面所述的制备方法得到的白炭黑制备用于环氧树脂的胶粘剂。
与现有技术方案相比，本申请至少具有以下有益效果：
(1)本申请提供的方案通过采用特定的混合盐溶液和氨气氛围相配合，提升了所得白炭黑的亲水性能，进一步提升了所得白炭黑的比表面积，并将该白炭黑用于环氧树脂的胶粘剂，提升了胶粘剂的粘结性和韧性。
(2)本申请中通过采用混合酸和硅酸钠预混实现晶体的预成核，之后采用盐混合溶液，调整晶体的生长过程、调控白炭黑的比表面积和亲水性能，最终通过引入特定的羟基乙酸，实现对所得白炭黑性能的进一步提升。所得白炭黑的接触角≤7°，BET比表面积≥162m 2/g，表面羟基数≥5.18个/nm 2。
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
本实施例提供一种亲水白炭黑的制备方法，所述制备方法包括：
将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为11，然后加入羟基乙酸溶液至液相pH值为6，经固液分离得到所述白炭黑；
所述硅酸钠溶液的质量浓度为25％；所述硅酸钠溶液和混合酸溶液的质量比为1:0.7；所述混合酸溶液为有机酸和无机酸的混合溶液；所述混合酸溶液中的有机酸为乙酸；所述混合酸溶液中的无机酸为盐酸；所述混合酸溶液中有机酸和无机酸的质量比为1:4；
所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:11；所述混合盐溶液的质量浓度为12％；所述反应在氨气氛围下进行；所述反应的温度为130℃；所述反应的时间为1.5h。
所得白炭黑的性能参数详见表1。
实施例2
本实施例提供一种亲水白炭黑的制备方法，所述制备方法包括：
将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5，然后加入羟基乙酸溶液至液相pH值为5，经固液分离得到所述白炭黑；
所述硅酸钠溶液的质量浓度为20％；所述硅酸钠溶液和混合酸溶液的质量比为1:0.8；所述混合酸溶液为有机酸和无机酸的混合溶液；所述混合酸溶液中的有机酸为乙二酸；所述混合酸溶液中的无机酸为硫酸；所述混合酸溶液中有机酸和无机酸的质量比为1:3；
所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:15；所述混合盐溶液的质量浓度为15％；所述反应在氨气氛围下进行；所述反应的温度为150℃；所述反应的时间为1h。
所得白炭黑的性能参数详见表1。
实施例3
本实施例提供一种亲水白炭黑的制备方法，所述制备方法包括：
将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为12，然后加入羟基乙酸溶液至液相pH值为7，经固液分离得到所述白炭黑；
所述硅酸钠溶液的质量浓度为30％；所述硅酸钠溶液和混合酸溶液的质量 比为1:0.6；所述混合酸溶液为有机酸和无机酸的混合溶液；所述混合酸溶液中的有机酸为甲酸；所述混合酸溶液中的无机酸为硝酸；所述混合酸溶液中有机酸和无机酸的质量比为1:5；
所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:8；所述混合盐溶液的质量浓度为10％；所述反应在氨气氛围下进行；所述反应的温度为110℃；所述反应的时间为2h。
所得白炭黑的性能参数详见表1。
对比例1
与实施例1的区别仅在于将混合酸替换为等量、等浓度的硫酸；所得白炭黑的性能参数详见表1。
对比例2
与实施例1的区别仅在于将混合酸替换为等量、等浓度的乙酸；所得白炭黑的性能参数详见表1。
对比例3
与实施例1的区别仅在于将混合盐溶液替换为等量、等浓度的硅酸钠；所得白炭黑的性能参数详见表1。
对比例4
与实施例1的区别仅在于将混合盐溶液替换为等量、等浓度的氯化钠；所得白炭黑的性能参数详见表1。
对比例5
与实施例1的区别仅在于将羟基乙酸溶液换为等量、等浓度的乙酸；所得白炭黑的性能参数详见表1。
对比例6
与实施例1的区别仅在于将羟基乙酸溶液换为等量、等浓度乙醇和乙酸(乙醇和乙酸的质量比为1:1)；所得白炭黑的性能参数详见表1。
对比例7
与实施例1的区别仅在于将羟基乙酸溶液换为等量、等浓度乙醇和硫酸(乙醇和乙酸的质量比为1:1)；所得白炭黑的性能参数详见表1。
对比例8
与实施例1的区别仅在于所述反应在二氧化碳氛围下进行；所得白炭黑的 性能参数详见表1。
表1
  接触角/° BET比表面积/m 2/g 表面羟基数/个/nm 2
实施例1 3 185 5.36
实施例2 7 162 5.18
