WO2020140401A1 - 一种低吸油值高比表面积磨擦型二氧化硅及其制备方法 - Google Patents

一种低吸油值高比表面积磨擦型二氧化硅及其制备方法 Download PDF

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WO2020140401A1
WO2020140401A1 PCT/CN2019/092145 CN2019092145W WO2020140401A1 WO 2020140401 A1 WO2020140401 A1 WO 2020140401A1 CN 2019092145 W CN2019092145 W CN 2019092145W WO 2020140401 A1 WO2020140401 A1 WO 2020140401A1
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silica
surface area
specific surface
sodium silicate
oil absorption
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PCT/CN2019/092145
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English (en)
French (fr)
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任振雪
梁少彬
高文颖
林英光
李丽峰
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广州市飞雪材料科技有限公司
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the invention belongs to the technical field of silica for toothpaste, in particular to a low-absorption-value high-surface-area friction type silica and a preparation method thereof.
  • Silica has stable physical and chemical properties, environmental friendliness, acid and alkali resistance, and high temperature resistance. It has good compatibility with toothpaste raw materials, high fluorine compatibility, and has the function of cleaning the oral cavity, so it is widely used as an abrasive and thickener Used in toothpaste.
  • silicon dioxide for toothpaste on the market is mainly prepared by the precipitation method and belongs to an amorphous mesoporous material.
  • Thickened silica has a large specific surface area (greater than 150m 2 /g), high oil absorption value, water absorption and powder viscosity; frictional silica has a small specific surface area (less than 130m 2 /g), oil absorption value, water absorption and The powder viscosity is low, so it is often necessary to mix with a sufficient amount of thickened silica to achieve the required toothpaste viscosity.
  • Thickened silica has a large average pore size (about 10 nm) and a high oil absorption value.
  • Patent document CN 108675307A discloses a method for preparing a low refractive index and high viscosity frictional silica.
  • the method includes S1. Inject 0.8-1.0M water glass solution into the reaction tank, increase the temperature to 70-80°C, start stirring, and drop Add 3 ⁇ 4M sulfuric acid solution, stop adding acid when the pH value is 10 ⁇ 11, prepare thickened silica sol solution; S2, inject sodium sulfate solution, and slowly add carboxymethylcellulose at the same time, warm up to 50 ⁇ 60°C; S3, add 1.5 ⁇ 2.0M water glass solution dropwise, add 8.0 ⁇ 10.0M sulfuric acid solution dropwise at the same time for the same drop reaction, control the pH value of the process 10.5 ⁇ 11.5 When the acid is at a pH value of 4.0 to 5.0, stop adding the acid, stir and age for 0.5 to 1 hour; S4, press filter, wash, dry and crush the silica.
  • the water absorption of the silica prepared by this method is 22-27mL/20g, the oil absorption value is 90-120mL/100g, the copper consumption value is 5.0-7.0mg, which meets the standard requirements of frictional silica, and its powder Body viscosity is 2000-3000cP, with thickening characteristics of toothpaste.
  • the preparation method is complicated, requiring the use of multiple concentrations of the reaction solution, and also requiring carboxymethyl cellulose as a modification aid. At the same time, its silica powder viscosity is low and the thickening effect is limited.
  • the present invention first provides A preparation method of frictional silica with low oil absorption value and high specific surface area is presented.
  • the preparation method is simple. It adopts a one-step hydrothermal precipitation method and controls key parameters such as reaction bottom liquid, material concentration, reaction pH value and reaction temperature. Friction silica with low oil absorption value, high specific surface area, small pore size and high powder viscosity is obtained.
  • the preparation method of the low oil absorption value high specific surface area friction silica provided by the present invention includes the following steps:
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the weight percent concentration of the sodium sulfate solution is 5.0-6.5%.
  • the modulus of the sodium silicate solution is 3.3-3.5, and the concentration is 2.5-3.5mol/L.
  • the concentration of the sulfuric acid solution is 8.0 to 12.0 mol/L.
  • the pH value of the reaction end point is 4.0-5.0.
  • the present invention also provides silica prepared by the above-mentioned method for preparing a low-absorption-value high-surface-area frictional silica.
