WO2023097548A1 - 一种用于提升流变特性白炭黑的制备方法及应用 - Google Patents

一种用于提升流变特性白炭黑的制备方法及应用 Download PDF

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WO2023097548A1
WO2023097548A1 PCT/CN2021/134747 CN2021134747W WO2023097548A1 WO 2023097548 A1 WO2023097548 A1 WO 2023097548A1 CN 2021134747 W CN2021134747 W CN 2021134747W WO 2023097548 A1 WO2023097548 A1 WO 2023097548A1
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solution
preparation
carbon black
white carbon
ammonium
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PCT/CN2021/134747
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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/CN2021/134747 priority Critical patent/WO2023097548A1/zh
Priority to CN202180004237.5A priority patent/CN114286799B/zh
Publication of WO2023097548A1 publication Critical patent/WO2023097548A1/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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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

  • the present application relates to the field of white carbon black, in particular to a preparation method for improving rheological properties of white carbon black.
  • silica is widely used in various industries due to its excellent physical and chemical properties and performance.
  • silane coupling agent modified white carbon black pre-dispersed masterbatch is made up of following mass parts raw materials: silane coupling agent modified white carbon black 50 ⁇ 90 parts, carrier rubber 5 ⁇ 50 parts, 1-10 parts of softening oil, 1-5 parts of dispersant; when the silane coupling agent modified silica pre-dispersed masterbatch is used to prepare rubber tires, the silica has a higher dispersion uniformity and can Effectively prevent the re-aggregation of its particles, which can increase the mixing speed, dispersion speed and dispersion uniformity; improve the compatibility between silica and rubber, thereby improving the performance of rubber tires; provide the preparation of "green tire” tread rubber Theoretical basis.
  • CN107163785A discloses a chrome-free dacromet coating containing white carbon black and a preparation method thereof, which is prepared from the following raw materials in parts by weight: white carbon black 1-3, corundum powder 3-5, silicon carbide 4-8, Asbestos powder 1-2, polytetrafluoroethylene powder 5-10, epoxy resin E42 10-15, zinc oxide 1-2, vinyltriamine 10-15, zinc powder 20-30, aluminum powder 20-30, silane Coupling agent KH550 40-50, ethanol 5-10, acetone 50-70, polydimethylsiloxane 0.3-0.6; this invention has high strength and wear resistance, showing good fluidity and adhesion , the formed coating is dense and smooth, which solves the shortcomings of the dacromet coating liquid such as low strength and poor wear resistance, and is very competitive in the market; with the addition of white carbon black, the wear resistance, strength, and wear resistance of the coating are improved. Anti-aging and improve the finish of the paint surface.
  • the white carbon black obtained in the current white carbon black preparation process still has the problems of poor rheological properties and poor product performance in the specific use process.
  • the present application provides a preparation method and application of white carbon black for improving rheological properties, which solves the problems of poor rheological properties and poor use performance of white carbon black in the current use process.
  • the application provides a preparation method for improving rheological properties of silica, the preparation method comprising:
  • the preparation method provided by this application by adjusting the preparation process of white carbon black, and introducing lignosulfonate and mixed salt solution, using the promotion effect between the two, under the condition of high-pressure aging, high-performance white carbon black is prepared.
  • Carbon black, the fluidity index and BET specific surface area of the obtained white carbon black are significantly improved, and the use as an auxiliary agent for PA66 or coating can significantly improve the performance of the obtained product.
  • the pH of the solution is adjusted to 8-10, such as 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9 or 10, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the lignosulfonate may be one or a combination of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate, or magnesium lignosulfonate.
  • the mass concentration of the Na 2 O ⁇ mSiO 2 solution is 5-25%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, etc., but not limited to the listed values , other unlisted combinations within this range are also applicable.
  • the added amount of the lignosulfonate is 2-8% of the mass of the Na2O ⁇ mSiO2 solution, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6% , 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8% or 8%, but not limited to the listed values, other unlisted combinations within this range are also applicable .
  • heating is carried out during the mixing until the solution temperature is 70-90°C, such as 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C, or 90°C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the heating method includes microwave heating.