实施例3 5 180 6.22
对比例1 30 132 2.22
对比例2 33 153 3.18
对比例3 43 113 1.53
对比例4 25 136 1.15
对比例5 36 145 2.13
对比例6 22 120 4.12
对比例7 29 123 3.55
对比例8 15 146 2.66
上述实施例和对比例中接触角测定的是液体接触固体时的角度，接触角的大小可以反映固体能不能被液体浸润。本文采用DSA25型接触角测定仪进行测定，具体操作步骤如下：将白炭黑样品放入模具中，在20Mpa的压力下压至3-5分钟，取出被压成片状的白炭黑并放置在载玻片上，然后使用仪器对其进行接触角测定；BET比表面积的检测方法：依据GB/T 10722-2014炭黑总表面积和外表面积的测定氮吸附法；改性白炭黑表面羟基数的检测方法如下：称取2.0g白炭黑于200mL烧杯中，加入25mL无水乙醇，然后加入75mL 20％的NaCl溶液。磁力搅拌均匀后，滴加0.1mol/L的NaOH(HCl)标准液调节试液pH为4，然后缓慢滴加0.1mol/L的NaOH使pH至9，保持20s，并维持pH不变。根据公式(3-2)计算得到每平方纳米白炭黑表面上的羟基个数(N)：
N＝0.001*C*V*N A/SM   (3-2)
式中：S：样品的比表面积(nm 2/g)；
V：使pH值从4增加到9所消耗的NaOH标准液体积(mL)；
M：白炭黑的质量(g)；
N A：阿伏伽德罗常数。
通过上述实施例和对比例的结果可知，采用多种混合溶液体系，并采用特 定的羟基乙酸及氨气氛围实现了高性能白炭黑的制备，使得制备得到的白炭黑的亲水性和比表面积显著提升。同时通过引入碳酸盐/碳酸氢盐和羟基乙酸配合，实现白炭黑表面羟基数量的进一步提升。
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 (11)

  1. 一种亲水白炭黑的制备方法，其包括：
    将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5-12，然后加入羟基乙酸溶液至液相pH值为5-7，经固液分离得到所述白炭黑。
  2. 如权利要求1所述的制备方法，其中，所述硅酸钠溶液的质量浓度为20-30％。
  3. 如权利要1或2所述的制备方法，其中，所述硅酸钠溶液和混合酸溶液的质量比为1:(0.6-0.8)。
  4. 如权利要1-3任一项所述的制备方法，其中，所述混合酸溶液为有机酸和无机酸的混合溶液。
  5. 如权利要求4所述的制备方法，其中，所述混合酸溶液中的有机酸包括一元羧酸和/或二元羧酸；
    任选地，所述混合酸溶液中的无机酸包括盐酸、硝酸或硫酸中的1种或至少2种的组合。
  6. 如权利要求1-5任一项所述的制备方法，其中，所述混合酸溶液中有机酸和无机酸的质量比为1:(3-5)。
  7. 如权利要求1-6任一项所述的制备方法，其中，所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:(8-15)；
    任选地，所述混合盐溶液的质量浓度为10-15％。
  8. 如权利要求1-7任一项所述的制备方法，其中，所述反应在氨气氛围下进行。
  9. 如权利要求1-8任一项所述的制备方法，其中，所述反应的温度为110-150℃；
    任选地，所述反应的时间为1-2h。
  10. 如权利要求1-9任一项所述的制备方法，其中，所述制备方法包括：
    将硅酸钠溶液和混合酸溶液混合，之后加入硅酸钠和碳酸盐/碳酸氢盐的混合盐溶液进行反应，并保持液相pH值为9.5-12，然后加入羟基乙酸溶液至液相pH值为5-7，经固液分离得到所述白炭黑；
    所述硅酸钠溶液的质量浓度为20-30％；所述硅酸钠溶液和混合酸溶液的质量比为1:(0.6-0.8)；所述混合酸溶液为有机酸和无机酸的混合溶液；所述混合酸 溶液中的有机酸包括一元羧酸和/或二元羧酸；所述混合酸溶液中的无机酸包括盐酸、硝酸或硫酸中的1种或至少2种的组合；所述混合酸溶液中有机酸和无机酸的质量比为1:(3-5)；
    所述混合盐溶液中硅酸钠和碳酸盐的质量比为1:(8-15)；所述混合盐溶液的质量浓度为10-15％；所述反应在氨气氛围下进行；所述反应的温度为110-150℃；所述反应的时间为1-2h。
  11. 一种胶黏剂的制备方法，其包括采用由权利要求1-10任一项所述的制备方法得到的白炭黑制备用于环氧树脂的胶粘剂。
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