  • the silica has an oil absorption value of 95-115 g/100 g and a specific surface area of 230 ⁇ 280m 2 /g, average pore diameter is 2.55 ⁇ 3.15nm, powder viscosity is 3200 ⁇ 4500cP, at the same time has good friction and cleaning characteristics and toothpaste thickening effect, used in toothpaste formula, not only can reduce thickening silica
  • the amount of silicon dioxide can also reduce the adsorption of silica on fragrance, improve the permeability of fragrance, enhance the taste of toothpaste, and reduce the cost of toothpaste.
  • the preparation method of the present invention uses sodium silicate solution with a modulus of 3.3 to 3.5 and a concentration of 2.5 to 3.5 mol/L and a high-concentration sulfuric acid solution with a concentration of 8.0 to 12.0 mol/L as reaction raw materials.
  • the mixed solution of sodium sulfate solution and sodium silicate solution is used as the reaction bottom liquid, and at the same time, the reaction is carried out with a higher concentration sodium silicate solution of the same modulus.
  • the reaction is carried out with a higher concentration sodium silicate solution of the same modulus.
  • the reaction starts to precipitate silica faster, and the primary particles are relatively small.
  • silica has the characteristics of small pore size, high specific surface area, high powder viscosity, but low oil absorption value.
  • the silica prepared by the preparation method of the present invention has a rich pore structure, and the use of surface spectrometer to characterize the pore structure of the particles shows that the pore size of the silica is distributed between 2-30 nm, most of which are between 2-10 nm, average The pore diameter is 2.55 to 3.15 nm, and the specific surface area is 230 to 280 m 2 /g. Because most of the pore diameters are small, and the molecular diameter of dibutyl phthalate (DBP) is relatively large, small pores do not absorb DBP, and only large pores have an absorption effect on DBP, so the oil absorption value of this silica is relatively low , Keep at 95 ⁇ 115g/100g. Due to the large specific surface area and complex pore structure, the surface energy is high, the surface activity is strong, and the powder viscosity is significantly increased, ranging from 3200 to 4500cp.
  • DBP dibutyl phthalate
  • the preparation method of the low-absorption-value high-surface-area friction silica of the present invention is simple, the process is stable, no modification additives are needed, the conditions are easy to control, the production cost is low, the environmental pollution is less, and the production can be industrialized.
  • the low-absorption-value high-surface-area friction silica of the present invention has high specific surface area and powder viscosity, strong surface activity, stronger affinity with thickeners such as sodium carboxymethyl cellulose, carrageenan, etc.
  • thickeners such as sodium carboxymethyl cellulose, carrageenan, etc.
  • the dosage can also meet the viscosity requirements of toothpaste, and its oil absorption value is low, thereby effectively improving the translucency of fragrance, enhancing the taste of toothpaste, and reducing the cost of toothpaste.
  • Example 1 The present invention has low oil absorption value and high specific surface area friction silica and its preparation method
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the modulus of the sodium silicate solution is 3.3 and the concentration is 2.5 mol/L; the concentration of the sulfuric acid solution is 8.0 mol/L.
  • Embodiment 2 The present invention has low oil absorption value and high specific surface area friction silica and its preparation method
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the modulus of the sodium silicate solution is 3.5 and the concentration is 3.5 mol/L; the concentration of the sulfuric acid solution is 12.0 mol/L.
  • Embodiment 3 The present invention has low oil absorption value and high specific surface area friction silica and its preparation method
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the modulus of the sodium silicate solution is 3.4, and the concentration is 2.8mol/L; the concentration of the sulfuric acid solution is 10.0mol/L.
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the modulus of the sodium silicate solution is 3.3 and the concentration is 3.5 mol/L; the concentration of the sulfuric acid solution is 8.0 mol/L.
  • the formed silica is press-filtered, washed, and spray-dried to obtain a friction type silica with a low oil absorption value and a high specific surface area.
  • the modulus of the sodium silicate solution is 3.3 and the concentration is 3.0 mol/L; the concentration of the sulfuric acid solution is 11.0 mol/L.
  • this comparative example differs only in that the modulus of the sodium silicate solution is 3.2.
  • this comparative example differs only in that the modulus of the sodium silicate solution is 3.6.
  • this comparative example differs only in that the concentration of the sulfuric acid solution is 7.0 mol/L.
  • this comparative example differs only in that the pH of the reaction system is maintained at 11.0.
  • this comparative example differs only in that the reaction is heated to 95°C.
  • this comparative example differs only in that the reaction is heated to 80°C.