  • the mixing time is 30-60min, such as 30min, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min, 58min Or 60min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mixed salt solution includes a mixed solution of sodium salt and ammonium salt.
  • the mass ratio of sodium salt and ammonium salt in the mixed salt solution is 1:(0.2-0.5), for example, it can be 1:0.2, 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1 :0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29, 1:0.3, 1:0.31, 1:0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37 , 1:0.38, 1:0.39, 1:0.4, 1:0.41, 1:0.42, 1:0.43, 1:0.44, 1:0.45, 1:0.46, 1:0.47, 1:0.48, 1:0.49, or 1 : 0.5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the sodium salt includes one or a combination of at least two of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
  • the ammonium salt includes one or a combination of at least two of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate or ammonium bicarbonate.
  • the added amount of the mixed salt solution is 10-20% of the mass of the Na2O ⁇ mSiO2 solution, for example, it can be 10%, 11%, 12%, 13%, 14% , 15%, 16%, 17%, 18%, 19% or 20%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the high-pressure aging treatment is performed under a carbon dioxide atmosphere.
  • the pressure of the high-pressure aging treatment is 50-100MPa, such as 50MPa, 52MPa, 54MPa, 56MPa, 58MPa, 60MPa, 62MPa, 64MPa, 66MPa, 68MPa, 70MPa, 72MPa, 74MPa, 76MPa, 78MPa, 80MPa , 82MPa, 84MPa, 86MPa, 88MPa, 90MPa, 92MPa, 94MPa, 96MPa, 98MPa or 100MPa, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the temperature of the high-pressure aging treatment is 120-140°C, such as 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 or 140°C, etc., but not limited to the listed values, other unlisted combinations within this range The same applies.
  • the time for the high-pressure aging treatment is 1-2h, for example, it can be 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 the Na 2 O ⁇ mSiO 2 solution is 5-25%; the added amount of the lignosulfonate is 2-8% of the mass of the Na 2 O ⁇ mSiO 2 solution; Heating until the solution temperature is 70-90°C; the heating method includes microwave heating; the mixing time is 30-60min;
  • Described mixed salt solution comprises the mixed solution of sodium salt and ammonium salt;
  • the mass ratio of sodium salt and ammonium salt is 1:(0.2-0.5) in described mixed salt solution;
  • Described sodium salt comprises sodium carbonate, sodium bicarbonate, 1 or a combination of at least 2 of potassium carbonate or potassium bicarbonate;
  • the ammonium salt includes 1 or a combination of at least 2 of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate or ammonium bicarbonate;
  • the added amount of the mixed salt solution is 10-20% of the mass of the Na2O ⁇ mSiO2 solution;
  • the high-pressure aging treatment is carried out under a carbon dioxide atmosphere; the pressure of the high-pressure aging treatment is 50-100MPa; the temperature of the high-pressure aging treatment is 120-140°C; the time of the high-pressure aging treatment is 1-2h.
  • the present application provides the application of the silica obtained by the preparation method described in the first aspect, and the application includes using the silica to prepare PA66 materials or coatings.
  • the preparation method provided by the application by introducing lignosulfonate in the reaction process and carrying out the formation of white carbon black under the condition of mixed salt solution, and then preparing high-performance white carbon black under high-pressure aging,
  • the fluidity index F1 of the obtained white carbon black is ⁇ 95
  • the BET specific surface is ⁇ 300.12 m 2 /g.
  • the flow properties of the prepared product are significantly improved, wherein the melt flow rate of PA66 containing the white carbon black of the present application is ⁇ 80.15g/min, and the tensile strength is ⁇ 145.66MPa, bending strength ⁇ 200.87MPa; when used as a coating additive, the wear resistance of the coating film after painting is 750g/500r, and the weight loss is ⁇ 0.001g.
  • the present embodiment provides a kind of preparation method that is used to improve rheological characteristic silica, and described preparation method comprises:
  • the mass concentration of the Na 2 O ⁇ mSiO 2 solution is 15%; the added amount of the lignosulfonate is 5% of the mass of the Na 2 O ⁇ mSiO 2 solution; heating to the solution temperature during the mixing 80°C; the heating method is microwave heating; the mixing time is 45min;
  • the mixed salt solution is a mixed solution of sodium salt and ammonium salt; the mass ratio of sodium salt and ammonium salt in the mixed salt solution is 1:0.35; the sodium salt is sodium carbonate; the ammonium salt is ammonium chloride ; The added amount of the mixed salt solution is 15% of the quality of the Na 2 O mSiO 2 solution;
  • the high-pressure aging treatment is performed under a carbon dioxide atmosphere; the pressure of the high-pressure aging treatment is 75 MPa; the temperature of the high-pressure aging treatment is 130° C.; the time of the high-pressure aging treatment is 1.5 h.
  • the present embodiment provides a kind of preparation method that is used to improve rheological characteristic silica, and described preparation method comprises:
  • the mass concentration of the Na 2 O ⁇ mSiO 2 solution is 5%; the added amount of the lignosulfonate is 8% of the mass of the Na 2 O ⁇ mSiO 2 solution; heating to the solution temperature during the mixing 70°C; the heating method is microwave heating; the mixing time is 60min;
  • the mixed salt solution is a mixed solution of sodium salt and ammonium salt; the mass ratio of sodium salt and ammonium salt in the mixed salt solution is 1:0.2; the sodium salt is sodium bicarbonate; the ammonium salt is ammonium sulfate ; The added amount of the mixed salt solution is 10% of the quality of the Na 2 O ⁇ mSiO 2 solution;
  • the high-pressure aging treatment is performed under a carbon dioxide atmosphere; the pressure of the high-pressure aging treatment is 50 MPa; the temperature of the high-pressure aging treatment is 120° C.; the time of the high-pressure aging treatment is 2 hours.
  • the present embodiment provides a kind of preparation method that is used to improve rheological characteristic silica, and described preparation method comprises:
  • the mass concentration of the Na 2 O ⁇ mSiO 2 solution is 25%; the added amount of the lignosulfonate is 2% of the mass of the Na 2 O ⁇ mSiO 2 solution; heating to the solution temperature during the mixing 90°C; the heating method is microwave heating; the mixing time is 30min;
  • the mixed salt solution is a mixed solution of sodium salt and ammonium salt; the mass ratio of sodium salt and ammonium salt in the mixed salt solution is 1:0.5; the sodium salt is sodium carbonate and carbonate with a mass ratio of 1:1 Sodium bicarbonate; the ammonium salt is ammonium chloride and ammonium bicarbonate in mass ratio; the added amount of the mixed salt solution is 20 % of the Na2OmSiO2 solution quality;
  • the high-pressure aging treatment is performed under a carbon dioxide atmosphere; the pressure of the high-pressure aging treatment is 100 MPa; the temperature of the high-pressure aging treatment is 140° C.; the time of the high-pressure aging treatment is 1 h.
  • Example 1 The difference from Example 1 is only that sodium lignosulfonate is replaced by an equivalent amount of polyvinylpyrrolidone, and the performance indicators 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 the mixed salt solution of sodium silicate and ammonium chloride in equal amounts and in equal proportions, and the performance indicators 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 an equal amount and equal proportion of sodium carbonate and sodium silicate mixed salt solution, and the performance indicators 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 ammonium carbonate solution, and the performance indexes of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the microwave heating in the mixing is replaced by conventional water bath heating, and the performance indicators of the obtained silica are shown in Table 1.
  • Example 1 The difference from Example 1 is that the aging treatment adopts normal pressure aging treatment, that is, aging is carried out at room temperature (25° C.), and the performance indexes of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference with Example 1 is only that the high-pressure aging process is carried out under a nitrogen atmosphere, that is, only a high-pressure state is provided, and the performance indicators of the gained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the high-pressure aging treatment is carried out under an ammonia atmosphere, and the performance indexes of the obtained white carbon black are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the added amount of the lignosulfonate is 15% of the mass of the Na 2 O ⁇ mSiO 2 solution, and the performance indexes of the obtained white carbon black are shown in Table 1.