  • this comparative example differs only in that: S1, a sodium sulfate solution 13m 3 with a weight percent concentration of 5.5% added to the reaction kettle is heated to 75°C, and sodium silicate solution is added dropwise while stirring 8m 3 and sulfuric acid solution, maintain the pH value of the reaction system at 10.5, and control the dropping time to 30min. That is, in step S1, sodium silicate solution is not added as a reaction bottom liquid.
  • Example 3 Compared with Example 3, the difference of this comparative example is only that: after the dropwise addition of S2 and sodium silicate solution, stop adding acid and aging for 15 minutes; then continue to dropwise add sulfuric acid solution to the reaction end point pH value is 4.4, stop adding Acid, aged for 10min. That is, no sodium silicate solution is added in step S2.
  • Test Example 1 Performance test of low-absorption-value high-surface-area friction silica of the present invention
  • the silica of Examples 1 to 5 of the present invention has an oil absorption value of 95 to 115 g/100 g, a specific surface area of 230 to 280 m 2 /g, an average pore diameter of 2.55 to 3.15 nm, and a powder viscosity of 3200 to 4500 cP.
  • the specific surface area and powder viscosity are greatly increased, the pore size and oil absorption value are significantly reduced, and it has the characteristics of high viscosity and no adsorption of fragrance.
  • the silica of Examples 1 to 5 of the present invention meets the industry standard requirements of abrasive silica for toothpaste, and can be used as an abrasive in toothpaste.
  • Comparative Example 1 and Comparative Example 2 changed the modulus of the sodium silicate solution.
  • Comparative Example 3 changed the concentration of the sulfuric acid solution, the pore size and oil absorption value of its silica increased significantly
  • Comparative Example 4 changed the pH of the reaction, its silica The specific surface area and powder viscosity decreased;
  • Comparative Example 5 increased the reaction temperature to 95°C, and the specific surface area, oil absorption value and powder viscosity of silica decreased significantly;