  • Example 1 The only difference from Example 1 is that the added amount of the mixed salt solution is 7% of the mass of the Na 2 O ⁇ mSiO 2 solution, and the performance indexes of the obtained white carbon black are shown in Table 1.
  • the fluidity of the white carbon black is evaluated by the Carr fluidity index, and the specific process can refer to the milk powder fluidity test method (Wang Xiaofei, Gao Yuan, Jiang Nan. Milk powder fluidity test method [J]. Food safety quality inspection Journal, 2015(9):7.).
  • the BET specific surface area is tested according to the nitrogen adsorption method for the determination of the total surface area and external area of carbon black in GB/T 10722-2014.
  • the concrete use process of gained white carbon black improving rheological property is as follows: Introduce the white carbon black in this application in PA66 modification process, the addition amount of white carbon black is 3% of total material mass as in glass fiber modified PA66 Adding during the process, the specific preparation process can be prepared with reference to Example 3 of CN105111730A.
  • the tensile strength of the material is 145.66-180.45MPa, and the bending strength is 200.87-250.65MPa.
  • the preparation process of the coating refers to Example 1 of CN107964265A.
  • the spray flow performance of coating additives is tested according to the following methods:
  • the viscometer Before and after the test, the viscometer should be wiped clean with gauze dipped in the solution, and dried in the air or blown dry with cold wind. The residual liquid of the past test solution is not allowed to adhere to the cup or the outflow tube hole.
  • the cup should be The inner arm and outflow hole of the tube should be kept clean, and the original finish should be observed under light.
  • test solution flows out vertically, start the stopwatch at the same time, the test solution flows out into lines, stop the stopwatch when it is disconnected, the measured time represents its conditional viscosity, and the unit is second.

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Abstract