  • Comparative Example 6 reduced the reaction temperature to 80°C, and its dioxide The specific surface area, pore size and oil absorption value of silicon increased significantly;
  • Comparative Example 7 changed the reaction bottom liquid, the pore size of its silica increased significantly, while the specific surface area and powder viscosity decreased significantly;
  • Comparative Example 8 did not Adding sodium silicate solution.
  • toothpaste was prepared according to the toothpaste formula, and the viscosity comparison of toothpastes prepared with different amounts of silica was tested.
  • the experimental results are shown in Table 2 below, and the content of other raw materials remains unchanged (mass fraction %).
  • the silicon dioxide content of Example 4 of the present invention is 20% in toothpaste, and only a 4.0% thickened silica can be added to achieve a viscosity value of 80,000 cp; while the existing M1 type dioxide is used If the silicon content is 20%, it is necessary to add 5.5% thickened silica to achieve a viscosity value of 79000 cp. Therefore, the use of the silica of the present invention can reduce the amount of thickened silica used, thereby reducing costs, and reducing the adsorption of fragrance, and improving the permeability of fragrance.

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Abstract

提供一种低吸油值高比表面积磨擦型二氧化硅及其制备方法，该方法包括：S1向反应釜中加入硫酸钠溶液和硅酸钠溶液，加热至85-90℃，同时滴加硅酸钠溶液与硫酸溶液，维持pH值为11.2-11.6；S2硅酸钠溶液滴加完后，停止加酸，再加入硅酸钠溶液，陈化，而后继续滴加硫酸溶液至终点pH值为4.0-5.0，停止加酸，陈化；S3将二氧化硅进行压滤，洗涤，干燥，破碎，得到产品二氧化硅。所得二氧化硅具有良好的磨擦清洁特性和牙膏增稠效果，能降低增稠型二氧化硅的用量和对香精的吸附，提高香精的诱发性、增强牙膏口感，降低牙膏成本。

Description

一种低吸油值高比表面积磨擦型二氧化硅及其制备方法 技术领域
本发明属于牙膏用二氧化硅技术领域，具体涉及一种低吸油值高比表面积磨擦型二氧化硅及其制备方法。
背景技术
二氧化硅的物理化学性质稳定，具有环境友好、耐酸碱耐高温等特征，而且与牙膏原料的配伍性良好，氟相容性高，具有清洁口腔功能，因而作为磨料和增稠剂广泛应用于牙膏中。
目前市面上牙膏用二氧化硅主要由沉淀法制备所得，属于无定型介孔材料。增稠型二氧化硅比表面积大(大于150m 2/g)，吸油值、吸水量及粉体粘度高；摩擦型二氧化硅比表面积小(小于130m 2/g)，吸油值、吸水量及粉体粘度低，故往往需要与足量的增稠型二氧化硅复配使用以达到所要求的牙膏粘度。增稠型二氧化硅由于平均孔径较大(约10nm)、吸油值高，对牙膏中香精等原料具有吸附性，导致香精的透发性差、添加量高。而小孔径的二氧化硅对香精几乎无吸附作用，能够通过降低增稠型二氧化硅的用量，从而降低二氧化硅对香精的吸附，提高香精的透发性、增强牙膏口感。
专利文献CN 108675307A公开了一种低折光高粘度磨擦型二氧化硅的制备方法，该方法包括S1、向反应罐中注入0.8～1.0M水玻璃溶液，升温至70～80℃，开启搅拌，滴加3～4M硫酸溶液，当pH值为10～11时停止加酸，制得增稠型二氧化硅溶胶溶液；S2、注入硫酸钠溶液，同时缓慢加入羧甲基纤维素，升温至50～60℃；S3、滴加1.5～2.0M水玻璃溶液，同时滴加8.0～10.0M硫酸溶液进行同滴反应，控制过程pH值为10.5～11.5，当水玻璃溶液滴加完毕后，继续滴加酸至pH值为4.0～5.0，停止加酸，搅拌陈化0.5～1h；S4、将二氧化硅进行压滤、洗涤，干燥、破碎，即可。该方法制得的该二氧化硅的吸水量为22～27mL/20g，吸油值为90～120mL/100g，铜耗值为5.0～7.0mg，符合磨擦型二氧化硅的标准要求，且其粉体粘度为2000～3000cP，具备牙膏增稠特性。然而该制备方法复杂，需要使用多种浓度的反应液，并且还需要羧甲基纤维素作为改性助剂，同时其二氧化硅的粉体粘度偏低，增稠效果有限。