本申请涉及一种用于提升流变特性白炭黑的制备方法及应用，将Na 2O·mSiO 2溶液和木质素磺酸盐进行混合，并调整溶液pH值至8-10，之后加入混合盐溶液进行高压陈化处理，经固液分离得到所述白炭黑。本申请提供的制备方法，通过调整白炭黑的制备过程，并引入木质素磺酸盐和混合盐溶液，利用二者间的促进效果在高压陈化的条件下，制备得到了高性能的白炭黑，所得白炭黑的流动性指数和BET比表面积均显著提升，并将该白炭黑作为PA66或涂料的助剂进行使用，显著提升了所得产品的使用性能。

Description

一种用于提升流变特性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，具体涉及一种用于提升流变特性白炭黑的制备方法。
背景技术
目前，白炭黑由于其优异的物化性能和使用性能，广泛的应用于各行各业。
如CN112143057A公开了一种硅烷偶联剂改性白炭黑预分散母胶粒，由以下质量份数原料组成：硅烷偶联剂改性白炭黑50～90份，载体橡胶5～50份，软化油1～10份，分散剂1～5份；该硅烷偶联剂改性白炭黑预分散母胶粒用于制备橡胶轮胎时，使白炭黑具有更高的分散均匀程度，并能有效防止其粒子的重聚集，其能增加混入速度、分散速度和分散均匀性；提高白炭黑与橡胶的相容性，从而提高橡胶轮胎的性能；为“绿色轮胎”胎面胶的制备提供理论依据。
CN107163785A公开了一种含白炭黑的无铬达克罗涂料及其制备方法，是由以下重量份的原料制得：白炭黑1-3，刚玉粉3-5，碳化硅4-8，石棉粉1-2，聚四氟乙烯粉5-10，环氧树脂E42 10-15，氧化锌1-2，乙烯基三胺10-15，锌粉20-30，铝粉20-30，硅烷偶联剂KH550 40-50，乙醇5-10，丙酮50-70，聚二甲基硅氧烷0.3-0.6；该发明具有较高的强度和耐磨性，表现出良好的流动性和附着性，形成的涂层致密光滑，解决了达克罗涂液强度较小、耐磨性不好的缺点，极具市场竞争力；配合添加了白炭黑，提高了涂料的耐磨性、强度、抗老化性和改善涂料表面的光洁度。
然而，目前白炭黑制备过程中得到的白炭黑在具体使用过程中仍存在改善流变性能差及产品性能较差的问题。
发明内容
本申请提供了一种用于提升流变特性白炭黑的制备方法及应用，解决了目前白炭黑在使用过程中存在的流变性能差，白炭黑使用性能较差的问题。
第一方面，本申请提供了一种用于提升流变特性白炭黑的制备方法，所述制备方法包括：
将Na 2O·mSiO 2溶液和木质素磺酸盐进行混合，并调整溶液pH值至8-10，之后加入混合盐溶液进行高压陈化处理，经固液分离得到所述白炭黑。
本申请提供的制备方法，通过调整白炭黑的制备过程，并引入木质素磺酸盐和混合盐溶液，利用二者间的促进效果在高压陈化的条件下，制备得到了高性能的白炭黑，所得白炭黑的流动性指数和BET比表面积显著提升，作为PA66或涂料的助剂进行使用可以显著提升所得产品的使用性能。
本申请中，所述调整溶液pH值至8-10，例如可以是8、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9、9.1、9.2、9.3、9.4、9.5、9.6、9.7、9.8、9.9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。
本申请中，所述木质素磺酸盐可以木质素磺酸钠、木质素磺酸钾、木质素磺酸钙或木质素磺酸镁等的1种或至少2种的组合。
作为本申请优选的技术方案，所述Na 2O·mSiO 2溶液的质量浓度为5-25％，例如可以是5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％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，所述木质素磺酸盐的添加量为所述Na 2O·mSiO 2溶液质量的2-8％，例如可以是2％、2.2％、2.4％、2.6％、2.8％、3％、3.2％、3.4％、3.6％、3.8％、4％、4.2％、4.4％、4.6％、4.8％、5％、5.2％、5.4％、5.6％、5.8％、6％、6.2％、6.4％、6.6％、6.8％、7％、7.2％、7.4％、7.6％、7.8％或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，所述混合中进行加热至溶液温度为70-90℃，例如可以是70℃、72℃、74℃、76℃、78℃、80℃、82℃、84℃、86℃、88℃或90℃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，所述加热的方式包括微波加热。
作为本申请优选的技术方案，所述混合的时间为30-60min，例如可以是30min、32min、34min、36min、38min、40min、42min、44min、46min、48min、50min、52min、54min、56min、58min或60min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，所述混合盐溶液包括钠盐和铵盐的混合溶液。