因此，急需一种可有效提高牙膏粘度，但吸油值低，孔径小的磨擦型二氧化硅，从而降低增稠型二氧化硅的添加量，以降低牙膏成本。
发明内容
为了解决现有磨擦型二氧化硅产品及制备中存在的问题(如方法复杂，二氧化硅孔径大、对香精吸附性强，粉体粘度偏低、增稠效果有限等)，本发明首先提供了一种低吸油值高比表面积磨擦型二氧化硅的制备方法，该制备方法简单，采用一步水热沉淀法，通过控制反应底液、物料浓度、反应pH值和反应温度等关键参数，制备得到吸油值低、比表面积高、孔径小、粉体粘度高的磨擦型二氧化硅。
本发明提供的低吸油值高比表面积磨擦型二氧化硅的制备方法，包括以下步骤：
S1、往反应釜中加入硫酸钠溶液12～14m 3和硅酸钠溶液330～360L，加热至85～90℃，搅拌下同时滴加硅酸钠溶液7～9m 3与硫酸溶液，维持反应体系的pH值为11.2～11.6，控制滴加时间为20～40min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液1～2m 3，陈化15～20min；再继续滴加硫酸溶液至反应终点pH值，停止加酸，陈化10～15min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10～13μm，得到低吸油值高比表面积磨擦型二氧化硅。
进一步地，所述硫酸钠溶液的重量百分比浓度为5.0～6.5％。
进一步地，所述硅酸钠溶液的模数为3.3～3.5，浓度为2.5～3.5mol/L。
进一步地，硫酸溶液的浓度为8.0～12.0mol/L。
进一步地，所述反应终点pH值为4.0～5.0。
相应地，本发明还提供了由上述低吸油值高比表面积磨擦型二氧化硅的制备方法所制得的二氧化硅，该二氧化硅的吸油值为95～115g/100g，比表面积为230～280m 2/g，平均孔径为2.55～3.15nm，粉体粘度为3200～4500cP，同时具备良好的磨擦清洁特性和牙膏增稠效果，应用于牙膏配方中，不仅能降低增稠型二氧化硅的用量，还能降低二氧化硅对香精的吸附，提高香精的透发性、增强牙膏口感，实现牙膏成本的降低。
由于现有水热沉淀法制备的磨擦型二氧化硅吸油值低，则其比表面积和粉体粘度也较低，将其用于牙膏，往往需要与足量的增稠型二氧化硅复配使用才能达到所要求的牙膏粘度。为此，本发明制备方法采用模数为3.3～3.5、浓度为2.5～3.5mol/L的硅酸钠溶液和浓度为8.0～12.0mol/L的高浓度硫酸溶液作为反应原料。首先，以硫酸钠溶液和硅酸钠溶液的混合液作为反应底液，同时以同一模数的较高浓度硅酸钠溶液进行反应，在此模数下，由于二氧化硅含量高，结合硫酸钠的盐析效应，反应开始析出二氧化硅的速率较快，一次粒子相对较小。其次，在pH值11.2～11.6及温度85～90℃的反应条件下，硅酸以H 2SiO 4 2-及H 3SiO 3- 的形式存在，羟基含量较少，所以空间体积小，发生聚合后形成的一次粒子粒径非常小，而一次粒子会迅速聚集成致密型小孔径的二氧化硅颗粒。最后，7～9m 3硅酸钠溶液滴加后，再加入1～2m 3硅酸钠溶液，陈化15～20min，二氧化硅颗粒在此强碱性条件下被刻蚀，容易生成小孔。因而该二氧化硅具备小孔径、高比表面积、高粉体粘度，但低吸油值的特性。
故由本发明制备方法制得的二氧化硅具有丰富的孔结构，利用比表面仪表征颗粒孔结构显示，该二氧化硅的孔径分布在2～30nm，其中大部分孔径介于2～10nm，平均孔径为2.55～3.15nm，比表面积为230～280m 2/g。由于大部分孔径较小，而邻苯二甲酸二丁酯(DBP)分子粒径较大，小孔不吸收DBP，仅有大孔对DBP有吸收作用，故该二氧化硅的吸油值比较低，保持在95～115g/100g。而由于比表面积较大，孔结构复杂，故表面能较高，表面活性强，粉体粘度明显提高，为3200～4500cp。
因此，与现有技术相比，本发明的优势在于：
(1)本发明低吸油值高比表面积磨擦型二氧化硅的制备方法简单，工艺稳定，无需加入改性助剂，条件易控，生产成本低，环境污染少，可工业化生产。
(2)本发明低吸油值高比表面积磨擦型二氧化硅的比表面积和粉体粘度高，表面活性较强，与羧甲基纤维素钠、卡拉胶等增稠剂亲和力更强，在牙膏中参与增稠剂的三维网络结构中，有利于提高膏体粘度，而且应用于牙膏后，可保持磨擦型二氧化硅用量不变，维持口腔清洁效果的同时，降低增稠型二氧化硅的用量也可达到牙膏粘度要求，并且其吸油值低，从而有效提高香精的透发性、增强牙膏口感，实现牙膏成本的降低。
具体实施方式
下面将结合具体实施例来详细说明本发明，在此本发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。
实施例1、本发明低吸油值高比表面积磨擦型二氧化硅及其制备方法