优选地，所述混合盐溶液中钠盐和铵盐的质量比为1:(0.2-0.5)，例如可以是 1:0.2、1:0.21、1:0.22、1:0.23、1:0.24、1:0.25、1:0.26、1:0.27、1:0.28、1:0.29、1:0.3、1:0.31、1:0.32、1:0.33、1:0.34、1:0.35、1:0.36、1:0.37、1:0.38、1:0.39、1:0.4、1:0.41、1:0.42、1:0.43、1:0.44、1:0.45、1:0.46、1:0.47、1:0.48、1:0.49或1:0.5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，所述钠盐包括碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾中的1种或至少2种的组合。
优选地，所述铵盐包括氯化铵、硝酸铵、硫酸铵、碳酸铵或碳酸氢铵中的1种或至少2种的组合。
作为本申请优选的技术方案，所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的10-20％，例如可以是10％、11％、12％、13％、14％、15％、16％、17％、18％、19％或20％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，所述高压陈化处理为在二氧化碳气氛下进行处理。
优选地，所述高压陈化处理的压力为50-100MPa，例如可以是50MPa、52MPa、54MPa、56MPa、58MPa、60MPa、62MPa、64MPa、66MPa、68MPa、70MPa、72MPa、74MPa、76MPa、78MPa、80MPa、82MPa、84MPa、86MPa、88MPa、90MPa、92MPa、94MPa、96MPa、98MPa或100MPa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，所述高压陈化处理的温度为120-140℃，例如可以是120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃或140℃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，所述高压陈化处理的时间为1-2h，例如可以是1h、1.1h、1.2h、1.3h、1.4h、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Na 2O·mSiO 2溶液和木质素磺酸盐进行混合，并调整溶液pH值至8-10，之后加入混合盐溶液进行高压陈化处理，经固液分离得到所述白炭黑；
所述Na 2O·mSiO 2溶液的质量浓度为5-25％；所述木质素磺酸盐的添加量为 所述Na 2O·mSiO 2溶液质量的2-8％；所述混合中进行加热至溶液温度为70-90℃；所述加热的方式包括微波加热；所述混合的时间为30-60min；
所述混合盐溶液包括钠盐和铵盐的混合溶液；所述混合盐溶液中钠盐和铵盐的质量比为1:(0.2-0.5)；所述钠盐包括碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾中的1种或至少2种的组合；所述铵盐包括氯化铵、硝酸铵、硫酸铵、碳酸铵或碳酸氢铵中的1种或至少2种的组合；所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的10-20％；
所述高压陈化处理为在二氧化碳气氛下进行处理；所述高压陈化处理的压力为50-100MPa；所述高压陈化处理的温度为120-140℃；所述高压陈化处理的时间为1-2h。
第二方面，本申请提供了如第一方面所述制备方法得到的白炭黑的应用，所述应用包括采用所述白炭黑制备PA66材料或涂料。
与现有技术方案相比，本申请至少具有以下有益效果：
(1)本申请提供的制备方法，通过在反应过程中引入木质素磺酸盐并在混合盐溶液的条件进行白炭黑的形成，进而在高压陈化下制备得到高性能的白炭黑，所得白炭黑的流动性指数F1≥95，BET比表面≥300.12m 2/g。
(2)本申请所得的白炭黑在使用过程中，显著改善了制备得到产品的流动性能，其中含有本申请的白炭黑的PA66的熔体流动速率≥80.15g/min，拉伸强度≥145.66MPa，弯曲强度≥200.87MPa；作为涂料助剂使用时，涂刷后涂膜的耐磨性能为750g/500r，失重≤0.001g。
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
本实施例提供了一种用于提升流变特性白炭黑的制备方法，所述制备方法包括：
将Na 2O·mSiO 2溶液和木质素磺酸钠进行混合，并调整溶液pH值至9，然后加入混合盐溶液进行高压陈化处理，之后经固液分离得到所述白炭黑；
所述Na 2O·mSiO 2溶液的质量浓度为15％；所述木质素磺酸盐的添加量为所 述Na 2O·mSiO 2溶液质量的5％；所述混合中进行加热至溶液温度为80℃；所述加热的方式为微波加热；所述混合的时间为45min；
所述混合盐溶液为钠盐和铵盐的混合溶液；所述混合盐溶液中钠盐和铵盐的质量比为1:0.35；所述钠盐为碳酸钠；所述铵盐为氯化铵；所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的15％；
所述高压陈化处理为在二氧化碳气氛下进行处理；所述高压陈化处理的压力为75MPa；所述高压陈化处理的温度为130℃；所述高压陈化处理的时间为1.5h。
所得白炭黑的性能指标详见表1。
实施例2
本实施例提供了一种用于提升流变特性白炭黑的制备方法，所述制备方法包括：
将Na 2O·mSiO 2溶液和木质素磺酸钾进行混合，并调整溶液pH值至10，然后加入混合盐溶液进行高压陈化处理，之后经固液分离得到所述白炭黑；
所述Na 2O·mSiO 2溶液的质量浓度为5％；所述木质素磺酸盐的添加量为所述Na 2O·mSiO 2溶液质量的8％；所述混合中进行加热至溶液温度为70℃；所述加热的方式为微波加热；所述混合的时间为60min；
所述混合盐溶液为钠盐和铵盐的混合溶液；所述混合盐溶液中钠盐和铵盐的质量比为1:0.2；所述钠盐为碳酸氢钠；所述铵盐为硫酸铵；所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的10％；
所述高压陈化处理为在二氧化碳气氛下进行处理；所述高压陈化处理的压力为50MPa；所述高压陈化处理的温度为120℃；所述高压陈化处理的时间为2h。
所得白炭黑的性能指标详见表1。
实施例3
本实施例提供了一种用于提升流变特性白炭黑的制备方法，所述制备方法包括：
将Na 2O·mSiO 2溶液和木质素磺酸镁进行混合，并调整溶液pH值至8，然后加入混合盐溶液进行高压陈化处理，之后经固液分离得到所述白炭黑；
所述Na 2O·mSiO 2溶液的质量浓度为25％；所述木质素磺酸盐的添加量为所 述Na 2O·mSiO 2溶液质量的2％；所述混合中进行加热至溶液温度为90℃；所述加热的方式为微波加热；所述混合的时间为30min；
所述混合盐溶液为钠盐和铵盐的混合溶液；所述混合盐溶液中钠盐和铵盐的质量比为1:0.5；所述钠盐为质量比为1:1的碳酸钠和碳酸氢钠；所述铵盐为质量比的氯化铵和碳酸氢铵；所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的20％；
所述高压陈化处理为在二氧化碳气氛下进行处理；所述高压陈化处理的压力为100MPa；所述高压陈化处理的温度为140℃；所述高压陈化处理的时间为1h。
所得白炭黑的性能指标详见表1。
对比例1
与实施例1的区别仅在于将木质磺酸钠替换为等量的聚乙烯吡咯烷酮，所得白炭黑的性能指标详见表1。
对比例2
与实施例1的区别仅在于将混合盐溶液替换为等量、等比例的硅酸钠和氯化铵的混合盐溶液，所得白炭黑的性能指标详见表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、等比例的碳酸钠和硅酸钠的混合盐溶液，所得白炭黑的性能指标详见表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碳酸铵溶液，所得白炭黑的性能指标详见表1。
对比例5
与实施例1的区别仅在于将混合中的微波加热替换为常规的水浴加热，所得白炭黑的性能指标详见表1。
对比例6
与实施例1的区别仅在于陈化处理采用常压陈化处理，即在室温(25℃)下进行陈化，所得白炭黑的性能指标详见表1。
对比例7
与实施例1的区别仅在于高压陈化处理在氮气气氛下进行，即仅提供高压 状态，所得白炭黑的性能指标详见表1。
对比例8
与实施例1的区别仅在于高压陈化处理在氨气氛围下进行，所得白炭黑的性能指标详见表1。
对比例9
与实施例1的区别仅在于所述木质素磺酸盐的添加量为所述Na 2O·mSiO 2溶液质量的15％，所得白炭黑的性能指标详见表1。
对比例10
与实施例1区别仅在于所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的7％，所得白炭黑的性能指标详见表1。
本申请中，所述白炭黑的流动性通过Carr流动性指数进行评估，具体过程可参考奶粉流动性测试方法(王小飞,高原,蒋楠.奶粉流动性测试方法[J].食品安全质量检测学报,2015(9):7.)。BET比表面积依据GB/T 10722-2014炭黑总表面积和外表面积的测定氮吸附法进行检测。
所得白炭黑改善流变性能的具体使用过程如下：在PA66改性过程中引入本申请中的白炭黑，白炭黑的添加量为总物料质量的3％如在玻纤改性PA66的过程中进行添加，具体制备过程可参考CN105111730A实施例3进行制备。
通过对玻纤改性PA66的力学性能进行检测(采用实施例1-3的白炭黑进行添加)，材料的拉伸强度为145.66-180.45MPa，弯曲强度为200.87-250.65MPa。