S1、往反应釜中加入的重量百分比浓度为5.0％的硫酸钠溶液12m 3和硅酸钠溶液330L，加热至85℃，搅拌下同时滴加硅酸钠溶液7m 3与硫酸溶液，维持反应体系的pH值为11.2，控制滴加时间为20min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液1m 3，陈化15min；再继续滴加硫酸溶液至反应终点pH值为4.0，停止加酸，陈化10min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为11μm，得到低吸油值高比表面积磨擦型二氧化硅。
所述硅酸钠溶液的模数为3.3，浓度为2.5mol/L；所述硫酸溶液的浓度为8.0mol/L。
实施例2、本发明低吸油值高比表面积磨擦型二氧化硅及其制备方法
S1、往反应釜中加入的重量百分比浓度为6.5％的硫酸钠溶液14m 3和硅酸钠溶液360L，加热至90℃，搅拌下同时滴加硅酸钠溶液9m 3与硫酸溶液，维持反应体系的pH值为11.6，控制滴加时间为40min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液2m 3，陈化20min；再继续滴加硫酸溶液至反应终点pH值为5.0，停止加酸，陈化15min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为11μm，得到低吸油值高比表面积磨擦型二氧化硅。
所述硅酸钠溶液的模数为3.5，浓度为3.5mol/L；所述硫酸溶液的浓度为12.0mol/L。
实施例3、本发明低吸油值高比表面积磨擦型二氧化硅及其制备方法
S1、往反应釜中加入的重量百分比浓度为5.5％的硫酸钠溶液13m 3和硅酸钠溶液340L，加热至87℃，搅拌下同时滴加硅酸钠溶液8m 3与硫酸溶液，维持反应体系的pH值为11.4，控制滴加时间为30min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液1.5m 3，陈化15min；再继续滴加硫酸溶液至反应终点pH值为4.4，停止加酸，陈化10min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为11μm，得到低吸油值高比表面积磨擦型二氧化硅。
所述硅酸钠溶液的模数为3.4，浓度为2.8mol/L；所述硫酸溶液的浓度为10.0mol/L。
实施例4、本发明低吸油值高比表面积磨擦型二氧化硅及其制备方法
S1、往反应釜中加入的重量百分比浓度为5.0％的硫酸钠溶液14m 3和硅酸钠溶液360L，加热至88℃，搅拌下同时滴加硅酸钠溶液7m 3与硫酸溶液，维持反应体系的pH值为11.3，控制滴加时间为30min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液1m 3，陈化20min；再继续滴加硫酸溶液至反应终点pH值为5.0，停止加酸，陈化15min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为11μm，得到低吸油值高比表面积磨擦型二氧化硅。
所述硅酸钠溶液的模数为3.3，浓度为3.5mol/L；所述硫酸溶液的浓度为8.0mol/L。
实施例5、本发明低吸油值高比表面积磨擦型二氧化硅及其制备方法
S1、往反应釜中加入的重量百分比浓度为6.0％的硫酸钠溶液12m 3和硅酸钠溶液330L，加热至85℃，搅拌下同时滴加硅酸钠溶液9m 3与硫酸溶液，维持反应体系的pH值为11.6，控制滴加时间为30min；
S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液2m 3，陈化15min；再继续滴加硫酸溶液至反应终点pH值为4.5，停止加酸，陈化10min；
S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为11μm，得到低吸油值高比表面积磨擦型二氧化硅。
所述硅酸钠溶液的模数为3.3，浓度为3.0mol/L；所述硫酸溶液的浓度为11.0mol/L。
对比例1
与实施例3相比，本对比例的区别仅在于：硅酸钠溶液的模数为3.2。
对比例2
与实施例3相比，本对比例的区别仅在于：硅酸钠溶液的模数为3.6。
对比例3
与实施例3相比，本对比例的区别仅在于：硫酸溶液的浓度为7.0mol/L。
对比例4
与实施例3相比，本对比例的区别仅在于：维持反应体系的pH值为11.0。
对比例5
与实施例3相比，本对比例的区别仅在于：反应加热至95℃。
对比例6
与实施例3相比，本对比例的区别仅在于：反应加热至80℃。
对比例7
与实施例3相比，本对比例的区别仅在于：S1、往反应釜中加入的重量百分比浓度为5.5％的硫酸钠溶液13m 3，加热至75℃，搅拌下同时滴加硅酸钠溶液8m 3与硫酸溶液，维持反应体系的pH值为10.5，控制滴加时间为30min。即步骤S1中不添加硅酸钠溶液作为反应底液。
对比例8
与实施例3相比，本对比例的区别仅在于：S2、硅酸钠溶液滴加完毕后，停止加酸，陈化15min；再继续滴加硫酸溶液至反应终点pH值为4.4，停止加酸，陈化10min。即步骤S2中不添加硅酸钠溶液。