另外如引入涂料作为助剂进行添加，评估涂料喷涂过程中的流动性能；所得涂料涂刷后的耐磨性能(750g/500r，失重≤0.001g，具体检测过程详见JG/T172-2005)和光泽度(≥98)，所述涂料的制备过程具体参见CN107964265A的实施例1。涂料助剂喷涂流动性能依据下述方法进行测试：
(1)在测试前后应用纱布蘸溶液将粘度计擦拭干净，并在空气中干燥或用冷风吹干，不允许有过去测试液的残存液体粘附在杯中或流出管孔中，应使杯的内臂和流出孔保持洁净，对光观察要原有光洁度。
(2)测试前，调整十字架平台保持水平位置。
(3)将待测液体搅拌均匀，并在多于567孔/平方厘米的筛网中过滤脱除气泡，在设定25℃±0.1℃下，持续15min后进行测定。
(4)将待测液体注入粘度计时，同时用一手指堵住流出孔，注满后用一金 属或玻璃平板在杯上刮平，将多余试液刮入粘度计边沿凹槽内，放好承接杯。
(5)将手指放开，试液垂直流出，同时开动秒表，试液流出成线条，断开时止动秒表，测得时间即代表其条件粘度，单位为秒。
表1
Figure PCTCN2021134747-appb-000001
Figure PCTCN2021134747-appb-000002
通过上述实施例和对比例的结果可知，本申请提供的制备方法，通过在反应过程中引入木质素磺酸盐，并在混合盐溶液的条件进行白炭黑的形成，进而在高压陈化下制备得到高性能的白炭黑，所得白炭黑的流动性指数F1≥95，BET比表面≥300.12m 2/g。
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. 一种用于提升流变特性白炭黑的制备方法，其包括：
    将Na 2O·mSiO 2溶液和木质素磺酸盐进行混合，并调整溶液pH值至8-10，之后加入混合盐溶液进行高压陈化处理，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Na 2O·mSiO 2溶液的质量浓度为5-25％。
  3. 如权利要求1或2所述的制备方法，其中，所述木质素磺酸盐的添加量为所述Na 2O·mSiO 2溶液质量的2-8％。
  4. 如权利要求1-3任一项所述的制备方法，其中，所述混合中进行加热至溶液温度为70-90℃；
    任选地，所述加热的方式包括微波加热。
  5. 如权利要求1-4任一项所述的制备方法，其中，所述混合的时间为30-60min。
  6. 如权利要求1-5任一项所述的制备方法，其中，所述混合盐溶液包括钠盐和铵盐的混合溶液；
    任选地，所述混合盐溶液中钠盐和铵盐的质量比为1:(0.2-0.5)；
    任选地，所述钠盐包括碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾中的1种或至少2种的组合；
    任选地，所述铵盐包括氯化铵、硝酸铵、硫酸铵、碳酸铵或碳酸氢铵中的1种或至少2种的组合。
  7. 如权利要求1-6任一项所述的制备方法，其中，所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的10-20％。
  8. 如权利要求1-7任一项所述的制备方法，其中，所述高压陈化处理为在二氧化碳气氛下进行处理；
    任选地，所述高压陈化处理的压力为50-100MPa；
    任选地，所述高压陈化处理的温度为120-140℃；
    任选地，所述高压陈化处理的时间为1-2h。
  9. 如权利要求1-8任一项所述的制备方法，其中，所述制备方法包括：
    将Na 2O·mSiO 2溶液和木质素磺酸盐进行混合，并调整溶液pH值至8-10，之后加入混合盐溶液进行高压陈化处理，经固液分离得到所述白炭黑；
    所述Na 2O·mSiO 2溶液的质量浓度为5-25％；所述木质素磺酸盐的添加量为 所述Na 2O·mSiO 2溶液质量的2-8％；所述混合中进行加热至溶液温度为70-90℃；所述加热的方式包括微波加热；所述混合的时间为30-60min；
    所述混合盐溶液包括钠盐和铵盐的混合溶液；所述混合盐溶液中钠盐和铵盐的质量比为1:(0.2-0.5)；所述钠盐包括碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾中的1种或至少2种的组合；所述铵盐包括氯化铵、硝酸铵、硫酸铵、碳酸铵或碳酸氢铵中的1种或至少2种的组合；所述混合盐溶液的添加量为所述Na 2O·mSiO 2溶液质量的10-20％；
    所述高压陈化处理为在二氧化碳气氛下进行处理；所述高压陈化处理的压力为50-100MPa；所述高压陈化处理的温度为120-140℃；所述高压陈化处理的时间为1-2h。
  10. 如权利要求1-9任一项所述制备方法所得白炭黑的应用，其包括采用所述白炭黑制备PA66材料或涂料。
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