试验例一、本发明低吸油值高比表面积磨擦型二氧化硅的性能检测
使用高性能比表面分析仪(品牌为精微高博，型号为JW-BK200)对实施例1～5和对比例1～8及市场现有磨擦型产品(M1)二氧化硅的比表面积和平均孔径进行检测，同时对上述产品的吸油值和粉体粘度进行检测，结果如下表1所示。
表1各二氧化硅的性能检测结果
二氧化硅 比表面积/(m 2/g) 平均孔径/nm 吸油值/(g/100g) 粉体粘度/cP
实施例1 279 3.02 108 4500
实施例2 247 3.14 115 3700
实施例3 269 2.57 96 4200
实施例4 233 2.63 99 3300
实施例5 263 2.71 102 4000
对比例1 272 3.50 124 3000
对比例2 185 2.37 90 2500
对比例3 270 5.76 130 3200
对比例4 157 4.59 103 2400
对比例5 131 4.13 85 2000
对比例6 340 11.06 130 3000
对比例7 120 8.65 97 1900
对比例8 179 6.21 92 2300
M1 37 12.08 125 1700
由上表1可知：
(1)本发明实施例1～5二氧化硅的的吸油值为95～115g/100g，比表面积为230～280m 2/g，平均孔径为2.55～3.15nm，粉体粘度为3200～4500cP，与现有市售产品相比，比表面积和粉体粘度大幅提高，孔径及吸油值明显减小，具备高粘度、不吸附香精的特性。同时经检测，本发明实施例1～5二氧化硅符合牙膏用磨擦型二氧化硅的行业标准要求，可作用磨擦剂应用于牙膏中。
(2)与实施例3相比，对比例1和对比例2改变了硅酸钠溶液的模数，结果对比例1二氧化硅的孔径及吸油值提高，而对比例2二氧化硅的比表面积、吸油值和粉体粘度有明显下降；对比例3改变了硫酸溶液的浓度，其二氧化硅的孔径及吸油值明显升高；对比例4改变了反应的pH值，其二氧化硅的比表面积和粉体粘度下降；对比例5提高了反应温度至95℃，其二氧化硅的比表面积、吸油值和粉体粘度明显下降；对比例6降低了反应温度至80℃，其二氧化硅的比表面积、孔径和吸油值明显升高；对比例7改变了反应底液，其二氧化硅的孔径明显增大，而比表面积和粉体粘度则明显下降；对比例8反应结束后不添加硅酸钠溶液，其二氧化硅的比表面积、吸油值和粉体粘度明显下降。提示本发明方法各步骤及参数相辅相成，协同制备得到低吸油值、高比表面积、高粉体粘度的磨擦型二氧化硅。
试验例二、本发明低吸油值高比表面积磨擦型二氧化硅的应用效果
利用本发明实施例3和4与M1产品，按照牙膏配方进行制备牙膏，测试不同添加量的二氧化硅所制备的牙膏粘度对比。实验结果如下表2所示，其他原料含量不变(质量分数％)。
表2 各牙膏粘度对比
Figure PCTCN2019092145-appb-000001
由上表2可知，牙膏中使用本发明实施例4的二氧化硅含量20％，只需添加4.0％的增稠型二氧化硅即可达到80000cp的粘度值；而使用现有M1型二氧化硅含量20％，则需要添加5.5％的增稠型二氧化硅才能达到79000cp的粘度值。因此，使用本发明的二氧化硅可降低增稠型二氧化硅的使用量，从而降低成本，并且减少对香精的吸附，提高香精的透发性。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (6)

  1. 一种低吸油值高比表面积磨擦型二氧化硅的制备方法，其特征在于，包括以下步骤：
    S1、往反应釜中加入硫酸钠溶液12～14m 3和硅酸钠溶液330～360L，加热至85～90℃，搅拌下同时滴加硅酸钠溶液7～9m 3与硫酸溶液，维持反应体系的pH值为11.2～11.6，控制滴加时间为20～40min；
    S2、硅酸钠溶液滴加完毕后，停止加酸，加入硅酸钠溶液1～2m 3，陈化15～20min；再继续滴加硫酸溶液至反应终点pH值，停止加酸，陈化10～15min；
    S3、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10～13μm，得到低吸油值高比表面积磨擦型二氧化硅。
  2. 根据权利要求1所述低吸油值高比表面积磨擦型二氧化硅的制备方法，其特征在于，所述硫酸钠溶液的重量百分比浓度为5.0～6.5％。
  3. 根据权利要求1所述低吸油值高比表面积磨擦型二氧化硅的制备方法，其特征在于，所述硅酸钠溶液的模数为3.3～3.5，浓度为2.5～3.5mol/L。
  4. 根据权利要求1所述低吸油值高比表面积磨擦型二氧化硅的制备方法，其特征在于，硫酸溶液的浓度为8.0～12.0mol/L。
  5. 根据权利要求1所述低吸油值高比表面积磨擦型二氧化硅的制备方法，其特征在于，所述反应终点pH值为4.0～5.0。
  6. 根据权利要求1～5任一项所述低吸油值高比表面积磨擦型二氧化硅的制备方法所制得的二氧化硅，其特征在于，所述二氧化硅的吸油值为95～115g/100g，比表面积为230～280m 2/g，平均孔径为2.55～3.15nm，粉体粘度为3200～4500cP。
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